WO2005031798A2 - Light-emitting device and method for manufacturing the same - Google Patents

Light-emitting device and method for manufacturing the same Download PDF

Info

Publication number
WO2005031798A2
WO2005031798A2 PCT/JP2004/014412 JP2004014412W WO2005031798A2 WO 2005031798 A2 WO2005031798 A2 WO 2005031798A2 JP 2004014412 W JP2004014412 W JP 2004014412W WO 2005031798 A2 WO2005031798 A2 WO 2005031798A2
Authority
WO
WIPO (PCT)
Prior art keywords
light
emitting element
layer
compound
group
Prior art date
Application number
PCT/JP2004/014412
Other languages
French (fr)
Other versions
WO2005031798A3 (en
Inventor
Hisao Ikeda
Junichiro Sakata
Original Assignee
Semiconductor Energy Laboratory Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to KR1020067005626A priority Critical patent/KR101286221B1/en
Priority to KR1020097018993A priority patent/KR101286219B1/en
Priority to EP04773500.6A priority patent/EP1776846B1/en
Priority to CN200480027991A priority patent/CN100596251C/en
Priority to US10/571,891 priority patent/US7732808B2/en
Priority to KR1020117030615A priority patent/KR101590148B1/en
Priority to KR1020147023148A priority patent/KR20140107696A/en
Priority to KR1020137011242A priority patent/KR20130062367A/en
Application filed by Semiconductor Energy Laboratory Co., Ltd. filed Critical Semiconductor Energy Laboratory Co., Ltd.
Priority to KR1020097018994A priority patent/KR20090111869A/en
Publication of WO2005031798A2 publication Critical patent/WO2005031798A2/en
Publication of WO2005031798A3 publication Critical patent/WO2005031798A3/en
Priority to US12/647,743 priority patent/US8178869B2/en
Priority to US12/767,902 priority patent/US8216875B2/en
Priority to US13/478,547 priority patent/US8507903B2/en

Links

Classifications

    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17Carrier injection layers

Definitions

  • the present invention relates to a light-emitting element formed to have the structure in which a plurality of layers is sandwiched between a pair of electrodes. More specifically, the present invention relates to the structure of a layer, which can be used as at least one layer, within the plurality of layers.
  • a light-emitting device utilizing light emission from an electroluminescent element has been attracted attention as a display device or a lighting device.
  • a light-emitting element used for a light-emitting device a light-emitting element including a layer containing light-emitting compounds interposed between a pair of electrodes is well known.
  • either of the electrodes serves as an anode, and another serves as a cathode, holes injected from the anode and electrons injected from the cathode are recombined with each other to form molecular exciton, and the molecular exciton radiates energy as light while returning to the ground state.
  • the demand for low power consumption is especially increased in display devices to be installed in various information processing devices, which have been drastically developed in recent years. In order to achieve low power consumption, it has been attempted to reduce a voltage for driving a light-emitting element. In consideration with commercialization, it is important not only to reduce a voltage for driving a light-emitting element but also extend a lifetime of a light-emitting device.
  • unexamined patent publication No. 9-63771 discloses that a voltage for driving a light-emitting element is reduced by forming an anode by a metal oxide having a large work function such as a molybdenum oxide. Moreover, a lifetime of the light-emitting element can be extended.
  • the means for extending a lifetime of a light-emitting element disclosed in the unexamined patent publication No. 9-63771 is insufficient, and so it is required to develop the technique for achieving a further long lifetime.
  • a light-emitting element that drives at low voltage and has a longer lifetime than the conventional light-emitting element, and a method for manufacturing the light-emitting element.
  • a light-emitting element includes a plurality of layers between a pair of electrodes, and at least one layer among the plurality of layers contains a hybrid material (a composite material) including an inorganic compound selected from the group consisting of oxide semiconductor and a metal oxide, and an inorganic compound having high hole transportation properties.
  • the plurality of layers is composed of layers formed respectively by a substance having high carrier injection properties, a substance having high carrier transportation properties, and the like, so that a light-emitting region is located away from electrodes.
  • Such the light-emitting element can suppress crystallization of a layer containing one compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having high hole transportation properties. As a result, a lifetime of a light-emitting element can be extended.
  • a molybdenum oxide (MoOx), a vanadium oxide (VOx), a ruthenium oxide (RuOx), a tungsten oxide (WOx), and the like can be used.
  • an indium tin oxide (ITO), a zinc oxide (ZnO), and a tin oxide (SnO) can be used.
  • Other substances than the foregoing substances can be used.
  • the compound having high hole transportation properties although not limited to the substances recited herein,
  • TDATA 4,4',4"-tris(N,N-diphenyl-amino)-triphenylamine
  • a light-emitting element includes a plurality of layers between a pair of electrodes, and at least one layer among the plurality of layers contains one compound selected from the group consisting of oxide semiconductor and a metal oxide, a compound having high hole transportation properties, and a compound having a high steric hindrance.
  • the plurality of layers is composed of layers respectively formed by a substance having high carrier injection properties, a substance having high carrier transportation properties, and the like, so that a light-emitting region is located away from electrodes.
  • Such the light-emitting element that includes a layer containing one compound selected from the group consisting of oxide semiconductor and a metal oxide, a compound having high hole transportation properties, and a compound having a high steric hindrance can suppress the crystallization of the layer. As a result, a lifetime of a light-emitting element can be extended.
  • the oxide semiconductor, the metal oxide, and the compound having high hole transportation properties are the same as those mentioned above.
  • a compound having a high steric hindrance that is, the compound having spatiality contrary to a plane structure
  • 5,6,11, 12-tetraphenyltetracene abbreviated rubrene
  • hexabenilbenzene, diphenylanthracene, t-butylperylene, 9,10-di(phenyl)anthracene, coumarin 545T, and the like can be used.
  • dendrimer or the like can be used. According to the present invention, aggregation of oxide semiconductor or a metal oxide can be suppressed, and crystallization of a layer containing the oxide semiconductor or the metal oxide can be suppressed. By suppression of the crystallization, a leak current can be prevented from generating due to the crystallization.
  • FIG. 1 is a graph for showing luminance variations with time of light-emitting elements according to certain aspects of the present invention and Comparative Example;
  • FIGS. 2A to 2C are explanatory cross-sectional views of a light-emitting element according to certain aspects of the present invention;
  • FIG. 3 is an explanatory cross-sectional view of a light-emitting element according to certain aspects of the present invention;
  • FIG. 4 shows luminance-voltage characteristics of light-emitting elements according to certain aspects of the present invention and Comparative Example 1;
  • FIG. 5A to 5C are cross-sectional views of a light-emitting element according to certain aspects of the present invention.
  • FIG 6 is a top view of a light-emitting device including a light-emitting element according to certain aspects of the present invention.
  • FIG. 7 is a view for showing an electric appliance mounted with a light-emitting device including a light-emitting element according to certain aspects of the present invention;
  • FIG. 8 shows luminance-voltage characteristics of light-emitting elements according to certain aspects of the present invention and Comparative Example 1;
  • FIG. 9 is a graph for showing luminance variations with time of a light-emitting element according to certain aspects of the present invention.
  • FIG. 10 shows luminance-voltage characteristics of light-emitting elements according to certain aspects of the present invention.
  • FIG. 11 is a graph for showing luminance variations with time of a light-emitting element according to certain aspects of the present invention.
  • FIG. 12 is a graph for showing voltages for electroluminescence of 1 cd/m 2 or more according to certain aspects of the present invention and Comparative Example 2.
  • FIG. 13 is a graph for showing current density-voltage characteristics of light-emitting elements according to certain aspects of the present invention.
  • FIG. 14 is a graph for showing current density-voltage characteristics of light-emitting elements according to certain aspects of Comparative Example 3.
  • FIG. 15 is a graph for showing current density-voltage characteristics of light-emitting elements according to certain aspects of Comparative Example 4.
  • FIG 16 is a graph for showing absorption characteristics of light-emitting element according certain aspects of the present invention.
  • a light-emitting element according to the present invention includes a plurality of layers between a pair of electrodes.
  • the plurality of layers is formed by stacking layers in combination with each other, which is formed respectively by a substance having high carrier injection properties or a substance having high carrier transportation properties, so that a light-emitting region is formed away from the electrodes, that is, carriers are recombined with each other in the region away from the electrodes.
  • FIG. 2A One mode of a light-emitting element according to the present invention is explained with reference to FIG. 2A.
  • a light-emitting element 210 is formed over a substrate 201 used for supporting the light-emitting element 210, and is composed of sequentially a first electrode 202, a first layer 203, a second layer 204, a third layer 205, a fourth layer 206, and a second electrode 207. Further, the first electrode 202 serves as an anode, and the second electrode 207 serves as a cathode in this embodiment.
  • the substrate 201 for example, glass or plastic can be used. Another material can be used for the substrate as long as it serves as a support medium for the light-emitting element during a manufacturing process.
  • the first electrode 202 is preferably formed by a metal having a large work function (at least 4.0 eV), an alloy, an electric conductive compound, or a mixture of the foregoing materials.
  • a metal having a large work function at least 4.0 eV
  • an indium tin oxide (ITO) an indium tin oxide containing silicon
  • an indium zinc oxide that is, an indium oxide mixed with zinc oxide of from 2 to 20 % (ZnO), aurum (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cu), molybdenum (Mo), ferrum (Fe), cobalt (Co), copper (Cu), palladium (Pd), or a nitride of a metal material (TiN), or the like can be used.
  • the first layer 203 is a layer containing a compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having high hole transportation properties.
  • oxide semiconductor and the metal oxide although not limited to the substances recited herein, a molybdenum oxide (MoOx), a vanadium oxide (VOx), a ruthenium oxide (RuOx), a tungsten oxide (WOx), and the like can be used. Other substances than the foregoing substances can. be used.
  • an aromatic amine compound that is, the one having a bond of a benzene ring and nitrogen
  • an aromatic amine compound such as 4,4'-bis[N-(l-naphtyl)-N-phenyl-amino]-biphenyl (abbreviated -NPD)
  • TPD 4,4'-bis[N-(3-methylphenyl)-N-phenyl-amino]-biphenyl
  • the foregoing substances are mainly the substances having hole mobility of 10 "6 cm 2 /Vs or more. Another substance can be used as long as it has higher hole transportation properties than electron transportation properties.
  • the first layer 203 having the structure as mentioned above has high hole injection properties. In the first layer 203, the aggregation of oxide semiconductor or a metal oxide is suppressed by a substance having high hole transportation properties contained in the layer. That is, crystallization of the fist layer 203 is suppressed.
  • the first layer 203 may be formed by, for example, at least two layers respectively containing semiconductor and a compound having high transportation properties with different mixture ratio from each other instead of being formed by one layer.
  • the first layer 203 may further includes a compound having a high steric hindrance (that is, the compound having spatiality contrary to a plane structure) in addition to a compound selected from oxide semiconductor and a metal oxide, and a compound having high hole transportation properties.
  • a compound having a high steric hindrance that is, the compound having spatiality contrary to a plane structure
  • a compound having high hole transportation properties As the compound having a high steric hindrance, 5,6,11, 12-tetraphenyltetracene (abbreviated rubrene) is preferably used.
  • the second layer 204 is a layer formed by a substance having high hole transportation properties, for example, an aromatic amine compound (that is, the one having a bond of a benzene ring-nitrogen) such as ⁇ -NPD, TPD, TDATA, MTDATA, and the like.
  • the foregoing substances are mainly the substances having hole mobility of 10 "6 cm 2 /Vs or more. Another substance can be used as long as it has higher hole transportation properties than electron transportation properties.
  • the second layer 204 may be formed by stacking at least two layers containing the foregoing substances instead of being formed by one layer.
  • the third layer 205 is a layer containing a substance having high light-emitting properties.
  • a substance having high light-emitting properties such as N'N-dimethylquinacridone (abbreviated DMQd), 2H-chromene-2-on (abbreviated coumarin), and a substance having high carrier transportation properties and a good film formation property, that is, a substance that is hard to be crystallized, such as tris(8-quinolmolato)aluminum (abbreviated Alq 3 ) or 9,10-di(2-naphtyl)anthracene (abbreviated DNA) can be used by freely combining with each other.
  • Alq 3 and D3NA have high light-emitting properties, consequently, the third layer 205 may be solely formed by Alq 3 or DNA.
  • the fourth layer 206 is a layer formed by a metal complex or the like having a quinoline skeleton or a benzoquinoline skeleton, for example, a substance having high electron transportation properties such as tris(8-quinolinolato)aluminum (abbreviated Alq 3 ), tris(5-methyl-8-quinolinolato)aluminum (abbreviated Almq 3 ), bis(10-hydroxybenz)[h]-quinolinato)beryllium (abbreviated BeBq 2 ), and bis(2-methyl-8-quinolinolato)-4-phenylphenolato-aluminum (abbreviated BAlq).
  • Alq 3 tris(8-quinolinolato)aluminum
  • Almq 3 tris(5-methyl-8-quinolinolato)aluminum
  • BeBq 2 bis(10-hydroxybenz)[h]-quinolinato)beryllium
  • BAlq bis(2-methyl-8
  • a metal complex having a oxadiazole ligand or a thiazole ligand such as bis[2-(2-hydroxyphenyl)-benzooxazolate]zinc (abbreviated Zn(BOX) 2 ), and bis[2-(2-hydroxyphenyl)-benzothiazolate]zinc (abbreviated Zn(BTZ) 2 ).
  • the foregoing substances are the substances having hole mobility of 10 "6 cm 2 /Vs or more. Another substance can be used as long as it has higher hole transportation properties than electron transportation properties.
  • the fourth layer 206 may be formed by at least two layers containing the foregoing substances instead of being formed by one layer.
  • a material for the second electrode 207 metals having a small work function (at most 3.8 eV), alloys, electric conductive compounds, or a mixture of the above are preferably used.
  • cathode materials metals belonging to a 1 or 2 group of the periodic table of the elements, that is, alkali metals such as lithium (Li) or cesium (Cs); alkali earth metals such as magnesium (Mg), calcium (Ca), strontium (Sr); and alloys including the above elements (Mg:Ag, Al:Li) can be used.
  • alkali metals such as lithium (Li) or cesium (Cs)
  • alkali earth metals such as magnesium (Mg), calcium (Ca), strontium (Sr); and alloys including the above elements (Mg:Ag, Al:Li)
  • various conductive materials such as Al, Ar, ITO containing silicon, and the like can be used regardless of their work function can be used for the second electrode 207.
  • a compound of an alkali metal or an alkali earth metal such as lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF 2 ), and the like.
  • a layer formed by a substance having election transportation properties containing an alkali metal or an alkali earth metal for example,
  • Alq 3 containing magnesium (Mg), or the like can be used.
  • the first layer 203, the second layer 204, the third layer 205, and the fourth layer 206 may be formed by the method other than vapor deposition. For example, ink jetting, spin coating, and the like can be used.
  • Each electrode or each layer may be formed by different film formation methods, respectively.
  • a current is flowed due to electric potential differences generated between the first electrode 201 and the second electrode 207, and holes and electrons are recombined with each other within the third layer 205, which is a layer containing high light-emitting properties, then, light is generated.
  • a light-emitting region is formed in the third layer 205.
  • the entire third layer 205 is not required to be served as a light emission region.
  • the light-emitting region may be formed either the side of the second layer 204 or the fourth layer 206 within the third layer 205.
  • Light is emitted to the outside passing through either the first electrode 202 or the second electrode 207, or both of them. Therefore, either the first electrode 202 or the second electrode 207, or both of them are formed by a substance having light-transmitting properties. In the case that only the first electrode 202 is formed by a substance having light-transmitting properties, light is emitted from the substrate passing through the first electrode 202 as shown in FIG. 2A.
  • the second electrode 207 is formed by a substance having light-transmitting properties
  • light is emitted from the opposite side of the substrate passing through the second electrode 207.
  • the first electrode 202 and the second electrode 207 are formed by substances having light-transmitting properties, light is emitted from both of the substrate and the opposite side of the substrate passing through the first electrode 202 and the second electrode 207.
  • the structure of a layer formed between the first electrode 202 and the second electrode 207 is not limited to the above described structure.
  • the layer structure may have the other structure than the foregoing one as long as the structure is formed to have an area for the recombination of holes and electrons is located away from the first electrode 202 and the second electrode 207 to prevent quenching due to that a light-emitting region and a metal are close to one another; and a layer containing a compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having high hole transportation properties (moreover, a compound having a high steric hindrance may be contained).
  • the lamination structure of the layer is not restricted especially.
  • a layer formed by a substance having high electron transportation properties or hole transportation properties, a substance having electron injection properties, a substance having hole injection properties, a substance having bipolar properties (high electron or hole transportation properties), or the like; and a layer formed by a compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having high hole transportation properties may be freely combined with each other. Further, an area for recombination of carriers may be controlled by providing an ultra thin layer such as a silicon oxide layer. For example, the structure shown in FIG. 3 may be formed. However, a layer structure is not limited thereto.
  • first electrode 502 serving as a cathode
  • first layer 503 formed by a substance having high electron transportation properties
  • second layer 504 formed by a substance having high light-emitting properties
  • third layer 505 formed by a substance having high hole transportation properties
  • fourth layer 506 containing a compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having high hole transportation properties
  • second electrode 507 serving as an anode.
  • reference numeral 501 shown in FIG. 3 denotes a substrate. According to this embodiment, a light-emitting element is manufactured over a glass or plastic substrate.
  • a passive type light-emitting device can be manufactured by manufacturing a plurality of such light-emitting elements over one substrate.
  • a light-emitting element can be manufactured over a thin film transistor (TFT) array.
  • TFT thin film transistor
  • an active matrix type light-emitting device that controls the drive of a light-emitting element by a TFT can be manufactured.
  • the structure of the TFT is not especially restricted.
  • the TFT may be either a staggered TFT or an inversely staggered TFT.
  • a drive circuit formed over the TFT array substrate may be formed by both an N-type TFT and a P-type TFT. Alternatively, the drive circuit may be formed by either an N-type TFT or a P-type TFT.
  • the crystallization of the layer can be suppressed in the light-emitting element including a layer containing a compound selected from the group consisting of oxide semiconductor and a metal oxide, and a substance having high hole transportation properties. Therefore, the generation of a leak current due to the crystallization of the layer can be suppressed, and a long-lived light-emitting element can be obtained.
  • the crystallization of the layer can be further suppressed, and a further long-lived light-emitting element can be obtained in the light-emitting element including a layer containing a compound selected from the group consisting of oxide semiconductor and a metal oxide, a substance having high hole transportation properties, and a substance having a high steric hindrance.
  • a first electrode is formed by depositing an indium tin oxide (ITO) over a glass substrate. Then, the glass substrate deposited with the ITO is processed in vacuum at 150 °C for 30 minutes. A first layer is formed by co-evaporation of a molybdenum oxide and ⁇ -NPD having high hole transporting properties over the first electrode. The weight ratio of the molybdenum oxide and the ⁇ -NPD is 0.245: 1. The first layer is formed to have a thickness of 130 nm.
  • ITO indium tin oxide
  • co-evaporation refers to a method for evaporating each of materials from a plurality of evaporation sources provided in one processing chamber, and mixing the evaporated materials in the gas phase to deposit the mixed materials onto a subject.
  • a second layer is formed by vapor deposition of ⁇ -NPD over the first layer to have a thickness of 10 nm.
  • a third layer is formed by co-evaporation of Alq 3 and coumarin-6 over the second layer. The weight ratio of the Alq 3 and the coumarin-6 is 1: 0.002.
  • the third layer is formed to have a thickness of 37. 5 nm.
  • a fourth layer is formed by vapor deposition of Alq 3 over the third layer to have a thickness of 37.5 nm.
  • a fifth layer is formed by vapor deposition of calcium fluoride (CaF 2 ) over the fourth layer to have a thickness of 1 nm.
  • a second electrode is formed by vapor deposition of aluminum over the fifth layer to have a thickness of 200 nm.
  • FIGS. 1 and 4 show device characteristics of thus manufactured light-emitting element.
  • FIG 4 shows luminance-voltage characteristics of a light-emitting element manufactured according to Example 1.
  • a horizontal axis shows an applied voltage (V)
  • a vertical axis shows luminance (cd/m ).
  • FIG. 4 shows that an onset voltage, which is a voltage for electroluminescence of 1 cd/m 2 or more, is approximately 2.5 V.
  • FIG. 1 shows a measurement result of the variation of luminance per hour of a light-emitting element manufactured according to Example 1.
  • a horizontal axis shows hour, and a vertical axis shows luminance.
  • the luminance is represented its relative value to initial luminance based on the initial value of 100.
  • the variation of luminance is measured by applying continuously a constant amount of current to a light-emitting element, that is, applying a stress to a light-emitting element; and the luminance of the light-emitting element is measured at given time intervals.
  • a current that has a current density required to obtain electroluminescence with a luminance of 1000 cs/m 2 at initial state is applied, and the luminance obtained at the applied current is measured.
  • FIG. 1 shows that after 100 hours luminance becomes the value of 82, that is, the luminance is decreased by 18% compared to the initial luminance.
  • a method for manufacturing a light-emitting element according to the present invention and characteristics of the light-emitting element is explained.
  • a first electrode is formed by depositing an indium tin oxide (ITO) over a glass substrate.
  • the glass substrate deposited with the ITO is processed in vacuum at 150 °C for 30 minutes.
  • a first layer is formed over the first electrode by co-evaporation of a molybdenum oxide, ⁇ -NPD having high hole transportation properties, and rubrene having a high steric hindrance.
  • the weight ratio of the molybdenum oxide and the rubrene is 0.245: 0.018.
  • the first layer is formed to have a thickness of 130 nm.
  • a second layer is formed by vapor deposition ⁇ -NPD over the first layer to have a thickness of 10 nm.
  • a third layer is formed over the second layer by co-evaporation of Alq 3 and coumarin-6 to have a thickness of 37.5 nm. The weight ratio of the Alq 3 and the coumarin-6 is 1: 0.002.
  • a fourth layer is formed by vapor deposition of Alq 3 over the third layer to have a thickness of 37.5 nm.
  • a fifth layer is formed by vapor deposition of calcium fluoride (CaF 2 ) over the fourth layer to have a thickness of 1 nm.
  • a second electrode is formed by vapor deposition of aluminum over the fifth layer to have a thickness of 200 nm.
  • FIG. 1 and 4 show device characteristics of thus manufactured light-emitting element.
  • the measurement method or the like is the same as that described in Example 1.
  • FIG. 4 shows that an onset voltage, which is a voltage for electroluminescence of 1 cd/m 2 or more, is approximately 2.5 V.
  • FIG. 1 shows that after 100 hours luminance becomes the value of 92, that is, the luminance is decreased by 8% compared to the initial luminance.
  • Example 3 A method for manufacturing a light-emitting element according to the present invention and properties of the light-emitting element is explained.
  • a first electrode is formed by depositing an indium tin oxide (ITO) over a glass substrate.
  • ITO indium tin oxide
  • the glass substrate deposited with the ITO is processed in vacuum at 150 °C for 30 minutes.
  • a first layer is formed over the first electrode by co-evaporation of a molybdenum - oxide,
  • the weight ratio of the molybdenum oxide, the DNTPD, and the rubrene is 0.5: 1: 0.05.
  • the first layer is formed to have a thickness of 120 nm.
  • a second layer is formed by vapor deposition of ⁇ -NPD over the first layer to have a thickness of 10 nm.
  • a third layer is formed over the second layer by co-evaporation of Alq 3 and coumarin-6 to have a thickness of 37.5 nm.
  • the weight ratio of the Alq 3 and the coumarin-6 is 1: 0.003.
  • a fourth layer is formed by vapor deposition of Alq 3 over the third layer to have a thickness of 37.5 nm.
  • a fifth layer is formed by vapor deposition of calcium fluoride (CaF ) over the fourth layer to have a thickness of 1 nm.
  • a second electrode is formed by vapor deposition of aluminum over the fifth layer to have a thickness of 200 nm.
  • FIGS. 8 and 9 shows device characteristics of thus manufactured light-emitting element. The measurement method or the like is the same as that described in
  • Example 1 In FIG. 8, a horizontal axis shows an applied voltage (V), and a vertical axis shows luminance (cd/m 2 ). In FIG 9, a horizontal axis shows hour, and a vertical axis shows luminance (relative value).
  • FIG. 8 shows that an onset voltage, which is a voltage for electroluminescence of 1 cd/m or more, is approximately 2.4 V.
  • FIG. 9 shows that after 100 hours luminance becomes the value of 93, that is, the luminance is decreased by 7% compared to the initial luminance.
  • Comparative Example 1 As a comparative example, a method for manufacturing a light-emitting element in which a second layer is formed by only a molybdenum oxide, and device characteristics of the light-emitting element are explained.
  • An indium tin oxide (ITO) is deposited over a glass substrate to form a first electrode.
  • the glass substrate deposited with the ITO is processed in vacuum at 150 °C for 30 minutes.
  • a first layer is formed by vapor deposition of a molybdenum oxide over the first electrode to have a thickness of 100 nm.
  • a second layer is formed by vapor deposition of ⁇ -NPD over the first layer to have a thickness of 60 nm.
  • a third layer is formed over the second layer by co-evaporation of Alq 3 and coumarin to have a thickness of 37.5 nm.
  • the weight ratio of the Alq 3 and the coumarin is 1: 0.002.
  • a fourth layer is formed by vapor deposition of Alq 3 over the third layer to have a thickness of 37.5 nm.
  • a fifth layer is formed by vapor deposition of calcium fluoride (CaF 2 ) over the fourth layer to have a thickness of 1 nm.
  • a second electrode is formed by vapor deposition of aluminum over the fifth layer to have a thickness of 200 nm.
  • FIGS. 1 and 4 shows device characteristics of thus manufactured light-emitting element. The measurement method or the like is the same as that described in Example 1.
  • FIG. 1 and 4 shows device characteristics of thus manufactured light-emitting element. The measurement method or the like is the same as that described in Example 1.
  • FIG. 1 and 4 shows device characteristics of thus manufactured light-emitting element. The measurement method or the like is
  • FIG 4 shows that an onset voltage, which is a voltage for electroluminescence of 1 cd/m 2 or more, is approximately 2.5 V.
  • FIG 1 shows that the luminance of a light-emitting element according to the comparative example after 100 hours is drastically decreased, and light emission cannot be generated. This is caused by the fact that a leak current is generated due to the crystallization of the second layer. Accordingly, the light-emitting element described in Example 1 or 2 emits light at the same driving voltage for the light-emitting element described in Comparative Example. As same as the light-emitting element having a layer formed by only a molybdenum oxide, a light-emitting element according to the invention is operated at a low voltage.
  • the lifetime of the light-emitting element described in Example 1 or 2 can be extended. This arises from the fact that the crystallization of P-type compounds is suppressed by being mixed with a compound having high transportation properties such as ⁇ -NPD or a compound having a high steric hindrance such as rubrene.
  • Example 4 An active matrix light-emitting device having a light-emitting element according to the present invention is explained in Example 4.
  • a drive transistor 91 and a light-emitting element 92 according to the invention are provided over a substrate 90.
  • the drive transistor 91 for driving a light-emitting element is electrically connected to the light-emitting element 92 according to the invention.
  • the term "light-emitting element” refers to a layer which includes a light-emitting layer between an electrode 93 and an electrode 94, and which includes partly a layer containing a molybdenum oxide, a substance with high transportation properties, a substance with a high steric hindrance.
  • the light-emitting element 92 is divided by a bank layer 95.
  • a light-emitting element according to the invention may have the structure in which an electrode serving as an anode is located at a lower side (the term “lower” refers to the region where a drive transistor is provided in response to the light-emitting element) and an electrode serving as a cathode is located at an upper side (the term “upper” refers to the region where a drive transistor is not provided in response to the light-emitting element).
  • the light-emitting element may have the structure in which the electrode serving as a cathode is located at the lower side, and the electrode serving as anode is located at the upper side.
  • the drive transistor 91 is a p-channel type, and in the case of the latter, the drive transistor 91 is an n-channel type.
  • the drive transistor 91 may be either a staggered type or an inversely staggered type.
  • the semiconductor layer of the drive transistor 91 may be any one of a crystalline semiconductor layer, an amorphous semiconductor layer, or a semiamorphous semiconductor layer.
  • the semiamorphous semiconductor has an intermediate structure between an amorphous structure and a crystalline structure (including single crystals and poly crystals).
  • the semiamorphous semiconductor has a stable third state with respect to free energy, and a crystalline region having a short-range order and lattice distortion.
  • At least a part of the semiconductor crystal grains with grain diameters of from 0.5 to 20 nm.
  • a raman spectrum is shifted to a lower wave number than 520 cm "1 .
  • diffraction peaks (111), (220) that may be derived from a Si crystalline lattice are observed.
  • Hydrogen or halogen of 1 atomic% or more is contained the semiconductor as neutralizer for dangling bond.
  • Such semiconductor is referred to as what is called micro crystal semiconductor.
  • a suicide gas is formed by glow discharge decomposition (plasma CVD).
  • As the suicide gas Si H 6 , SiH 2 Cl 2 , SiHCl 3 , SiCl , SiF 4 , or the like in addition to Sith can be used.
  • the suicide gas can be diluted by H , or the H and one or a plurality of rare gas elements selected from the group consisting of He, Ar, Kr, and Ne.
  • the dilution rate is in the range of from 2 to 1000 times.
  • An applied voltage is in the range of from 0.1 to 133 Pa.
  • a power source frequency is in the range of from 1 to 120 MHz, preferably, 13 to 60 MHz.
  • a heat temperature for a substrate is at most 300 °C, preferably, 100 to 250 °C.
  • atmospheric constituents such as oxygen, nitrogen, carbon, and the like have preferably concentrations of at most 1 x 10 /cm , especially, oxygen concentration is at most 5 x 10 19 /cm 3 , preferably, 1 x 10 1 /cm 3 .
  • a TFT (thin film transistor) including semiamorphous semiconductor has mobility of approximately from 1 to 10 m 2 /Vsec. Either the electrode serving as an anode or the electrode serving as a cathode, or both of them are formed by a material having light-transmitting properties.
  • an electrode serving as an anode is located at the lower side, and only the electrode serving as an anode is formed by a substance having light-transmitting properties; light is emitted through the side provided with a drive transistor as shown in FIG. 5A.
  • an electrode serving as a cathode is located at the lower side, and only the electrode serving as a cathode is formed by a material having light-transmitting properties, light is emitted through the side provided with a drive transistor as shown in FIG. 5A.
  • an electrode serving as an anode is located at the lower side, and only the electrode serving as a cathode is formed by a material having light-transmitting properties, light is emitted through the opposite side provided with a drive transistor as shown in FIG. 5B.
  • an electrode serving as a cathode is located at the lower side, and only the electrode serving as an anode is formed by a material having light-transmitting properties, light is emitted through the opposite side provided with a drive transistor as shown in FIG. 5B.
  • both of an electrode serving as an anode and an electrode serving as a cathode are formed by materials having light-transmitting properties, light is emitted from both sides as shown in FIG 5C irrespective of which electrode is provided to lower side or upper side.
  • the light-emitting element may emit either monochromatic light or light in full color such as red (R), green (G), blue (B), and the like.
  • Each light-emitting element is preferably divided by a bank layer.
  • the bank layer may be formed by a material that contains either an inorganic substance or an organic substance, or both of the inorganic substance and organic substance. For example, a silicon oxide film may be used.
  • a material having a skeleton structure formed by the bond of acrylic, polyimide, and (a substance in which a skeleton is formed by the bond of silicon (Si) and oxygen (O); and at least hydrogen is included as a substituent, or at least one element selected from the group consisting of fluoride, alkyl group, and aromatic hydrocarbon is included as the substituent), or the like may also be used.
  • the bank layer is preferably formed to have a curved edge portion whose radius of curvature is continuously varied. Since a light-emitting element according to the present invention has a long lifetime, a light-emitting device manufactured by practicing the present invention can display images and emit light in a long term.
  • Example 5 A light-emitting device including a light-emitting element according to the present invention as shown in Example 4 is mounted on various electric appliances after attached with an external input terminal. Such electric appliances manufactured by practicing the present invention can display high quality images in a long term. This arises from the fact that a light-emitting element according to the invention has long lifetime.
  • Example 5 a light-emitting device including a light-emitting element and electric appliances mounted with the light-emitting element are explained with reference to FIGS. 6 and 7.
  • FIG 6 is a top view of a light-emitting device including a light-emitting element according to the present invention.
  • reference numeral 401 indicated by dotted line denotes a drive circuit portion (a source side drive circuit); 402, a pixel portion; and 403, a drive circuit portion (a gate side drive circuit).
  • Reference numeral 404 denotes a sealing substrate, and 405 denotes a portion applied with sealing agent. Signals are inputted to the source side drive circuit 401 and the gate side drive circuit 403 when these circuits receive video signals, clock signals, start signals, reset signals, and the like via wirings provided to a device substrate 410 from an FPC (flexible print circuit) 409 serving as an external input terminal.
  • FPC flexible print circuit
  • the FPC may be provided with a printed wiring board (PWB).
  • a light-emitting device according to Example 5 refers to not only a main body of a light-emitting device, but also a main body provided with an FPC or a PWB.
  • FIG. 7 is one embodiment of an electric appliance installed with a light-emitting device as shown in FIG 6.
  • FIG 7 shows a laptop computer manufactured by practicing the present invention composed of a main body 5501, a housing 5502, a display portion 5503, a keyboard 5504, and the like.
  • a display device can be completed by incorporating a light-emitting device including a light-emitting element according to the invention into the laptop computer.
  • a cellular phone, a TV reception set, a car navigation, a lighting system, and the like may be installed with a light-emitting device including a light-emitting element according to the Invention.
  • Example 6 A method for manufacturing a light-emitting element according to the present invention, and device characteristics of the light-emitting element are explained in Example 6.
  • four light-emitting elements that is, a light-emitting element (1), a light-emitting element (2), a light-emitting element (3), and a light-emitting element (4), all of which have first layers with different thicknesses, are manufactured.
  • a first electrode is formed by an indium tin oxide (ITO) containing a silicon oxide over a glass substrate. Then, the glass substrate provided with the first electrode is treated in vacuum at 150 °C for 30 minutes.
  • ITO indium tin oxide
  • a first layer is formed by co-evaporation of a molybdenum oxide, rubrene, and DNTPD over the first electrode to have a weight ratio of 0.67: 1: 0.02, respectively.
  • the first layer of a light-emitting element (1) is formed to have a thickness of 40 nm.
  • the first layer of a light-emitting element (2) is formed to have a thickness of 80 nm.
  • the first layer of a light-emitting element (3) is formed to have a thickness of 120 nm.
  • the first layer of a light-emitting element (4) is formed to have a thickness of 160 nm.
  • a second layer is formed by vapor deposition of ⁇ -NPD over the first layer to have a thickness of 10 nm.
  • a third layer is formed by co-evaporation of Alq 3 and coumarin 6 over the second layer to have a weight ratio of 1: 0.005.
  • the third layer is formed to have a thickness of 37.5 nm.
  • a fourth layer is formed by vapor deposition of Alq 3 over the third layer to have a thickness of 37.5 nm.
  • a fifth layer is formed by vapor deposition of lithium fluoride (LiF) over the fourth layer to have a thickness of 1 nm.
  • a second electrode is formed by vapor deposition of aluminum over the fifth layer to have a thickness of 200 nm.
  • FIGS. 10 and 11 show the device characteristics of thus manufactured light-emitting elements.
  • FIG. 10 shows luminance- voltage characteristics of the light-emitting elements manufactured according to Example 6. In FIG.
  • a horizontal axis shows voltage (V), and a vertical axis shows luminance (cg m 2 ).
  • closed circles indicate characteristics of the light-emitting element (1); open circles indicate characteristics of the light-emitting element (2); closed squares indicate characteristics of the light-emitting element (3); and open squares indicate characteristics of the light-emitting element (4).
  • FIG. 10 shows that an onset voltage, which is a voltage for electroluminescence of 1 cd/m 2 or more, is approximately 2.5 V in each light-emitting element. The onset voltages are approximately the same with each other despite the thickness of the first layer of each the light-emitting element.
  • FIG. 11 shows a measurement result of the variation of luminance per hour of a light-emitting element manufactured according to Example 6.
  • a horizontal axis shows hour
  • a vertical axis shows luminance.
  • the luminance is represented its relative value to initial luminance based on the initial value of 100.
  • the variation of luminance is measured by applying continuously a constant amount of current to a light-emitting element, that is, applying a stress to a light-emitting element; and the luminance of the light-emitting element is measured at given time intervals.
  • a current that has a current density required to obtain electroluminescence with a luminance of 3000 cs/m 2 at an initial state is applied, and the luminance obtained at the applied current is measured.
  • FIG. 11 shows that after 100 hours the luminance is decreased by 14% or less to the initial luminance in each the light-emitting element (1), (2), (3), and (4).
  • the luminance of a light-emitting element practiced by the present invention is hardly deteriorated.
  • Example 7 A method for manufacturing a light-emitting element according to the present invention and device characteristics of the light-emitting element are explained in Example 7.
  • nine light-emitting elements that is, a light-emitting element (11), a light-emitting element (12), a light-emitting element (13), a light-emitting element (14), a light-emitting element (15), a light-emitting element (16), a light-emitting element (17), a light-emitting element (18), and a light-emitting element (19), all of which have first electrodes formed by different materials, are manufactured.
  • a first electrode for the light-emitting element (11) is formed by aluminum containing several % silicon over a glass substrate.
  • a first electrode for the light-emitting element (12) is formed by aluminum containing several % titanium over a glass substrate.
  • a first electrode of the light-emitting element (13) is formed by titanium over a glass substrate.
  • a first electrode of the light-emitting element (14) is formed by titanium nitride over a glass substrate.
  • a first electrode of the light-emitting element (15) is formed by tantalum over a glass substrate.
  • a first electrode of the light-emitting element (16) is formed by tantalum nitride over a glass substrate.
  • a first electrode of the light-emitting element (17) is formed by tungsten over a glass substrate.
  • a first electrode of the light-emitting element (18) is formed by chromium over a glass substrate.
  • a first electrode of the light-emitting element (19) is formed by molybdenum over a glass substrate. Then, the glass substrate provided with the first electrode is treated in vacuum at 150 °C for 30 minutes. A first layer is formed by co-evaporation of a molybdenum oxide, rubrene, and ⁇ -NPD over the first electrode to have a weight ratio of 0.1: 1: 0.02, respectively. The first layer is formed to have thickness of 60 nm. A second layer is formed by vapor deposition of ⁇ -NPD over the first layer to have a thickness of 10 nm. A third layer is formed by co-evaporation of Alq 3 and coumarin 6 over the second layer to have a weight ratio of 1: 0.005.
  • the third layer is formed to have a thickness of 40 nm.
  • a fourth layer is formed by vapor deposition of Alq over third layer to have a thickness of 20 nm.
  • a fifth layer is formed by co-evaporation of lithium (Li) and 4,4'-bis(5-methylbenzoxazole-2-yl)stilbene (abbreviated BzOs) over the fourth layer to have a weight ratio of 0.02: 1, respectively.
  • the fifth layer is formed to have a thickness of 20 nm.
  • a second electrode is formed by an indium tin oxide (ITO) over the fifth layer to have a thickness of 110 nm.
  • ITO indium tin oxide
  • FIG. 12 shows the measurement results indicated by closed squares.
  • a horizontal axis shows the manufactured light-emitting elements
  • a vertical axis shows voltage (V).
  • Example 7 a light-emitting element (21), a light-emitting element (22), a light-emitting element (23), a light-emitting element (24), a light-emitting element (25), a light-emitting element (26), a light-emitting element (27), a light-emitting element (28), and a light-emitting element (29) are explained hereinafter.
  • Each layer composing the light-emitting elements (21) to (29) is manufactured by the same material to have the same thickness as those of the light-emitting elements (11) to (19) except that the first layer of each the light-emitting elements (21) to (29) is formed by copper phthalocyanine.
  • a first electrode of the light-emitting element (21) is formed by aluminum containing several % silicon.
  • a first electrode of the light-emitting element (22) is formed by aluminum containing several % titanium.
  • a first electrode of the light-emitting element (23) is formed by titanium.
  • a first electrode of the light-emitting element (24) is formed by titanium nitride.
  • a first electrode of the light-emitting element (25) is formed by tantalum.
  • a first electrode of the light-emitting element (26) is formed by tantalum nitride.
  • a first electrode of the light-emitting element (27) is formed by tungsten.
  • a first electrode of the light-emitting element (28) is formed by chromium.
  • a first electrode of the light-emitting element (29) is formed by molybdenum.
  • voltage is applied to each of thus manufactured light-emitting element so that an electric potential of the first electrode is higher than that of the second electrode.
  • FIG. 12 shows the measurement results indicated by closed triangles.
  • FIG. 12 shows that the onset voltages of the light-emitting elements (21) to (29) having first layers formed by copper phthalocyanine are different from each other, that is, the onset voltages depend on the material for forming the first electrode.
  • the onset voltages of the light-emitting elements (11) to (21) practiced by the present invention are almost the same with each other despite a material for forming the first electrode.
  • the light-emitting element according to the present invention is less subject to kinds of materials for forming an electrode or the like. Therefore, it becomes easy to select an electrode formed by a material having better reflectivity in the case that a light-emitting element in which an electrode is used to reflect light emission is manufactured according to the present invention.
  • Example 8 A method for manufacturing a light-emitting element according to the present invention and characteristics of the light-emitting element are explained hereinafter.
  • Example 8 light-emitting elements, all of which have first layers with different thicknesses, are manufactured. The film thickness dependence of a driving voltage of the light-emitting elements will be revealed.
  • the light-emitting elements (1) to (4) manufactured in Example 6 are used as samples.
  • the first layer in the light-emitting element (1) is formed to have a thickness of 40 nm.
  • the first layer in the light-emitting element (2) is formed to have a thickness of 80 nm.
  • the first layer in the light-emitting element (3) is formed to have a thickness of 120 nm.
  • the first layer in the light-emitting element (4) is formed to have a thickness of 160 nm.
  • FIG. 13 shows current density-voltage characteristics of the light-emitting elements (1) to (4).
  • the current density-voltage characteristics of the light-emitting elements (1) to (4) are hardly different from each other despite the difference in the thicknesses of the first layers. Therefore, the increase of a thickness of the first layer that is formed by a molybdenum oxide, rubrene, and DNTPD does not result in the increase of a driving voltage.
  • a light-emitting element (30), a light-emitting element (31), a light-emitting element (32), a light-emitting element (33), a light-emitting element (34), and a light-emitting element (35) are explained hereinafter.
  • the light-emitting elements (30) to (35), all of which have second layers with different thicknesses, are manufactured.
  • a first layer is formed by copper phthalocyanine to have a thickness of 20 nm.
  • the second layer is formed by ⁇ -NPD by vapor deposition.
  • the second layer of the light-emitting element (30) is formed to have a thickness of 60 nm.
  • the second layer of the light-emitting element (31) is formed to have a thickness of 80 nm.
  • the second layer of the light-emitting element (32) is formed to have a thickness of 100 nm.
  • the second layer of the light-emitting element (33) is formed to have a thickness of 120 nm.
  • the second layer of the light-emitting element (34) is formed to have a thickness of 140 nm.
  • the second layer of the light-emitting element (35) is formed to have a thickness of 160 nm.
  • a third layer is formed by co-evaporation of Alq 3 and coumarin-6 over a second layer to have a weight ratio of 1: 0.005.
  • the third layer is formed to have a thickness of 37.5 nm.
  • a fourth layer is formed by vapor deposition of Alq 3 to have a thickness of 37.5 nm over the third layer.
  • a fifth layer is formed by vapor deposition of calcium fluoride (CaF 2 ) to have a thickness of 1 nm over the fourth layer.
  • a second electrode is formed by vapor deposition of aluminum to have a thickness of 200 nm over the fifth layer.
  • FIG. 14 shows current density-voltage characteristics of the light-emitting elements (30) to (35). The driving voltages of the light-emitting elements are increased with increasing the thicknesses of the second layers. Therefore, the increase of a thickness of the second layer formed by ⁇ -NPD results in the increase of the driving voltage.
  • a light-emitting element (36), a light-emitting element (37), and a light-emitting element (38) are explained hereinafter.
  • Each of first layers is formed by a molybdenum oxide to have a different thickness form each other.
  • a second layer is formed by copper phthalocyanine to have a thickness of 20 nm.
  • a third layer is formed by vapor deposition of ⁇ -NPD to have a thickness of 40 nm.
  • a fourth layer is formed by co-evaporation of Alq 3 and coumarin-6 to have a thickness of 37.5 nm over the third layer.
  • a fifth layer is formed by vapor deposition of Alq 3 to have a thickness of 37.5 nm over the fourth layer.
  • a sixth layer is formed by vapor deposition of CaF 2 to have a thickness of 1 nm over the fifth layer.
  • a second electrode is formed by vapor deposition of aluminum to have a thickness of 200 nm over the sixth layer.
  • FIG. 15 shows current density-voltage characteristics of the light-emitting elements (36) to (38).
  • the driving voltages of the light-emitting elements are increased with increasing the thicknesses of the first layers formed by molybdenum oxides.
  • Table 1 shows the results of film thickness dependence of driving voltage provided by Example 8, Comparative Example 3, and Comparative Example 4.
  • Table 1 shows the data of a driving voltage required to apply a current of 100 mA/cm to a light-emitting element. [Table 1]
  • Example 8 a driving voltage of 6.1 to 6.3 V is required to apply a current of
  • Table 1 shows that a driving voltage of a light-emitting element provided with a layer formed by a mixture of an organic compound and an inorganic can be lower than that of a light-emitting element provided with a layer formed by ⁇ -NPD or a molybdenum oxide that is an inorganic compound. Moreover, it also shows that the increase of the driving voltage can be prevented even if the thickness of the layer is increased. Therefore, a driving voltage can be reduced by using the light-emitting element according to the present invention, accordingly, the power consumption of the light-emitting element can be reduced. Further, a thickness of a light-emitting element can be increased, and so it becomes possible to reduce short-circuit deterioration between a pair of electrodes.
  • Example 9 Characteristics of a QVGA active matrix light-emitting device having a screen size of 2.4 inches are explained in Example 9.
  • the active matrix light-emitting device drives a light-emitting element by a transistor as in the case with Example 4.
  • the light-emitting device has the configuration explained in the following.
  • a first electrode is formed by an indium tin oxide containing a silicon oxide.
  • a first layer is formed by co-evaporation of a molybdenum oxide and ⁇ -NPD having high hole transportation properties over the first electrode.
  • a light-emitting device in which the first layer is formed by a mixture of a molybdenum oxide and ⁇ -NPD to have a thickness of 120 nm is referred to as a light-emitting device 1.
  • a light-emitting device in which the first layer is formed to have a thickness of 240 nm is referred to as a light-emitting device 2.
  • a second layer is formed by vapor deposition of ⁇ -NPD to have a thickness of 10 nm over the first layer.
  • a third layer is formed by co-evaporation of Alq 3 and coumarin-6 to have a thickness of 40 nm over the second layer.
  • a fourth layer is formed by vapor deposition of Alq 3 to have a thickness of 30 nm over the third layer.
  • a fifth layer is formed by vapor deposition of calcium fluoride (CaF 2 ) to have a thickness of 1 nm over the fourth layer.
  • a second electrode is formed by vapor deposition of aluminum to have a thickness of 200 nm over the fifth layer.
  • the number of dark spots (pixels that do not emit light) in the light-emitting devices 1 and 2 is checked at the beginning of electrical conduction and after a temperature cycle test (+85 °C (four hours) to -40 °C (four hours)) for 60 hours.
  • the light-emitting device 1 has the average of the number of dark spots of 0.7 at the beginning of electrical conduction, and 2.3 after the temperature cycle test.
  • the light-emitting device 2 has the average of the number of dark spots of 0.5 at the beginning of electrical conduction, and 0.5 after the temperature cycle test.
  • the term "average of the number of dark spots" refers to an average value in examined closed triangle numbers of light-emitting device.
  • Example 5 As a comparative example for Example 9, an active matrix light-emitting device 3 in which a light-emitting element has a different configuration is manufactured.
  • the light-emitting element is formed in the following manner.
  • a first layer is formed by copper phthalocyanine to have a thickness of 20 nm.
  • a second layer is formed by ⁇ -NPD to have a thickness of 40 nm.
  • a third layer is formed by co-evaporation of Alq 3 and coumarin 6 to have a thickness of 40 nm over the second layer.
  • a fourth layer is formed by vapor deposition of Alq 3 to have a thickness of 40 nm over the third layer.
  • a fifth layer is formed by vapor deposition of calcium fluoride (CaF ) to have a thickness of 1 nm over the fourth layer.
  • a second electrode is formed by vapor deposition of aluminum to have a thickness of 200 nm over the fifth layer.
  • the number of dark spots in the light-emitting device 3 is checked at the beginning of electrical conduction and after a temperature cycle test (+85 °C (four hours) to -40 °C (four hours)) for 60 hours.
  • the light-emitting device 3 has the average of the number of dark spots of 18 at the beginning of electrical conduction, and 444 after the temperature cycle test.
  • the average of the number of dark spots after the temperature cycle test is increased by 25 times as many as that at the beginning of electrical conduction.
  • Table 2 illustrates the results of the number of dark spots after the temperature cycle test (+85 °C (four hours) to -40 °C (four hours)) for 60 hours in Example 9 and Comparative Example 5. [Table 2]
  • Example 8 According to the result from Example 8, it is clear that a driving voltage is not increased with increasing the thickness of a light-emitting element. Therefore, a light-emitting device with a low driving voltage and with drastically inhibited dark pixel defects can be provided according to the present invention.
  • Example 10 Characteristics of a film formed by a molybdenum oxide that is a metal oxide, a film formed by ⁇ -NPD that is an organic compound with high hole transporting properties, and a film formed by a mixture of a molybdenum oxide and ⁇ -NPD are examined. These films are formed by vapor deposition. As illustrated in Table 3, the ionization potential of the film formed by a mixture of a molybdenum oxide and ⁇ -NPD is approximately 0.1 to 0.2 eV less than that of the film formed by a molybdenum oxide and the film formed by ⁇ -NPD.
  • FIG. 16 shows absorption spectra of these films.
  • the spectra of the film of a molybdenum oxide and the film of ⁇ -NPD have no characteristic peak in a visible light region.
  • the absorption of the film formed by a mixture of a molybdenum oxide and ⁇ -NPD (OMOx) is less than that of the film formed by a molybdenum oxide.
  • absorption loss of light can be reduced by using a layer formed by a mixture of a molybdenum oxide and ⁇ -NPD rather than using a layer formed by a molybdenum oxide.
  • the spectrum of the film formed by a mixture of a molybdenum oxide and ⁇ -NPD has newly an absorption peak at around 500 nm.
  • the absorption peak may be resulted from the formation of a charge-transfer complex between the molybdenum oxide and the ⁇ -NPD in the film.
  • the molybdenum oxide is an accepter, while the ⁇ -NPD is a donor. Further, it has been confirmed that not only ⁇ -NPD but also an amine-based compound such as DNTPD serves as a donor.
  • the lifetime can be extended of a light-emitting element that includes a layer containing a compound selected from the group of metal oxides and a compound having high hole transporting properties since the crystallization of the layer can be suppressed.
  • the mixing of an inorganic material and an organic material can generate a synergistic effect that cannot be obtained by using these materials separately.

Abstract

A light-emitting element is disclosed that can drive at a low driving voltage and that has a longer lifetime than the conventional light-emitting element, and a method is disclosed for manufacturing the light-emitting element. The disclosed light-emitting element includes a plurality of layers between a pair of electrodes; and at least one layer among the plurality of layers contains one compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having high hole transportation properties. Such the light-emitting element can suppress the crystallization of a layer containing one compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having high hole transportation properties. As a result, a lifetime of the light-emitting element can be extended.

Description

DESCRIPTION
LIGHT-EMITTING DEVICE AND METHOD FOR MANUFACTURING THE SAME
TECHNICAL FIELD The present invention relates to a light-emitting element formed to have the structure in which a plurality of layers is sandwiched between a pair of electrodes. More specifically, the present invention relates to the structure of a layer, which can be used as at least one layer, within the plurality of layers.
BACKGROUND ART A light-emitting device utilizing light emission from an electroluminescent element (light-emitting element) has been attracted attention as a display device or a lighting device. As a light-emitting element used for a light-emitting device, a light-emitting element including a layer containing light-emitting compounds interposed between a pair of electrodes is well known. Within such a light-emitting element, either of the electrodes serves as an anode, and another serves as a cathode, holes injected from the anode and electrons injected from the cathode are recombined with each other to form molecular exciton, and the molecular exciton radiates energy as light while returning to the ground state. The demand for low power consumption is especially increased in display devices to be installed in various information processing devices, which have been drastically developed in recent years. In order to achieve low power consumption, it has been attempted to reduce a voltage for driving a light-emitting element. In consideration with commercialization, it is important not only to reduce a voltage for driving a light-emitting element but also extend a lifetime of a light-emitting device. Therefore, a light-emitting device has been developed to achieve low power consumption and a long lifetime. For example, unexamined patent publication No. 9-63771 discloses that a voltage for driving a light-emitting element is reduced by forming an anode by a metal oxide having a large work function such as a molybdenum oxide. Moreover, a lifetime of the light-emitting element can be extended. The means for extending a lifetime of a light-emitting element disclosed in the unexamined patent publication No. 9-63771 is insufficient, and so it is required to develop the technique for achieving a further long lifetime.
DISCLOSURE OF VΕNTION It is an object of the present invention to provide a light-emitting element that drives at low voltage and has a longer lifetime than the conventional light-emitting element, and a method for manufacturing the light-emitting element. According to one aspect of the present invention, a light-emitting element includes a plurality of layers between a pair of electrodes, and at least one layer among the plurality of layers contains a hybrid material (a composite material) including an inorganic compound selected from the group consisting of oxide semiconductor and a metal oxide, and an inorganic compound having high hole transportation properties. The plurality of layers is composed of layers formed respectively by a substance having high carrier injection properties, a substance having high carrier transportation properties, and the like, so that a light-emitting region is located away from electrodes. Such the light-emitting element can suppress crystallization of a layer containing one compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having high hole transportation properties. As a result, a lifetime of a light-emitting element can be extended. As specific examples of the oxide semiconductor and the metal oxide, although not limited to the substances recited herein, a molybdenum oxide (MoOx), a vanadium oxide (VOx), a ruthenium oxide (RuOx), a tungsten oxide (WOx), and the like can be used. Besides, an indium tin oxide (ITO), a zinc oxide (ZnO), and a tin oxide (SnO) can be used. Other substances than the foregoing substances can be used. As the compound having high hole transportation properties, although not limited to the substances recited herein,
4,4'-bis[N-(l-naphtyl)-N-phenyl-amino]-biphenyl (abbreviated α-NPD), an aromatic amine compound (that is, the one having a bond of benzene ring and nitrogen) such as 4,4'-bis[N-(3-methylphenyl)-N-phenyl-amino]-biphenyl (abbreviated TPD),
4,4',4"-tris(N,N-diphenyl-amino)-triphenylamine (abbreviated TDATA),
4,4',4"-tris[N-(3-methylphenyl)-N-phenyl-amino]-triphenylamine (abbreviated
MTDATA) can be used. Other substances than the foregoing substances can be used. According to one aspect of the present invention, a light-emitting element includes a plurality of layers between a pair of electrodes, and at least one layer among the plurality of layers contains one compound selected from the group consisting of oxide semiconductor and a metal oxide, a compound having high hole transportation properties, and a compound having a high steric hindrance. As same as the aforementioned light-emitting element, the plurality of layers is composed of layers respectively formed by a substance having high carrier injection properties, a substance having high carrier transportation properties, and the like, so that a light-emitting region is located away from electrodes. Such the light-emitting element that includes a layer containing one compound selected from the group consisting of oxide semiconductor and a metal oxide, a compound having high hole transportation properties, and a compound having a high steric hindrance can suppress the crystallization of the layer. As a result, a lifetime of a light-emitting element can be extended. The oxide semiconductor, the metal oxide, and the compound having high hole transportation properties are the same as those mentioned above. As a compound having a high steric hindrance (that is, the compound having spatiality contrary to a plane structure), 5,6,11, 12-tetraphenyltetracene (abbreviated rubrene) is preferably used. Besides, hexabenilbenzene, diphenylanthracene, t-butylperylene, 9,10-di(phenyl)anthracene, coumarin 545T, and the like can be used.
In addition, dendrimer or the like can be used. According to the present invention, aggregation of oxide semiconductor or a metal oxide can be suppressed, and crystallization of a layer containing the oxide semiconductor or the metal oxide can be suppressed. By suppression of the crystallization, a leak current can be prevented from generating due to the crystallization.
Accordingly, a long-lived light-emitting element can be obtained. These and other objects, features and advantages of the present invention will become more apparent upon reading of the following detailed description along with the accompanied drawings.
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a graph for showing luminance variations with time of light-emitting elements according to certain aspects of the present invention and Comparative Example; FIGS. 2A to 2C are explanatory cross-sectional views of a light-emitting element according to certain aspects of the present invention; FIG. 3 is an explanatory cross-sectional view of a light-emitting element according to certain aspects of the present invention; FIG. 4 shows luminance-voltage characteristics of light-emitting elements according to certain aspects of the present invention and Comparative Example 1; FIGS. 5A to 5C are cross-sectional views of a light-emitting element according to certain aspects of the present invention; FIG 6 is a top view of a light-emitting device including a light-emitting element according to certain aspects of the present invention; FIG. 7 is a view for showing an electric appliance mounted with a light-emitting device including a light-emitting element according to certain aspects of the present invention; FIG. 8 shows luminance-voltage characteristics of light-emitting elements according to certain aspects of the present invention and Comparative Example 1; and FIG. 9 is a graph for showing luminance variations with time of a light-emitting element according to certain aspects of the present invention. FIG. 10 shows luminance-voltage characteristics of light-emitting elements according to certain aspects of the present invention. FIG. 11 is a graph for showing luminance variations with time of a light-emitting element according to certain aspects of the present invention. FIG. 12 is a graph for showing voltages for electroluminescence of 1 cd/m2 or more according to certain aspects of the present invention and Comparative Example 2. FIG. 13 is a graph for showing current density-voltage characteristics of light-emitting elements according to certain aspects of the present invention. FIG. 14 is a graph for showing current density-voltage characteristics of light-emitting elements according to certain aspects of Comparative Example 3. FIG. 15 is a graph for showing current density-voltage characteristics of light-emitting elements according to certain aspects of Comparative Example 4. FIG 16 is a graph for showing absorption characteristics of light-emitting element according certain aspects of the present invention.
BEST MODE FOR CARRYING OUT THE INVENTION A light-emitting element according to the present invention includes a plurality of layers between a pair of electrodes. The plurality of layers is formed by stacking layers in combination with each other, which is formed respectively by a substance having high carrier injection properties or a substance having high carrier transportation properties, so that a light-emitting region is formed away from the electrodes, that is, carriers are recombined with each other in the region away from the electrodes. One mode of a light-emitting element according to the present invention is explained with reference to FIG. 2A. In this embodiment, a light-emitting element 210 is formed over a substrate 201 used for supporting the light-emitting element 210, and is composed of sequentially a first electrode 202, a first layer 203, a second layer 204, a third layer 205, a fourth layer 206, and a second electrode 207. Further, the first electrode 202 serves as an anode, and the second electrode 207 serves as a cathode in this embodiment. As the substrate 201, for example, glass or plastic can be used. Another material can be used for the substrate as long as it serves as a support medium for the light-emitting element during a manufacturing process. The first electrode 202 is preferably formed by a metal having a large work function (at least 4.0 eV), an alloy, an electric conductive compound, or a mixture of the foregoing materials. Specifically, an indium tin oxide (ITO), an indium tin oxide containing silicon, an indium zinc oxide, that is, an indium oxide mixed with zinc oxide of from 2 to 20 % (ZnO), aurum (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cu), molybdenum (Mo), ferrum (Fe), cobalt (Co), copper (Cu), palladium (Pd), or a nitride of a metal material (TiN), or the like can be used. The first layer 203 is a layer containing a compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having high hole transportation properties. As specific examples of the oxide semiconductor and the metal oxide, although not limited to the substances recited herein, a molybdenum oxide (MoOx), a vanadium oxide (VOx), a ruthenium oxide (RuOx), a tungsten oxide (WOx), and the like can be used. Other substances than the foregoing substances can. be used. As a compound having high hole transportation properties, for example, an aromatic amine compound (that is, the one having a bond of a benzene ring and nitrogen) such as 4,4'-bis[N-(l-naphtyl)-N-phenyl-amino]-biphenyl (abbreviated -NPD),
4,4'-bis[N-(3-methylphenyl)-N-phenyl-amino]-biphenyl (abbreviated TPD),
4,4',4"-tris(N,N-diphenyl-amino)-triphenylamine (abbreviated DATA), 4,4' ,4"-tris[N-(3-methylphenyl)-N-phenyl-amino]-triphenylamine (abbreviated
MTDATA) can be used. The foregoing substances are mainly the substances having hole mobility of 10"6 cm2/Vs or more. Another substance can be used as long as it has higher hole transportation properties than electron transportation properties. The first layer 203 having the structure as mentioned above has high hole injection properties. In the first layer 203, the aggregation of oxide semiconductor or a metal oxide is suppressed by a substance having high hole transportation properties contained in the layer. That is, crystallization of the fist layer 203 is suppressed. In addition, the first layer 203 may be formed by, for example, at least two layers respectively containing semiconductor and a compound having high transportation properties with different mixture ratio from each other instead of being formed by one layer. Further, the first layer 203 may further includes a compound having a high steric hindrance (that is, the compound having spatiality contrary to a plane structure) in addition to a compound selected from oxide semiconductor and a metal oxide, and a compound having high hole transportation properties. As the compound having a high steric hindrance, 5,6,11, 12-tetraphenyltetracene (abbreviated rubrene) is preferably used. Besides, hexabenilbenzene, diphenylanfhracene, t-butylperylene,
9,10-di(phenyl)anthracene, coumarin 545T, and the like can be used. In addition, dendrimer or the like can be used. Thus, crystallization of a molybdenum oxide can be further suppressed by mixing a substance with a structure having a high steric hindrance, that is, having spatiality contrary to a plane structure, into the first layer 203. The second layer 204 is a layer formed by a substance having high hole transportation properties, for example, an aromatic amine compound (that is, the one having a bond of a benzene ring-nitrogen) such as α-NPD, TPD, TDATA, MTDATA, and the like. The foregoing substances are mainly the substances having hole mobility of 10"6 cm2/Vs or more. Another substance can be used as long as it has higher hole transportation properties than electron transportation properties. In addition, the second layer 204 may be formed by stacking at least two layers containing the foregoing substances instead of being formed by one layer. The third layer 205 is a layer containing a substance having high light-emitting properties. For example, a substance having high light-emitting properties such as N'N-dimethylquinacridone (abbreviated DMQd), 2H-chromene-2-on (abbreviated coumarin), and a substance having high carrier transportation properties and a good film formation property, that is, a substance that is hard to be crystallized, such as tris(8-quinolmolato)aluminum (abbreviated Alq3) or 9,10-di(2-naphtyl)anthracene (abbreviated DNA) can be used by freely combining with each other. Alq3 and D3NA have high light-emitting properties, consequently, the third layer 205 may be solely formed by Alq3 or DNA. The fourth layer 206 is a layer formed by a metal complex or the like having a quinoline skeleton or a benzoquinoline skeleton, for example, a substance having high electron transportation properties such as tris(8-quinolinolato)aluminum (abbreviated Alq3), tris(5-methyl-8-quinolinolato)aluminum (abbreviated Almq3), bis(10-hydroxybenz)[h]-quinolinato)beryllium (abbreviated BeBq2), and bis(2-methyl-8-quinolinolato)-4-phenylphenolato-aluminum (abbreviated BAlq). Further, a metal complex having a oxadiazole ligand or a thiazole ligand such as bis[2-(2-hydroxyphenyl)-benzooxazolate]zinc (abbreviated Zn(BOX)2), and bis[2-(2-hydroxyphenyl)-benzothiazolate]zinc (abbreviated Zn(BTZ)2). Besides the metal complexes, 2-(4-biphenyl)-5-(4-tert-butylphenyl)-l,3,4-oxadiazole (abbreviated PBD), and l,3-bis[5-(p-tert-butylphenyl)-l,3,4-oxadiazole-2-yl]benzene (abbreviated OXD-7), 3-(4-tert-butylphenyl)-4-phenyl-5-(4-biphenylyl)-l,2,4-triazole (abbreviated TAZ), and 3-(4-tert-butylphenyl)-4-(4-ethylphenyl)-5-(4-biphenylyl)-l,2,4-triazole (abbreviated p-EtTAZ), bathophenanthroline (abbreviated BPhen), bathocuproin (abbreviated BCP), and the like can be used. The foregoing substances are the substances having hole mobility of 10"6 cm2/Vs or more. Another substance can be used as long as it has higher hole transportation properties than electron transportation properties. In addition, the fourth layer 206 may be formed by at least two layers containing the foregoing substances instead of being formed by one layer. As a material for the second electrode 207, metals having a small work function (at most 3.8 eV), alloys, electric conductive compounds, or a mixture of the above are preferably used. As a specific example of cathode materials, metals belonging to a 1 or 2 group of the periodic table of the elements, that is, alkali metals such as lithium (Li) or cesium (Cs); alkali earth metals such as magnesium (Mg), calcium (Ca), strontium (Sr); and alloys including the above elements (Mg:Ag, Al:Li) can be used. In case that a layer promoting electron injection is stacked between the second electrode 207 and a light-emitting layer, various conductive materials such as Al, Ar, ITO containing silicon, and the like can be used regardless of their work function can be used for the second electrode 207. As the layer promoting electron injection, a compound of an alkali metal or an alkali earth metal such as lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF2), and the like. Besides, a layer formed by a substance having election transportation properties containing an alkali metal or an alkali earth metal, for example,
Alq3 containing magnesium (Mg), or the like can be used. The first layer 203, the second layer 204, the third layer 205, and the fourth layer 206 may be formed by the method other than vapor deposition. For example, ink jetting, spin coating, and the like can be used. Each electrode or each layer may be formed by different film formation methods, respectively. Within a light-emitting element according to the invention having the foregoing structure, a current is flowed due to electric potential differences generated between the first electrode 201 and the second electrode 207, and holes and electrons are recombined with each other within the third layer 205, which is a layer containing high light-emitting properties, then, light is generated. Therefore, a light-emitting region is formed in the third layer 205. However, the entire third layer 205 is not required to be served as a light emission region. For example, the light-emitting region may be formed either the side of the second layer 204 or the fourth layer 206 within the third layer 205. Light is emitted to the outside passing through either the first electrode 202 or the second electrode 207, or both of them. Therefore, either the first electrode 202 or the second electrode 207, or both of them are formed by a substance having light-transmitting properties. In the case that only the first electrode 202 is formed by a substance having light-transmitting properties, light is emitted from the substrate passing through the first electrode 202 as shown in FIG. 2A. In the case that only the second electrode 207 is formed by a substance having light-transmitting properties, light is emitted from the opposite side of the substrate passing through the second electrode 207. In the case that the first electrode 202 and the second electrode 207 are formed by substances having light-transmitting properties, light is emitted from both of the substrate and the opposite side of the substrate passing through the first electrode 202 and the second electrode 207. The structure of a layer formed between the first electrode 202 and the second electrode 207 is not limited to the above described structure. The layer structure may have the other structure than the foregoing one as long as the structure is formed to have an area for the recombination of holes and electrons is located away from the first electrode 202 and the second electrode 207 to prevent quenching due to that a light-emitting region and a metal are close to one another; and a layer containing a compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having high hole transportation properties (moreover, a compound having a high steric hindrance may be contained). The lamination structure of the layer is not restricted especially. A layer formed by a substance having high electron transportation properties or hole transportation properties, a substance having electron injection properties, a substance having hole injection properties, a substance having bipolar properties (high electron or hole transportation properties), or the like; and a layer formed by a compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having high hole transportation properties may be freely combined with each other. Further, an area for recombination of carriers may be controlled by providing an ultra thin layer such as a silicon oxide layer. For example, the structure shown in FIG. 3 may be formed. However, a layer structure is not limited thereto. The light-emitting element shown in FIG. 3 is formed by stacking a first electrode 502 serving as a cathode; a first layer 503 formed by a substance having high electron transportation properties; a second layer 504 formed by a substance having high light-emitting properties; a third layer 505 formed by a substance having high hole transportation properties; a fourth layer 506 containing a compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having high hole transportation properties; and a second electrode 507 serving as an anode. In addition, reference numeral 501 shown in FIG. 3 denotes a substrate. According to this embodiment, a light-emitting element is manufactured over a glass or plastic substrate. A passive type light-emitting device can be manufactured by manufacturing a plurality of such light-emitting elements over one substrate. Instead of the glass or plastic substrate, a light-emitting element can be manufactured over a thin film transistor (TFT) array. Thus, an active matrix type light-emitting device that controls the drive of a light-emitting element by a TFT can be manufactured. The structure of the TFT is not especially restricted. The TFT may be either a staggered TFT or an inversely staggered TFT. A drive circuit formed over the TFT array substrate may be formed by both an N-type TFT and a P-type TFT. Alternatively, the drive circuit may be formed by either an N-type TFT or a P-type TFT. Accordingly, the crystallization of the layer can be suppressed in the light-emitting element including a layer containing a compound selected from the group consisting of oxide semiconductor and a metal oxide, and a substance having high hole transportation properties. Therefore, the generation of a leak current due to the crystallization of the layer can be suppressed, and a long-lived light-emitting element can be obtained. The crystallization of the layer can be further suppressed, and a further long-lived light-emitting element can be obtained in the light-emitting element including a layer containing a compound selected from the group consisting of oxide semiconductor and a metal oxide, a substance having high hole transportation properties, and a substance having a high steric hindrance.
[Example 1] Hereinafter, a method for manufacturing a light-emitting element according to the present invention and properties of the light-emitting element is explained. A first electrode is formed by depositing an indium tin oxide (ITO) over a glass substrate. Then, the glass substrate deposited with the ITO is processed in vacuum at 150 °C for 30 minutes. A first layer is formed by co-evaporation of a molybdenum oxide and α-NPD having high hole transporting properties over the first electrode. The weight ratio of the molybdenum oxide and the α-NPD is 0.245: 1. The first layer is formed to have a thickness of 130 nm. As used herein, the term "co-evaporation" refers to a method for evaporating each of materials from a plurality of evaporation sources provided in one processing chamber, and mixing the evaporated materials in the gas phase to deposit the mixed materials onto a subject. A second layer is formed by vapor deposition of α-NPD over the first layer to have a thickness of 10 nm. A third layer is formed by co-evaporation of Alq3 and coumarin-6 over the second layer. The weight ratio of the Alq3 and the coumarin-6 is 1: 0.002. The third layer is formed to have a thickness of 37. 5 nm. A fourth layer is formed by vapor deposition of Alq3 over the third layer to have a thickness of 37.5 nm. A fifth layer is formed by vapor deposition of calcium fluoride (CaF2) over the fourth layer to have a thickness of 1 nm. A second electrode is formed by vapor deposition of aluminum over the fifth layer to have a thickness of 200 nm. FIGS. 1 and 4 show device characteristics of thus manufactured light-emitting element. FIG 4 shows luminance-voltage characteristics of a light-emitting element manufactured according to Example 1. In FIG 4, a horizontal axis shows an applied voltage (V), and a vertical axis shows luminance (cd/m ). FIG. 4 shows that an onset voltage, which is a voltage for electroluminescence of 1 cd/m2 or more, is approximately 2.5 V. FIG. 1 shows a measurement result of the variation of luminance per hour of a light-emitting element manufactured according to Example 1. In FIG. 1, a horizontal axis shows hour, and a vertical axis shows luminance. The luminance is represented its relative value to initial luminance based on the initial value of 100. The variation of luminance is measured by applying continuously a constant amount of current to a light-emitting element, that is, applying a stress to a light-emitting element; and the luminance of the light-emitting element is measured at given time intervals. A current that has a current density required to obtain electroluminescence with a luminance of 1000 cs/m2 at initial state is applied, and the luminance obtained at the applied current is measured. FIG. 1 shows that after 100 hours luminance becomes the value of 82, that is, the luminance is decreased by 18% compared to the initial luminance.
[Example 2] A method for manufacturing a light-emitting element according to the present invention and characteristics of the light-emitting element is explained. A first electrode is formed by depositing an indium tin oxide (ITO) over a glass substrate. The glass substrate deposited with the ITO is processed in vacuum at 150 °C for 30 minutes. A first layer is formed over the first electrode by co-evaporation of a molybdenum oxide, α-NPD having high hole transportation properties, and rubrene having a high steric hindrance. The weight ratio of the molybdenum oxide and the rubrene is 0.245: 0.018. The first layer is formed to have a thickness of 130 nm. A second layer is formed by vapor deposition α-NPD over the first layer to have a thickness of 10 nm. A third layer is formed over the second layer by co-evaporation of Alq3 and coumarin-6 to have a thickness of 37.5 nm. The weight ratio of the Alq3 and the coumarin-6 is 1: 0.002. A fourth layer is formed by vapor deposition of Alq3 over the third layer to have a thickness of 37.5 nm. A fifth layer is formed by vapor deposition of calcium fluoride (CaF2) over the fourth layer to have a thickness of 1 nm. A second electrode is formed by vapor deposition of aluminum over the fifth layer to have a thickness of 200 nm. FIGS. 1 and 4 show device characteristics of thus manufactured light-emitting element. The measurement method or the like is the same as that described in Example 1. FIG. 4 shows that an onset voltage, which is a voltage for electroluminescence of 1 cd/m2 or more, is approximately 2.5 V. FIG. 1 shows that after 100 hours luminance becomes the value of 92, that is, the luminance is decreased by 8% compared to the initial luminance.
[Example 3] A method for manufacturing a light-emitting element according to the present invention and properties of the light-emitting element is explained. A first electrode is formed by depositing an indium tin oxide (ITO) over a glass substrate. The glass substrate deposited with the ITO is processed in vacuum at 150 °C for 30 minutes. A first layer is formed over the first electrode by co-evaporation of a molybdenum - oxide,
4,4-bis(N-(4-(N,N-di-m-trylamino)phenyl)-N-phenylamino)biphenyl (abbreviated
DNTPD) having high hole transportation properties, and rubrene having a high steric hindrance. The weight ratio of the molybdenum oxide, the DNTPD, and the rubrene is 0.5: 1: 0.05. The first layer is formed to have a thickness of 120 nm. A second layer is formed by vapor deposition of α-NPD over the first layer to have a thickness of 10 nm. A third layer is formed over the second layer by co-evaporation of Alq3 and coumarin-6 to have a thickness of 37.5 nm. The weight ratio of the Alq3 and the coumarin-6 is 1: 0.003. A fourth layer is formed by vapor deposition of Alq3 over the third layer to have a thickness of 37.5 nm. A fifth layer is formed by vapor deposition of calcium fluoride (CaF ) over the fourth layer to have a thickness of 1 nm. A second electrode is formed by vapor deposition of aluminum over the fifth layer to have a thickness of 200 nm. FIGS. 8 and 9 shows device characteristics of thus manufactured light-emitting element. The measurement method or the like is the same as that described in
Example 1. In FIG. 8, a horizontal axis shows an applied voltage (V), and a vertical axis shows luminance (cd/m2). In FIG 9, a horizontal axis shows hour, and a vertical axis shows luminance (relative value). FIG. 8 shows that an onset voltage, which is a voltage for electroluminescence of 1 cd/m or more, is approximately 2.4 V. FIG. 9 shows that after 100 hours luminance becomes the value of 93, that is, the luminance is decreased by 7% compared to the initial luminance.
[Comparative Example 1] As a comparative example, a method for manufacturing a light-emitting element in which a second layer is formed by only a molybdenum oxide, and device characteristics of the light-emitting element are explained. An indium tin oxide (ITO) is deposited over a glass substrate to form a first electrode. The glass substrate deposited with the ITO is processed in vacuum at 150 °C for 30 minutes. A first layer is formed by vapor deposition of a molybdenum oxide over the first electrode to have a thickness of 100 nm. A second layer is formed by vapor deposition of α-NPD over the first layer to have a thickness of 60 nm. A third layer is formed over the second layer by co-evaporation of Alq3 and coumarin to have a thickness of 37.5 nm. The weight ratio of the Alq3 and the coumarin is 1: 0.002. A fourth layer is formed by vapor deposition of Alq3 over the third layer to have a thickness of 37.5 nm. A fifth layer is formed by vapor deposition of calcium fluoride (CaF2) over the fourth layer to have a thickness of 1 nm. A second electrode is formed by vapor deposition of aluminum over the fifth layer to have a thickness of 200 nm. FIGS. 1 and 4 shows device characteristics of thus manufactured light-emitting element. The measurement method or the like is the same as that described in Example 1. FIG. 4 shows that an onset voltage, which is a voltage for electroluminescence of 1 cd/m2 or more, is approximately 2.5 V. FIG 1 shows that the luminance of a light-emitting element according to the comparative example after 100 hours is drastically decreased, and light emission cannot be generated. This is caused by the fact that a leak current is generated due to the crystallization of the second layer. Accordingly, the light-emitting element described in Example 1 or 2 emits light at the same driving voltage for the light-emitting element described in Comparative Example. As same as the light-emitting element having a layer formed by only a molybdenum oxide, a light-emitting element according to the invention is operated at a low voltage. The lifetime of the light-emitting element described in Example 1 or 2 can be extended. This arises from the fact that the crystallization of P-type compounds is suppressed by being mixed with a compound having high transportation properties such as α-NPD or a compound having a high steric hindrance such as rubrene.
[Example 4] An active matrix light-emitting device having a light-emitting element according to the present invention is explained in Example 4. As shown in FIG 5, a drive transistor 91 and a light-emitting element 92 according to the invention are provided over a substrate 90. The drive transistor 91 for driving a light-emitting element is electrically connected to the light-emitting element 92 according to the invention. As used herein, the term "light-emitting element" refers to a layer which includes a light-emitting layer between an electrode 93 and an electrode 94, and which includes partly a layer containing a molybdenum oxide, a substance with high transportation properties, a substance with a high steric hindrance. The light-emitting element 92 is divided by a bank layer 95. A light-emitting element according to the invention may have the structure in which an electrode serving as an anode is located at a lower side (the term "lower" refers to the region where a drive transistor is provided in response to the light-emitting element) and an electrode serving as a cathode is located at an upper side (the term "upper" refers to the region where a drive transistor is not provided in response to the light-emitting element). Alternatively, the light-emitting element may have the structure in which the electrode serving as a cathode is located at the lower side, and the electrode serving as anode is located at the upper side. In the case of the former, the drive transistor 91 is a p-channel type, and in the case of the latter, the drive transistor 91 is an n-channel type. The drive transistor 91 may be either a staggered type or an inversely staggered type. The semiconductor layer of the drive transistor 91 may be any one of a crystalline semiconductor layer, an amorphous semiconductor layer, or a semiamorphous semiconductor layer. The semiamorphous semiconductor has an intermediate structure between an amorphous structure and a crystalline structure (including single crystals and poly crystals). The semiamorphous semiconductor has a stable third state with respect to free energy, and a crystalline region having a short-range order and lattice distortion. At least a part of the semiconductor, crystal grains with grain diameters of from 0.5 to 20 nm. A raman spectrum is shifted to a lower wave number than 520 cm"1. By X-ray diffraction, diffraction peaks (111), (220) that may be derived from a Si crystalline lattice are observed. Hydrogen or halogen of 1 atomic% or more is contained the semiconductor as neutralizer for dangling bond. Such semiconductor is referred to as what is called micro crystal semiconductor. A suicide gas is formed by glow discharge decomposition (plasma CVD). As the suicide gas, Si H6, SiH2Cl2, SiHCl3, SiCl , SiF4, or the like in addition to Sith can be used. The suicide gas can be diluted by H , or the H and one or a plurality of rare gas elements selected from the group consisting of He, Ar, Kr, and Ne. The dilution rate is in the range of from 2 to 1000 times. An applied voltage is in the range of from 0.1 to 133 Pa. A power source frequency is in the range of from 1 to 120 MHz, preferably, 13 to 60 MHz. A heat temperature for a substrate is at most 300 °C, preferably, 100 to 250 °C. As impurity elements in the semiconductor film, atmospheric constituents such as oxygen, nitrogen, carbon, and the like have preferably concentrations of at most 1 x 10 /cm , especially, oxygen concentration is at most 5 x 1019/cm3, preferably, 1 x 101 /cm3. A TFT (thin film transistor) including semiamorphous semiconductor has mobility of approximately from 1 to 10 m2/Vsec. Either the electrode serving as an anode or the electrode serving as a cathode, or both of them are formed by a material having light-transmitting properties. In case that an electrode serving as an anode is located at the lower side, and only the electrode serving as an anode is formed by a substance having light-transmitting properties; light is emitted through the side provided with a drive transistor as shown in FIG. 5A. Further, in case that an electrode serving as a cathode is located at the lower side, and only the electrode serving as a cathode is formed by a material having light-transmitting properties, light is emitted through the side provided with a drive transistor as shown in FIG. 5A. In case that an electrode serving as an anode is located at the lower side, and only the electrode serving as a cathode is formed by a material having light-transmitting properties, light is emitted through the opposite side provided with a drive transistor as shown in FIG. 5B. In case that an electrode serving as a cathode is located at the lower side, and only the electrode serving as an anode is formed by a material having light-transmitting properties, light is emitted through the opposite side provided with a drive transistor as shown in FIG. 5B. In case that both of an electrode serving as an anode and an electrode serving as a cathode are formed by materials having light-transmitting properties, light is emitted from both sides as shown in FIG 5C irrespective of which electrode is provided to lower side or upper side. The light-emitting element may emit either monochromatic light or light in full color such as red (R), green (G), blue (B), and the like. Each light-emitting element is preferably divided by a bank layer. The bank layer may be formed by a material that contains either an inorganic substance or an organic substance, or both of the inorganic substance and organic substance. For example, a silicon oxide film may be used. A material having a skeleton structure formed by the bond of acrylic, polyimide, and (a substance in which a skeleton is formed by the bond of silicon (Si) and oxygen (O); and at least hydrogen is included as a substituent, or at least one element selected from the group consisting of fluoride, alkyl group, and aromatic hydrocarbon is included as the substituent), or the like may also be used. Further, the bank layer is preferably formed to have a curved edge portion whose radius of curvature is continuously varied. Since a light-emitting element according to the present invention has a long lifetime, a light-emitting device manufactured by practicing the present invention can display images and emit light in a long term.
[Example 5] A light-emitting device including a light-emitting element according to the present invention as shown in Example 4 is mounted on various electric appliances after attached with an external input terminal. Such electric appliances manufactured by practicing the present invention can display high quality images in a long term. This arises from the fact that a light-emitting element according to the invention has long lifetime. In Example 5, a light-emitting device including a light-emitting element and electric appliances mounted with the light-emitting element are explained with reference to FIGS. 6 and 7. FIG 6 is a top view of a light-emitting device including a light-emitting element according to the present invention. FIG. 7 is one embodiment of an electric appliance only, and the structure of a light-emitting device is not limited thereto. In FIG. 6, reference numeral 401 indicated by dotted line denotes a drive circuit portion (a source side drive circuit); 402, a pixel portion; and 403, a drive circuit portion (a gate side drive circuit). Reference numeral 404 denotes a sealing substrate, and 405 denotes a portion applied with sealing agent. Signals are inputted to the source side drive circuit 401 and the gate side drive circuit 403 when these circuits receive video signals, clock signals, start signals, reset signals, and the like via wirings provided to a device substrate 410 from an FPC (flexible print circuit) 409 serving as an external input terminal. Despite illustrated only the FPC in FIG. 6, the FPC may be provided with a printed wiring board (PWB). A light-emitting device according to Example 5 refers to not only a main body of a light-emitting device, but also a main body provided with an FPC or a PWB. FIG. 7 is one embodiment of an electric appliance installed with a light-emitting device as shown in FIG 6. FIG 7 shows a laptop computer manufactured by practicing the present invention composed of a main body 5501, a housing 5502, a display portion 5503, a keyboard 5504, and the like. A display device can be completed by incorporating a light-emitting device including a light-emitting element according to the invention into the laptop computer. Despite explained a laptop computer in Example 5, a cellular phone, a TV reception set, a car navigation, a lighting system, and the like may be installed with a light-emitting device including a light-emitting element according to the Invention.
[Example 6] A method for manufacturing a light-emitting element according to the present invention, and device characteristics of the light-emitting element are explained in Example 6. In Example 6, four light-emitting elements, that is, a light-emitting element (1), a light-emitting element (2), a light-emitting element (3), and a light-emitting element (4), all of which have first layers with different thicknesses, are manufactured. A first electrode is formed by an indium tin oxide (ITO) containing a silicon oxide over a glass substrate. Then, the glass substrate provided with the first electrode is treated in vacuum at 150 °C for 30 minutes. A first layer is formed by co-evaporation of a molybdenum oxide, rubrene, and DNTPD over the first electrode to have a weight ratio of 0.67: 1: 0.02, respectively. The first layer of a light-emitting element (1) is formed to have a thickness of 40 nm. The first layer of a light-emitting element (2) is formed to have a thickness of 80 nm. The first layer of a light-emitting element (3) is formed to have a thickness of 120 nm. The first layer of a light-emitting element (4) is formed to have a thickness of 160 nm. A second layer is formed by vapor deposition of α-NPD over the first layer to have a thickness of 10 nm. A third layer is formed by co-evaporation of Alq3 and coumarin 6 over the second layer to have a weight ratio of 1: 0.005. The third layer is formed to have a thickness of 37.5 nm. A fourth layer is formed by vapor deposition of Alq3 over the third layer to have a thickness of 37.5 nm. A fifth layer is formed by vapor deposition of lithium fluoride (LiF) over the fourth layer to have a thickness of 1 nm. A second electrode is formed by vapor deposition of aluminum over the fifth layer to have a thickness of 200 nm. FIGS. 10 and 11 show the device characteristics of thus manufactured light-emitting elements. FIG. 10 shows luminance- voltage characteristics of the light-emitting elements manufactured according to Example 6. In FIG. 10, a horizontal axis shows voltage (V), and a vertical axis shows luminance (cg m2). In addition, closed circles indicate characteristics of the light-emitting element (1); open circles indicate characteristics of the light-emitting element (2); closed squares indicate characteristics of the light-emitting element (3); and open squares indicate characteristics of the light-emitting element (4). FIG. 10 shows that an onset voltage, which is a voltage for electroluminescence of 1 cd/m2 or more, is approximately 2.5 V in each light-emitting element. The onset voltages are approximately the same with each other despite the thickness of the first layer of each the light-emitting element. That is, the onset voltage for a light-emitting element practiced by the present invention is insensitive to the thickness of the first layer. Therefore, external coupling efficiency of light emission from a light-emitting element in which an electrode is used to reflect light emission becomes easily improved by controlling an optical path length by variations of the thickness of a first layer according to the present invention. FIG. 11 shows a measurement result of the variation of luminance per hour of a light-emitting element manufactured according to Example 6. In FIG. 11, a horizontal axis shows hour, and a vertical axis shows luminance. The luminance is represented its relative value to initial luminance based on the initial value of 100. The variation of luminance is measured by applying continuously a constant amount of current to a light-emitting element, that is, applying a stress to a light-emitting element; and the luminance of the light-emitting element is measured at given time intervals. A current that has a current density required to obtain electroluminescence with a luminance of 3000 cs/m2 at an initial state is applied, and the luminance obtained at the applied current is measured. FIG. 11 shows that after 100 hours the luminance is decreased by 14% or less to the initial luminance in each the light-emitting element (1), (2), (3), and (4). Hence, the luminance of a light-emitting element practiced by the present invention is hardly deteriorated.
[Example 7] A method for manufacturing a light-emitting element according to the present invention and device characteristics of the light-emitting element are explained in Example 7. In Example 7, nine light-emitting elements, that is, a light-emitting element (11), a light-emitting element (12), a light-emitting element (13), a light-emitting element (14), a light-emitting element (15), a light-emitting element (16), a light-emitting element (17), a light-emitting element (18), and a light-emitting element (19), all of which have first electrodes formed by different materials, are manufactured. A first electrode for the light-emitting element (11) is formed by aluminum containing several % silicon over a glass substrate. A first electrode for the light-emitting element (12) is formed by aluminum containing several % titanium over a glass substrate. A first electrode of the light-emitting element (13) is formed by titanium over a glass substrate. A first electrode of the light-emitting element (14) is formed by titanium nitride over a glass substrate. A first electrode of the light-emitting element (15) is formed by tantalum over a glass substrate. A first electrode of the light-emitting element (16) is formed by tantalum nitride over a glass substrate. A first electrode of the light-emitting element (17) is formed by tungsten over a glass substrate. A first electrode of the light-emitting element (18) is formed by chromium over a glass substrate. A first electrode of the light-emitting element (19) is formed by molybdenum over a glass substrate. Then, the glass substrate provided with the first electrode is treated in vacuum at 150 °C for 30 minutes. A first layer is formed by co-evaporation of a molybdenum oxide, rubrene, and α-NPD over the first electrode to have a weight ratio of 0.1: 1: 0.02, respectively. The first layer is formed to have thickness of 60 nm. A second layer is formed by vapor deposition of α-NPD over the first layer to have a thickness of 10 nm. A third layer is formed by co-evaporation of Alq3 and coumarin 6 over the second layer to have a weight ratio of 1: 0.005. The third layer is formed to have a thickness of 40 nm. A fourth layer is formed by vapor deposition of Alq over third layer to have a thickness of 20 nm. A fifth layer is formed by co-evaporation of lithium (Li) and 4,4'-bis(5-methylbenzoxazole-2-yl)stilbene (abbreviated BzOs) over the fourth layer to have a weight ratio of 0.02: 1, respectively. The fifth layer is formed to have a thickness of 20 nm. A second electrode is formed by an indium tin oxide (ITO) over the fifth layer to have a thickness of 110 nm. To measure an onset voltage for electroluminescence of 1 cd/m or more, voltage is applied to each of thus manufactured light-emitting element so that an electric potential of the first electrode is higher than that of the second electrode. FIG. 12 shows the measurement results indicated by closed squares. In FIG 12, a horizontal axis shows the manufactured light-emitting elements, and a vertical axis shows voltage (V). [Comparative Example 2] As a comparative example for the light-emitting elements described in
Example 7, a light-emitting element (21), a light-emitting element (22), a light-emitting element (23), a light-emitting element (24), a light-emitting element (25), a light-emitting element (26), a light-emitting element (27), a light-emitting element (28), and a light-emitting element (29) are explained hereinafter. Each layer composing the light-emitting elements (21) to (29) is manufactured by the same material to have the same thickness as those of the light-emitting elements (11) to (19) except that the first layer of each the light-emitting elements (21) to (29) is formed by copper phthalocyanine. A first electrode of the light-emitting element (21) is formed by aluminum containing several % silicon. A first electrode of the light-emitting element (22) is formed by aluminum containing several % titanium. A first electrode of the light-emitting element (23) is formed by titanium. A first electrode of the light-emitting element (24) is formed by titanium nitride. A first electrode of the light-emitting element (25) is formed by tantalum. A first electrode of the light-emitting element (26) is formed by tantalum nitride. A first electrode of the light-emitting element (27) is formed by tungsten. A first electrode of the light-emitting element (28) is formed by chromium. A first electrode of the light-emitting element (29) is formed by molybdenum. To measure an onset voltage for electroluminescence of 1 cd/m2 or more, voltage is applied to each of thus manufactured light-emitting element so that an electric potential of the first electrode is higher than that of the second electrode. FIG. 12 shows the measurement results indicated by closed triangles. FIG. 12 shows that the onset voltages of the light-emitting elements (21) to (29) having first layers formed by copper phthalocyanine are different from each other, that is, the onset voltages depend on the material for forming the first electrode. On the other hand, the onset voltages of the light-emitting elements (11) to (21) practiced by the present invention are almost the same with each other despite a material for forming the first electrode. The light-emitting element according to the present invention is less subject to kinds of materials for forming an electrode or the like. Therefore, it becomes easy to select an electrode formed by a material having better reflectivity in the case that a light-emitting element in which an electrode is used to reflect light emission is manufactured according to the present invention.
[Example 8] A method for manufacturing a light-emitting element according to the present invention and characteristics of the light-emitting element are explained hereinafter. In
Example 8, light-emitting elements, all of which have first layers with different thicknesses, are manufactured. The film thickness dependence of a driving voltage of the light-emitting elements will be revealed. The light-emitting elements (1) to (4) manufactured in Example 6 are used as samples. The first layer in the light-emitting element (1) is formed to have a thickness of 40 nm. The first layer in the light-emitting element (2) is formed to have a thickness of 80 nm. The first layer in the light-emitting element (3) is formed to have a thickness of 120 nm. The first layer in the light-emitting element (4) is formed to have a thickness of 160 nm. Voltage is applied to each of the light-emitting elements so that an electric potential of a first electrode is higher than that of a second electrode. FIG. 13 shows current density-voltage characteristics of the light-emitting elements (1) to (4). The current density-voltage characteristics of the light-emitting elements (1) to (4) are hardly different from each other despite the difference in the thicknesses of the first layers. Therefore, the increase of a thickness of the first layer that is formed by a molybdenum oxide, rubrene, and DNTPD does not result in the increase of a driving voltage.
[Comparative Example 3] As a comparative example for the light-emitting elements described in Example 8, a light-emitting element (30), a light-emitting element (31), a light-emitting element (32), a light-emitting element (33), a light-emitting element (34), and a light-emitting element (35) are explained hereinafter. The light-emitting elements (30) to (35), all of which have second layers with different thicknesses, are manufactured. A first layer is formed by copper phthalocyanine to have a thickness of 20 nm. The second layer is formed by α-NPD by vapor deposition. The second layer of the light-emitting element (30) is formed to have a thickness of 60 nm. The second layer of the light-emitting element (31) is formed to have a thickness of 80 nm. The second layer of the light-emitting element (32) is formed to have a thickness of 100 nm. The second layer of the light-emitting element (33) is formed to have a thickness of 120 nm. The second layer of the light-emitting element (34) is formed to have a thickness of 140 nm. The second layer of the light-emitting element (35) is formed to have a thickness of 160 nm. Then, a third layer is formed by co-evaporation of Alq3 and coumarin-6 over a second layer to have a weight ratio of 1: 0.005. The third layer is formed to have a thickness of 37.5 nm. A fourth layer is formed by vapor deposition of Alq3 to have a thickness of 37.5 nm over the third layer. A fifth layer is formed by vapor deposition of calcium fluoride (CaF2) to have a thickness of 1 nm over the fourth layer. A second electrode is formed by vapor deposition of aluminum to have a thickness of 200 nm over the fifth layer. To operate each of the light-emitting elements, voltage is applied thereto so that an electric potential of the first electrode is higher than that of the second electrode. FIG. 14 shows current density-voltage characteristics of the light-emitting elements (30) to (35). The driving voltages of the light-emitting elements are increased with increasing the thicknesses of the second layers. Therefore, the increase of a thickness of the second layer formed by α-NPD results in the increase of the driving voltage.
[Comparative Example 4] As a comparative example for the light-emitting elements described in Example 8, a light-emitting element (36), a light-emitting element (37), and a light-emitting element (38) are explained hereinafter. Each of first layers is formed by a molybdenum oxide to have a different thickness form each other. A second layer is formed by copper phthalocyanine to have a thickness of 20 nm. A third layer is formed by vapor deposition of α-NPD to have a thickness of 40 nm. Then, a fourth layer is formed by co-evaporation of Alq3 and coumarin-6 to have a thickness of 37.5 nm over the third layer. A fifth layer is formed by vapor deposition of Alq3 to have a thickness of 37.5 nm over the fourth layer. A sixth layer is formed by vapor deposition of CaF2 to have a thickness of 1 nm over the fifth layer. A second electrode is formed by vapor deposition of aluminum to have a thickness of 200 nm over the sixth layer. To operate each of the light-emitting elements, voltage is applied thereto so that an electric potential of the first electrode is higher than that of the second electrode. FIG. 15 shows current density-voltage characteristics of the light-emitting elements (36) to (38). The driving voltages of the light-emitting elements are increased with increasing the thicknesses of the first layers formed by molybdenum oxides. Table 1 shows the results of film thickness dependence of driving voltage provided by Example 8, Comparative Example 3, and Comparative Example 4. Table 1 shows the data of a driving voltage required to apply a current of 100 mA/cm to a light-emitting element. [Table 1]
Figure imgf000033_0001
In Example 8, a driving voltage of 6.1 to 6.3 V is required to apply a current of
100 mA/cm2 to the light-emitting elements (1) to (4). On the other hand, in Comparative Example 3, a driving voltage of 12.5 to 19.9 V is required to apply a current of 100 mA/cm to the light-emitting elements (30) to (35). In Comparative Example 4, a driving voltage of 11.7 to 12.7 V is required to apply a current of 100 mA/cm2 to the light-emitting elements (36) to (38). The results illustrated in Table 1 shows that a driving voltage of a light-emitting element provided with a layer formed by a mixture of an organic compound and an inorganic can be lower than that of a light-emitting element provided with a layer formed by α-NPD or a molybdenum oxide that is an inorganic compound. Moreover, it also shows that the increase of the driving voltage can be prevented even if the thickness of the layer is increased. Therefore, a driving voltage can be reduced by using the light-emitting element according to the present invention, accordingly, the power consumption of the light-emitting element can be reduced. Further, a thickness of a light-emitting element can be increased, and so it becomes possible to reduce short-circuit deterioration between a pair of electrodes.
[Example 9] Characteristics of a QVGA active matrix light-emitting device having a screen size of 2.4 inches are explained in Example 9. The active matrix light-emitting device drives a light-emitting element by a transistor as in the case with Example 4. The light-emitting device has the configuration explained in the following. A first electrode is formed by an indium tin oxide containing a silicon oxide.
A first layer is formed by co-evaporation of a molybdenum oxide and α-NPD having high hole transportation properties over the first electrode. A light-emitting device in which the first layer is formed by a mixture of a molybdenum oxide and α-NPD to have a thickness of 120 nm is referred to as a light-emitting device 1. Similarly, a light-emitting device in which the first layer is formed to have a thickness of 240 nm is referred to as a light-emitting device 2. A second layer is formed by vapor deposition of α-NPD to have a thickness of 10 nm over the first layer. A third layer is formed by co-evaporation of Alq3 and coumarin-6 to have a thickness of 40 nm over the second layer. A fourth layer is formed by vapor deposition of Alq3 to have a thickness of 30 nm over the third layer. A fifth layer is formed by vapor deposition of calcium fluoride (CaF2) to have a thickness of 1 nm over the fourth layer. A second electrode is formed by vapor deposition of aluminum to have a thickness of 200 nm over the fifth layer. The number of dark spots (pixels that do not emit light) in the light-emitting devices 1 and 2 is checked at the beginning of electrical conduction and after a temperature cycle test (+85 °C (four hours) to -40 °C (four hours)) for 60 hours. The light-emitting device 1 has the average of the number of dark spots of 0.7 at the beginning of electrical conduction, and 2.3 after the temperature cycle test. The light-emitting device 2 has the average of the number of dark spots of 0.5 at the beginning of electrical conduction, and 0.5 after the temperature cycle test. As used herein, the term "average of the number of dark spots" refers to an average value in examined closed triangle numbers of light-emitting device.
[Comparative Example 5] As a comparative example for Example 9, an active matrix light-emitting device 3 in which a light-emitting element has a different configuration is manufactured. The light-emitting element is formed in the following manner. A first layer is formed by copper phthalocyanine to have a thickness of 20 nm. A second layer is formed by α-NPD to have a thickness of 40 nm. A third layer is formed by co-evaporation of Alq3 and coumarin 6 to have a thickness of 40 nm over the second layer. A fourth layer is formed by vapor deposition of Alq3 to have a thickness of 40 nm over the third layer. A fifth layer is formed by vapor deposition of calcium fluoride (CaF ) to have a thickness of 1 nm over the fourth layer. A second electrode is formed by vapor deposition of aluminum to have a thickness of 200 nm over the fifth layer. The number of dark spots in the light-emitting device 3 is checked at the beginning of electrical conduction and after a temperature cycle test (+85 °C (four hours) to -40 °C (four hours)) for 60 hours. The light-emitting device 3 has the average of the number of dark spots of 18 at the beginning of electrical conduction, and 444 after the temperature cycle test. The average of the number of dark spots after the temperature cycle test is increased by 25 times as many as that at the beginning of electrical conduction. Table 2 illustrates the results of the number of dark spots after the temperature cycle test (+85 °C (four hours) to -40 °C (four hours)) for 60 hours in Example 9 and Comparative Example 5. [Table 2]
Figure imgf000036_0001
Dark spots are hardly observed in the light-emitting devices 1 and 2 according to Example 9 at the beginning of electrical conduction, and are not increased after a temperature cycle test. On the other hand, a great number of dark spots are observed in the light-emitting device 3 according to Comparative Example 5 at the beginning of electrical conduction, and increased by 25 times after the temperature cycle test as many as those at the beginning of electrical conduction. The difference in the results may be resulted from the fact that the thickness of the first layer formed by a mixture of a molybdenum oxide and α-NPD is increased. The result from Example 9 shows that the number of dark pixel defects can be drastically reduced by increasing the thickness of a light-emitting element. According to the result from Example 8, it is clear that a driving voltage is not increased with increasing the thickness of a light-emitting element. Therefore, a light-emitting device with a low driving voltage and with drastically inhibited dark pixel defects can be provided according to the present invention.
[Example 10] Characteristics of a film formed by a molybdenum oxide that is a metal oxide, a film formed by α-NPD that is an organic compound with high hole transporting properties, and a film formed by a mixture of a molybdenum oxide and α-NPD are examined. These films are formed by vapor deposition. As illustrated in Table 3, the ionization potential of the film formed by a mixture of a molybdenum oxide and α-NPD is approximately 0.1 to 0.2 eV less than that of the film formed by a molybdenum oxide and the film formed by α-NPD.
Consequently, hole injection properties of the film formed by a mixture of a molybdenum oxide and α-NPD are improved. [Table 3]
Figure imgf000038_0001
a: mol/mol. b: Ionization Potential (Surveyed Value by AC-2)
FIG. 16 shows absorption spectra of these films. In the absorption spectra, the spectra of the film of a molybdenum oxide and the film of α-NPD have no characteristic peak in a visible light region. On the other hand, the absorption of the film formed by a mixture of a molybdenum oxide and α-NPD (OMOx) is less than that of the film formed by a molybdenum oxide. Hence, absorption loss of light can be reduced by using a layer formed by a mixture of a molybdenum oxide and α-NPD rather than using a layer formed by a molybdenum oxide. In FIG. 16, the spectrum of the film formed by a mixture of a molybdenum oxide and α-NPD has newly an absorption peak at around 500 nm. The absorption peak may be resulted from the formation of a charge-transfer complex between the molybdenum oxide and the α-NPD in the film. The molybdenum oxide is an accepter, while the α-NPD is a donor. Further, it has been confirmed that not only α-NPD but also an amine-based compound such as DNTPD serves as a donor. As described in Example 1 or 2, the lifetime can be extended of a light-emitting element that includes a layer containing a compound selected from the group of metal oxides and a compound having high hole transporting properties since the crystallization of the layer can be suppressed. As mentioned above, the mixing of an inorganic material and an organic material can generate a synergistic effect that cannot be obtained by using these materials separately.
Although the present invention has been fully described by way of examples with reference to the accompanying drawings, it is to be understood that various changes and modifications will be apparent to those skilled in the art. Therefore, unless otherwise such changes and modifications depart from the scope of the present invention hereinafter described, they should be construed as being included therein.

Claims

1. Alight-emitting element comprising: a layer formed between a pair of electrodes, wherein the layer comprises a compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having hole mobility of 10"6 cm2/Vs or more.
2. A light-emitting element comprising: a layer formed between a pair of electrodes, wherein the layer comprises a compound selected from the group consisting of oxide semiconductor and a metal oxide, and an aromatic amine compound.
3. A light-emitting element comprising: a layer formed between a pair of electrodes, wherein the layer comprises a molybdenum oxide and 4,4'-bis[N-(l-naphtyl)-N-phenyl-amino]-biphenyl.
4. Alight-emitting element comprising: a layer formed between a pair of electrodes, wherein the layer comprises a compound selected from the group consisting of oxide semiconductor and a metal oxide, a compound having a compound having hole mobility of 10"6 cm2/Vs or more, and a compound selected from the group consisting of 5,6,11,12-tetraphenyltetracene, hexabenilbenzene, diphenylanthracene, t-butylperylene, 9,10-di(ρhenyl)anthracene and coumarin 545T.
5. Alight-emitting element comprising: a layer formed between a pair of electrodes, wherein the layer comprises a compound selected from the group consisting of oxide semiconductor and a metal oxide, a compound having hole mobility of 10"6 cm2/Vs or more, and a compound comprising dendrimer.
6. A light-emitting element comprising: a layer formed between a pair of electrodes, wherein the layer comprises a compound selected from the group consisting of oxide semiconductor and a metal oxide, an aromatic amine compound, and a compound selected from the group consisting of 5,6,11,12-tetraphenyltetracene, hexabenilbenzene, diphenylanthracene, t-butylperylene, 9,10-di(phenyl)anthracene and coumarin 545T.
7. A light-emitting element comprising: a layer formed between a pair of electrodes, wherein the layer comprises a molybdenum oxide, 4,4'-bis[N-(l-naphtyl)-N-phenyl-amino]-biphenyl, and 5,6,11,12-tetraphenyltetracene.
8. A method for manufacturing a light-emitting element comprising the step of: depositing a compound selected from the group consisting of oxide semiconductor and a metal oxide, and a compound having hole mobility of 10" cm /Vs or more by co-evaporation.
9. A method for manufacturing a light-emitting element comprising the step of: depositing a compound selected from the group consisting of oxide semiconductor and a metal oxide, and an aromatic amine compound by co-evaporation.
10. A method for manufacturing a light-emitting element comprising the step of: depositing a molybdenum oxide and
4,4 ' -bis[N-(l -naphtyl)-N-phenyl-amino] -biphenyl by co-evaporation.
11. A method for manufacturing a light-emitting element according to claim 10, wherein the molybdenum oxide and the
4,4'-bis[N-(l-naphtyl)-N-phenyl-amino]-biphenyl are deposited by co-evaporation to have a weight ratio of 0.245: 1, respectively.
12. A method for manufacturing a light-emitting element comprising the step of: depositing a compound selected from the group consisting of oxide semiconductor and a metal oxide; a compound having hole mobility of 10"6 cm2/Vs or more; and a compound selected from the group consisting of
5,6,11,12-tetraphenyltetracene, hexabenilbenzene, diphenylanthracene, t-butylperylene, 9,10-di(phenyl)anthracene and coumarin 545T by co-evaporation.
13. A method for manufacturing a light-emitting element comprising the step of: depositing a compound selected from the group consisting of oxide semiconductor and a metal oxide, an aromatic amine compound and a compound selected from the group consisting of 5,6,11,12-tetraphenyltetracene, hexabenilbenzene, diphenylanthracene, t-butylperylene, 9,10-di(phenyl)anthracene and coumarin 545T by co-evaporation.
14. A method for manufacturing a light-emitting element comprising the step of: depositing a molybdenum oxide,
4,4'-bis[N-(l-naphtyl)-N-phenyl-amino]-biphenyl, and 5,6,11,12-tetraphenyltetracene by co-evaporation.
15. A method for manufacturing a light-emitting element according to claim 14, wherein the molybdenum oxide, the 4,4'-bis[N-(l-naphtyl)-N-phenyl-amino]-biphenyl, and the 5,6,11,12-tetraphenyltetracene are deposited by co-evaporation to have a weight ratio of 0.245: 1: 0.018, respectively.
16. A light-emitting device including a pixel portion having the light-emitting element according to claim 1.
17. A light-emitting device including a pixel portion having the light-emitting element according to claim 2.
18. A light-emitting device including a pixel portion having the light-emitting element according to claim 3.
19. A light-emitting device including a pixel portion having the light-emitting element according to claim 4.
20. A light-emitting device including a pixel portion having the light-emitting element according to claim 5.
21. A light-emitting device including a pixel portion having the light-emitting element according to claim 6.
22. A light-emitting device including a pixel portion having the light-emitting element according to claim 7.
23. An electric appliance including a display portion having the light-emitting device according to claim 16, wherein the electric appliance is selected from the group consisting of a personal computer, a portable phone, a television, a navigation system and a lighting system.
24. An electric appliance including a display portion having the light-emitting device according to claim 17, wherein the electric appliance is selected from the group consisting of a personal computer, a portable phone, a television, a navigation system and a lighting system.
25. An electric appliance including a display portion having the light-emitting device according to claim 18, wherein the electric appliance is selected from the group consisting of a personal computer, a portable phone, a television, a navigation system and a lighting system.
26. An electric appliance including a display portion having the light-emitting device according to claim 19, wherein the electric appliance is selected from the group consisting of a personal computer, a portable phone, a television, a navigation system and a lighting system.
27. An electric appliance including a display portion having the light-emitting device according to claim 20, wherein the electric appliance is selected from the group consisting of a personal computer, a portable phone, a television, a navigation system and a lighting system.
28. An electric appliance including a display portion having the light-emitting device according to claim 21, wherein the electric appliance is selected from the group consisting of a personal computer, a portable phone, a television, a navigation system and a lighting system.
29. An electric appliance including a display portion having the light-emitting device according to claim 22, wherein the electric appliance is selected from the group consisting of a personal computer, a portable phone, a television, a navigation system and a lighting system.
PCT/JP2004/014412 2003-09-26 2004-09-24 Light-emitting device and method for manufacturing the same WO2005031798A2 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
KR1020147023148A KR20140107696A (en) 2003-09-26 2004-09-24 Light emitting device
EP04773500.6A EP1776846B1 (en) 2003-09-26 2004-09-24 Light-emitting device and method for manufacturing the same
CN200480027991A CN100596251C (en) 2003-09-26 2004-09-24 Light emitting component and method for manufacturing same
US10/571,891 US7732808B2 (en) 2003-09-26 2004-09-24 Light-emitting device and method for manufacturing the same
KR1020117030615A KR101590148B1 (en) 2003-09-26 2004-09-24 Light emitting device and method for manufacturing light emitting element
KR1020067005626A KR101286221B1 (en) 2003-09-26 2004-09-24 Light-emitting device
KR1020137011242A KR20130062367A (en) 2003-09-26 2004-09-24 Light emitting device
KR1020097018993A KR101286219B1 (en) 2003-09-26 2004-09-24 A method for manufacturing a light-emitting element
KR1020097018994A KR20090111869A (en) 2003-09-26 2004-09-24 A lighting system
US12/647,743 US8178869B2 (en) 2003-09-26 2009-12-28 Light-emitting device and method for manufacturing the same
US12/767,902 US8216875B2 (en) 2003-09-26 2010-04-27 Light-emitting device and method for manufacturing the same
US13/478,547 US8507903B2 (en) 2003-09-26 2012-05-23 Light-emitting device and method for manufacturing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003-336295 2003-09-26
JP2003336295 2003-09-26

Related Child Applications (3)

Application Number Title Priority Date Filing Date
US10/571,891 A-371-Of-International US7732808B2 (en) 2003-09-26 2004-09-24 Light-emitting device and method for manufacturing the same
US12/647,743 Continuation US8178869B2 (en) 2003-09-26 2009-12-28 Light-emitting device and method for manufacturing the same
US12/767,902 Continuation US8216875B2 (en) 2003-09-26 2010-04-27 Light-emitting device and method for manufacturing the same

Publications (2)

Publication Number Publication Date
WO2005031798A2 true WO2005031798A2 (en) 2005-04-07
WO2005031798A3 WO2005031798A3 (en) 2005-05-26

Family

ID=34386090

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/014412 WO2005031798A2 (en) 2003-09-26 2004-09-24 Light-emitting device and method for manufacturing the same

Country Status (6)

Country Link
US (4) US7732808B2 (en)
EP (1) EP1776846B1 (en)
KR (7) KR20130062367A (en)
CN (4) CN101789497B (en)
TW (6) TWI407830B (en)
WO (1) WO2005031798A2 (en)

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1524706A2 (en) * 2003-10-17 2005-04-20 Junji Kido Organic electroluminescent device
US20060263637A1 (en) * 2005-05-20 2006-11-23 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element and light-emitting device
WO2007013478A1 (en) 2005-07-25 2007-02-01 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic appliance
JP2007073932A (en) * 2005-07-25 2007-03-22 Semiconductor Energy Lab Co Ltd Light emitting element, light emitting device, and electronic apparatus
EP1777758A1 (en) * 2005-10-18 2007-04-25 Semiconductor Energy Laboratory Co., Ltd. Organic light emitting device
JP2007142378A (en) * 2005-10-18 2007-06-07 Semiconductor Energy Lab Co Ltd Light emitting element, light emitting device and electronic apparatus
WO2007064009A1 (en) * 2005-11-30 2007-06-07 Semiconductor Energy Laboratory Co., Ltd. Light emitting element, light emitting device and electronic device
JP2007180526A (en) * 2005-11-30 2007-07-12 Semiconductor Energy Lab Co Ltd Light emitting element, light emitting device and electronic equipment
JP2008021665A (en) * 2005-06-22 2008-01-31 Semiconductor Energy Lab Co Ltd Light-emitting device, and electronic equipment using the same
US7462883B2 (en) 2004-08-04 2008-12-09 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element having hole generating layer
US7521855B2 (en) 2004-12-06 2009-04-21 Semiconductor Energy Laboratory Co., Ltd. Electronic appliance and light-emitting device
US7626198B2 (en) 2005-03-22 2009-12-01 Semiconductor Energy Laboratory Co., Ltd. Nonlinear element, element substrate including the nonlinear element, and display device
US7646010B2 (en) 2004-11-26 2010-01-12 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic device
US7649197B2 (en) 2005-03-23 2010-01-19 Semiconductor Energy Laboratory Co., Ltd. Composite material, and light emitting element and light emitting device using the composite material
US7667389B2 (en) 2004-12-06 2010-02-23 Semiconductor Energy Laboratory Co., Ltd. Light emitting element, light emitting device, and electronic device
US7777232B2 (en) 2005-04-11 2010-08-17 Semiconductor Energy Laboratory Co., Ltd. Display device and electronic device using the same
EP2276088A3 (en) * 2003-10-03 2011-03-09 Semiconductor Energy Laboratory Co, Ltd. Light emitting element and manufacturing method thereof, and light emitting device using the light emitting element
US7951470B2 (en) 2004-08-23 2011-05-31 Semiconductor Energy Laboratory Co., Ltd. Light emitting element, light emitting device, and lighting system
US20110127510A1 (en) * 2009-12-01 2011-06-02 Semiconductor Energy Laboratory Co., Ltd. Light-Emitting Element, Light-Emitting Device, Electronic Device, and Lighting Device
US7989694B2 (en) 2004-12-06 2011-08-02 Semiconductor Energy Laboratory Co., Ltd. Photoelectric conversion element, solar battery, and photo sensor
US7994711B2 (en) 2005-08-08 2011-08-09 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and manufacturing method thereof
US8017252B2 (en) 2005-06-22 2011-09-13 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and electronic appliance using the same
US8018152B2 (en) * 2004-05-20 2011-09-13 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element including intermediate conductive layer having a hole-injection layer with an island-like structure
US8049208B2 (en) 2005-04-22 2011-11-01 Semiconductor Energy Laboratory Co., Ltd. Organic semiconductor device having composite electrode
US8093806B2 (en) 2007-06-20 2012-01-10 Semiconductor Energy Laboratory Co., Ltd. Light-emitting device, method for manufacturing the same, and electronic apparatus
US8158969B2 (en) * 2005-05-20 2012-04-17 Hitachi Displays, Ltd. Organic light emitting display device
US8269227B2 (en) 2005-06-09 2012-09-18 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and electronic device
US8288180B2 (en) 2005-07-04 2012-10-16 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing light emitting device
US8415878B2 (en) 2005-07-06 2013-04-09 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic device
US8420227B2 (en) * 2005-03-23 2013-04-16 Semiconductor Energy Laboratory Co., Ltd. Composite material, light emitting element and light emitting device
US8426034B2 (en) * 2005-02-08 2013-04-23 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic appliance
US8569742B2 (en) 2004-12-06 2013-10-29 Semiconductor Energy Laboratory Co., Ltd. Organic field-effect transistor and semiconductor device including the same
KR101338098B1 (en) 2006-06-30 2013-12-06 엘지디스플레이 주식회사 Organic electro luminescence display device and fabrication method thereof
US8633473B2 (en) 2004-12-28 2014-01-21 Semiconductor Energy Laboratory Co., Ltd. High contrast light emitting device and method for manufacturing the same
US8659008B2 (en) 2005-07-08 2014-02-25 Semiconductor Energy Laboratory Co., Ltd. Composite material and light emitting element, light emitting device, and electronic device using the composite material
US8729795B2 (en) 2005-06-30 2014-05-20 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and electronic device
US8927114B2 (en) 2004-11-30 2015-01-06 Semiconductor Energy Laboratory Co., Ltd. Light emitting element and electronic device using the same
JP2015092578A (en) * 2005-02-28 2015-05-14 株式会社半導体エネルギー研究所 Composite material
JP2015181189A (en) * 2005-04-21 2015-10-15 株式会社半導体エネルギー研究所 light-emitting element
US9530968B2 (en) 2005-02-15 2016-12-27 Semiconductor Energy Laboratory Co., Ltd. Light emitting element and light emitting device
US9595678B2 (en) 2010-07-23 2017-03-14 Basf Se Dye solar cell with improved stability
US10134996B2 (en) 2004-10-29 2018-11-20 Semicondcutor Energy Laboratory Co., Ltd. Composite material, light-emitting element, light-emitting device, and manufacturing method thereof

Families Citing this family (71)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101789497B (en) * 2003-09-26 2013-03-13 株式会社半导体能源研究所 Light-emitting device and method for manufacturing the same
US7605534B2 (en) * 2003-12-02 2009-10-20 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element having metal oxide and light-emitting device using the same
CN101673808B (en) * 2003-12-26 2012-05-23 株式会社半导体能源研究所 Light-emitting element
CN101640254B (en) 2004-05-21 2016-01-20 株式会社半导体能源研究所 Light-emitting component and luminaire
JP2006295104A (en) * 2004-07-23 2006-10-26 Semiconductor Energy Lab Co Ltd Light emitting element and light emitting device using the same
EP1803172B1 (en) 2004-09-24 2017-10-25 Semiconductor Energy Laboratory Co., Ltd. Light emitting device
CN101656302B (en) * 2004-09-30 2012-01-18 株式会社半导体能源研究所 Light emitting device and display using the same
WO2006035958A1 (en) * 2004-09-30 2006-04-06 Semiconductor Energy Laboratory Co., Ltd. Light emitting element
US7683532B2 (en) 2004-11-02 2010-03-23 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device and light emitting device
US20060091397A1 (en) * 2004-11-04 2006-05-04 Kengo Akimoto Display device and method for manufacturing the same
US7714501B2 (en) * 2004-12-01 2010-05-11 Semiconductor Energy Laboratory Co., Ltd. Light emitting element, light emitting device and electronic equipment
US8217569B2 (en) 2004-12-28 2012-07-10 Semiconductor Energy Laboratory Co., Ltd. Low drive voltage light emitting element
EP1844504A4 (en) * 2005-01-31 2010-08-04 Semiconductor Energy Lab Hole-injecting material, material for light-emitting element, light-emitting element, organic compound, monomer, and monomer mixture
EP2528127B1 (en) * 2005-03-23 2017-04-19 Semiconductor Energy Laboratory Co., Ltd. Light-emitting device and electronic device
US7851989B2 (en) 2005-03-25 2010-12-14 Semiconductor Energy Laboratory Co., Ltd. Light emitting device
US7926726B2 (en) * 2005-03-28 2011-04-19 Semiconductor Energy Laboratory Co., Ltd. Survey method and survey system
US8030643B2 (en) 2005-03-28 2011-10-04 Semiconductor Energy Laboratory Co., Ltd. Memory device and manufacturing method the same
WO2006109878A1 (en) 2005-04-11 2006-10-19 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and vapor deposition apparatus
US20060270066A1 (en) 2005-04-25 2006-11-30 Semiconductor Energy Laboratory Co., Ltd. Organic transistor, manufacturing method of semiconductor device and organic transistor
US20060244373A1 (en) * 2005-04-28 2006-11-02 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and method for manufacturing thereof
US7745019B2 (en) * 2005-04-28 2010-06-29 Semiconductor Energy Laboratory Co., Ltd. Light emitting element and light emitting device and method of manufacturing light emitting element
US8334057B2 (en) * 2005-06-08 2012-12-18 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic device
US7745989B2 (en) * 2005-06-30 2010-06-29 Semiconductor Energy Laboratory Co., Ltd Light emitting element, light emitting device, and electronic apparatus
KR20140028143A (en) * 2005-09-12 2014-03-07 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Quinoxaline derivative, and light emitting element, light emitting device, and electronic appliance using the same
TWI475737B (en) 2006-03-08 2015-03-01 Semiconductor Energy Lab Light emitting element, light emitting device, and electronic device
US9112170B2 (en) * 2006-03-21 2015-08-18 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic device
US7875881B2 (en) * 2007-04-03 2011-01-25 Semiconductor Energy Laboratory Co., Ltd. Memory device and semiconductor device
WO2008146470A1 (en) * 2007-05-28 2008-12-04 Panasonic Corporation Organic el device and display apparatus
US7764014B2 (en) * 2007-05-30 2010-07-27 Panasonic Corporation Organic EL display panel with banks defining line-state pixels
JP4280301B2 (en) 2007-05-31 2009-06-17 パナソニック株式会社 Organic EL device and method for manufacturing the same
JP5208591B2 (en) 2007-06-28 2013-06-12 株式会社半導体エネルギー研究所 Light emitting device and lighting device
CN102017216B (en) * 2008-04-28 2013-03-27 大日本印刷株式会社 Device having hole injection/transport layer, method for manufacturing the same, and ink for forming hole injection/transport layer
KR20140069342A (en) 2008-05-16 2014-06-09 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Light-emitting element and electronic device
JP2010153365A (en) * 2008-11-19 2010-07-08 Semiconductor Energy Lab Co Ltd Light-emitting element, light-emitting device, electronic equipment, and illumination device
TWI486097B (en) 2008-12-01 2015-05-21 Semiconductor Energy Lab Light-emitting element, light-emitting device, lighting device, and electronic device
JP5759669B2 (en) 2008-12-01 2015-08-05 株式会社半導体エネルギー研究所 LIGHT EMITTING ELEMENT, LIGHT EMITTING DEVICE, ELECTRONIC DEVICE, AND LIGHTING DEVICE
KR101750301B1 (en) 2009-05-29 2017-06-23 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Light-emitting element, light-emitting device, electronic device, and lighting device
US8389979B2 (en) * 2009-05-29 2013-03-05 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, electronic device, and lighting device
JP2011009205A (en) * 2009-05-29 2011-01-13 Semiconductor Energy Lab Co Ltd Light emitting element, light emitting device, and method of manufacturing the same
CN105742515A (en) * 2009-05-29 2016-07-06 株式会社半导体能源研究所 Light-Emitting Element, Light-Emitting Device, Lighting Device, and Electronic Appliance
EP2474204B1 (en) * 2009-09-04 2017-01-25 Semiconductor Energy Laboratory Co, Ltd. Light-emitting device
CN102484922B (en) * 2009-09-07 2015-08-19 株式会社半导体能源研究所 Light-emitting component, luminescent device, illuminating device and electronic device
US8404500B2 (en) * 2009-11-02 2013-03-26 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing light-emitting element, light-emitting element, light-emitting device, lighting device, and electronic appliance
EP2365556B1 (en) 2010-03-08 2014-07-23 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, electronic device, and lighting device
CN102201541B (en) * 2010-03-23 2015-11-25 株式会社半导体能源研究所 Light-emitting component, light-emitting device, electronic equipment and lighting device
TWI506121B (en) 2010-03-31 2015-11-01 Semiconductor Energy Lab Light-emitting element, light-emitting device, electronic device, and lighting device
JP5801579B2 (en) 2010-03-31 2015-10-28 株式会社半導体エネルギー研究所 LIGHT EMITTING ELEMENT, LIGHT EMITTING DEVICE, ELECTRONIC DEVICE, AND LIGHTING DEVICE
US9142792B2 (en) * 2010-06-18 2015-09-22 Basf Se Organic electronic devices comprising a layer comprising at least one metal organic compound and at least one metal oxide
WO2011162105A1 (en) 2010-06-25 2011-12-29 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, display, and electronic device
WO2012046560A1 (en) 2010-10-04 2012-04-12 Semiconductor Energy Laboratory Co., Ltd. Composite material, light-emitting element, light-emitting device, electronic device, and lighting device
CN102054938A (en) * 2010-11-10 2011-05-11 陕西科技大学 Sandwich anode structure of organic electroluminescent device and preparation method thereof
US8421346B2 (en) 2011-01-28 2013-04-16 Semiconductor Energy Laboratory Co., Ltd. Composite material, light-emitting element, light-emitting device, lighting device, electronic device, and fluorene derivative
JP2012182443A (en) 2011-02-11 2012-09-20 Semiconductor Energy Lab Co Ltd Light-emitting element and light-emitting device
JP5969216B2 (en) 2011-02-11 2016-08-17 株式会社半導体エネルギー研究所 Light emitting element, display device, lighting device, and manufacturing method thereof
KR20120095790A (en) 2011-02-21 2012-08-29 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Photoelectric conversion device
US9437758B2 (en) 2011-02-21 2016-09-06 Semiconductor Energy Laboratory Co., Ltd. Photoelectric conversion device
EP2503618B1 (en) 2011-03-23 2014-01-01 Semiconductor Energy Laboratory Co., Ltd. Composite material, light-emitting element, light-emitting device, electronic device, and lighting device
US9083000B2 (en) 2011-04-29 2015-07-14 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and lighting device
JP6023461B2 (en) 2011-05-13 2016-11-09 株式会社半導体エネルギー研究所 Light emitting element, light emitting device
US9419239B2 (en) 2011-07-08 2016-08-16 Semiconductor Energy Laboratory Co., Ltd. Composite material, light-emitting element, light-emitting device, electronic device, lighting device, and organic compound
US9159939B2 (en) 2011-07-21 2015-10-13 Semiconductor Energy Laboratory Co., Ltd. Photoelectric conversion device
JP2013058562A (en) 2011-09-07 2013-03-28 Semiconductor Energy Lab Co Ltd Photoelectric conversion device
JP6111578B2 (en) 2011-10-25 2017-04-12 大日本印刷株式会社 Hole injecting and transporting layer material, hole injecting and transporting layer forming ink, device, and production method thereof
TWI686971B (en) 2013-08-09 2020-03-01 日商半導體能源研究所股份有限公司 Light-emitting element, display module, lighting module, light-emitting device, display device, electronic device, and lighting device
US9755177B2 (en) 2013-10-09 2017-09-05 Sharp Kabushiki Kaisha Organic electroluminescent display panel
US9748316B2 (en) * 2013-10-28 2017-08-29 Sharp Kabushiki Kaisha Organic electroluminescent panel
JP2015187982A (en) 2014-03-13 2015-10-29 株式会社半導体エネルギー研究所 Light-emitting element, light-emitting device, electronic apparatus, and lighting system
US10797113B2 (en) 2016-01-25 2020-10-06 Semiconductor Energy Laboratory Co., Ltd. Light-emitting device with layered electrode structures
WO2019220283A1 (en) 2018-05-18 2019-11-21 株式会社半導体エネルギー研究所 Light-emitting element, light-emitting device, electronic device, and illumination device
US11903232B2 (en) 2019-03-07 2024-02-13 Semiconductor Energy Laboratory Co., Ltd. Light-emitting device comprising charge-generation layer between light-emitting units
CN112786663A (en) 2019-11-08 2021-05-11 株式会社半导体能源研究所 Light-emitting device, electronic apparatus, and lighting device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0963771A (en) 1995-08-25 1997-03-07 Toyota Central Res & Dev Lab Inc Organic thin film luminescent element
US20030160260A1 (en) 2002-02-28 2003-08-28 Fuji Photo Film Co., Ltd. Light-emitting element and method of producing the same
EP1351558A1 (en) 2002-03-26 2003-10-08 Junji Kido Organic electroluminescent device

Family Cites Families (83)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0719925B2 (en) 1985-03-05 1995-03-06 株式会社東芝 Conductive thin film
JP2636341B2 (en) 1988-06-09 1997-07-30 日本電気株式会社 Organic thin film EL device
JP2666428B2 (en) 1988-11-18 1997-10-22 日本電気株式会社 Organic thin film EL device
JP2773297B2 (en) 1989-09-28 1998-07-09 日本電気株式会社 Organic thin film EL device
JPH03190088A (en) 1989-12-20 1991-08-20 Sanyo Electric Co Ltd Organic el element
JP2926845B2 (en) 1990-03-23 1999-07-28 日本電気株式会社 Organic thin film EL device
JPH04357694A (en) * 1991-06-03 1992-12-10 Denki Kagaku Kogyo Kk Thin organic film el element
AU1848292A (en) 1991-06-28 1993-01-14 Russell Drago Oxidation dehydrogenation
JPH05182766A (en) * 1991-12-26 1993-07-23 Toyota Central Res & Dev Lab Inc Thin film el element
JPH06267658A (en) 1993-03-09 1994-09-22 Mitsubishi Kasei Corp Organic el element
JP3189480B2 (en) 1993-04-02 2001-07-16 富士電機株式会社 Organic thin film light emitting device
JP3534445B2 (en) * 1993-09-09 2004-06-07 隆一 山本 EL device using polythiophene
JPH0790256A (en) * 1993-09-22 1995-04-04 Pioneer Electron Corp Organic electroluminescent device
JPH07312289A (en) 1994-05-18 1995-11-28 Mitsubishi Chem Corp Organic electroluminescent element
JP3561549B2 (en) * 1995-04-07 2004-09-02 三洋電機株式会社 Organic electroluminescence device
JPH10172762A (en) * 1996-12-11 1998-06-26 Sanyo Electric Co Ltd Manufacture of display device using electroluminescent element and display device therefor
JP4054082B2 (en) * 1997-01-08 2008-02-27 株式会社Kri Thin film light emitting device and manufacturing method thereof
JPH10270171A (en) * 1997-01-27 1998-10-09 Junji Kido Organic electroluminescent element
US5989737A (en) 1997-02-27 1999-11-23 Xerox Corporation Organic electroluminescent devices
JP3571171B2 (en) 1997-05-08 2004-09-29 出光興産株式会社 Organic electroluminescence device
JPH11144773A (en) * 1997-09-05 1999-05-28 Fuji Photo Film Co Ltd Photoelectric converting element and light regenerating type photoelectric chemical battery
GB9803764D0 (en) * 1998-02-23 1998-04-15 Cambridge Display Tech Ltd Display devices
JPH11251067A (en) * 1998-03-02 1999-09-17 Junji Kido Organic electroluminescence element
JP3755986B2 (en) 1998-04-06 2006-03-15 アイセル株式会社 Fastening method
JP3468089B2 (en) 1998-04-07 2003-11-17 松下電器産業株式会社 Organic electroluminescent device
JPH11307264A (en) 1998-04-17 1999-11-05 Matsushita Electric Ind Co Ltd Organic electroluminescent element
JPH11307259A (en) 1998-04-23 1999-11-05 Tdk Corp Organic el element
EP1009198A4 (en) 1998-06-26 2006-08-23 Idemitsu Kosan Co Luminescent device
JP4198253B2 (en) 1999-02-02 2008-12-17 出光興産株式会社 Organic electroluminescence device and method for producing the same
JP4420486B2 (en) 1999-04-30 2010-02-24 出光興産株式会社 Organic electroluminescence device and method for producing the same
JP2000315581A (en) * 1999-04-30 2000-11-14 Idemitsu Kosan Co Ltd Organic electroluminescence element and manufacture thereof
JP4666722B2 (en) 1999-06-28 2011-04-06 株式会社半導体エネルギー研究所 EL display device and electronic device
TW515109B (en) * 1999-06-28 2002-12-21 Semiconductor Energy Lab EL display device and electronic device
JP2001043980A (en) 1999-07-29 2001-02-16 Sony Corp Organic electroluminescent element and display device
KR20010050711A (en) * 1999-09-29 2001-06-15 준지 키도 Organic electroluminescent device, group of organic electroluminescent devices and controlling method of emission spectrum in such devices
JP4824848B2 (en) * 2000-02-29 2011-11-30 淳二 城戸 Organic electroluminescent device, organic electroluminescent device group, and method for identifying emission spectrum thereof
JP4780826B2 (en) 1999-10-12 2011-09-28 株式会社半導体エネルギー研究所 Method for manufacturing electro-optical device
TW480722B (en) * 1999-10-12 2002-03-21 Semiconductor Energy Lab Manufacturing method of electro-optical device
TW511298B (en) * 1999-12-15 2002-11-21 Semiconductor Energy Lab EL display device
US20010053559A1 (en) * 2000-01-25 2001-12-20 Semiconductor Energy Laboratory Co., Ltd. Method of fabricating display device
KR20010085420A (en) * 2000-02-23 2001-09-07 기타지마 요시토시 Electroluminescence element and method manufacturing the same
TW521303B (en) * 2000-02-28 2003-02-21 Semiconductor Energy Lab Electronic device
JP4357694B2 (en) * 2000-04-18 2009-11-04 日新製鋼株式会社 Ferritic stainless steel for exhaust gas path members of gas turbines
US6608449B2 (en) * 2000-05-08 2003-08-19 Semiconductor Energy Laboratory Co., Ltd. Luminescent apparatus and method of manufacturing the same
US6692845B2 (en) * 2000-05-12 2004-02-17 Semiconductor Energy Laboratory Co., Ltd. Light-emitting device
US6483236B1 (en) * 2000-05-24 2002-11-19 Eastman Kodak Company Low-voltage organic light-emitting device
US6489638B2 (en) * 2000-06-23 2002-12-03 Semiconductor Energy Laboratory Co., Ltd. Light emitting device
JP3755390B2 (en) * 2000-09-08 2006-03-15 株式会社日立製作所 Phosphor, display device using the same, and light source
US6893743B2 (en) * 2000-10-04 2005-05-17 Mitsubishi Chemical Corporation Organic electroluminescent device
DE10052423C1 (en) * 2000-10-23 2002-01-03 Thyssenkrupp Stahl Ag Production of a magnesium hot strip comprises continuously casting a magnesium alloy melt to a pre-strip, and hot rolling the pre-strip directly from the casting heat at a specified roller starting temperature to form a hot strip
DE10058578C2 (en) 2000-11-20 2002-11-28 Univ Dresden Tech Light-emitting component with organic layers
SG138467A1 (en) 2000-12-28 2008-01-28 Semiconductor Energy Lab Luminescent device
JP4076769B2 (en) * 2000-12-28 2008-04-16 株式会社半導体エネルギー研究所 Light emitting device and electric appliance
JP3955744B2 (en) * 2001-05-14 2007-08-08 淳二 城戸 Manufacturing method of organic thin film element
JP3773423B2 (en) 2001-06-11 2006-05-10 Tdk株式会社 Organic EL device
US6657224B2 (en) * 2001-06-28 2003-12-02 Emagin Corporation Organic light emitting diode devices using thermostable hole-injection and hole-transport compounds
ATE546844T1 (en) * 2001-08-29 2012-03-15 Univ Princeton ORGANIC LIGHT EMITTING DEVICES WITH SUPPORT BLOCKING LAYERS WITH METAL COMPLEXES
JP2003068472A (en) * 2001-08-29 2003-03-07 Hitachi Ltd Organic light-emitting element and organic light-emitting display using it
US6660186B2 (en) * 2001-10-31 2003-12-09 Matsushita Electric Industrial Co., Ltd. Method of making blue emitting aluminate phosphor for VUV excited light emitting device
JP3742054B2 (en) 2001-11-30 2006-02-01 株式会社半導体エネルギー研究所 Display device
US7141817B2 (en) * 2001-11-30 2006-11-28 Semiconductor Energy Laboratory Co., Ltd. Light emitting device
JP4192592B2 (en) 2001-12-26 2008-12-10 三菱化学株式会社 Organic iridium complex and organic electroluminescent device using the same
JP3779625B2 (en) 2002-01-29 2006-05-31 日本化薬株式会社 Light emitting element
JP2003264082A (en) 2002-03-08 2003-09-19 Sharp Corp Organic led element
JP4243328B2 (en) * 2002-03-11 2009-03-25 財団法人神奈川科学技術アカデミー Phenylazomethine-based carbazole dendrimers and organic EL devices
JP2003272835A (en) 2002-03-13 2003-09-26 Matsushita Electric Ind Co Ltd Organic light emitting element, and driving method of the same
JP2004055177A (en) 2002-07-16 2004-02-19 Dainippon Printing Co Ltd Electroluminescent display device and manufacturing method of the same
US7158161B2 (en) * 2002-09-20 2007-01-02 Matsushita Electric Industrial Co., Ltd. Organic electroluminescence element and an exposure unit and image-forming apparatus both using the element
JP2004134395A (en) 2002-09-20 2004-04-30 Matsushita Electric Ind Co Ltd Organic electroluminescence element, exposure device using the same, and image forming apparatus
US20040140758A1 (en) * 2003-01-17 2004-07-22 Eastman Kodak Company Organic light emitting device (OLED) display with improved light emission using a metallic anode
JP4624653B2 (en) 2003-05-20 2011-02-02 出光興産株式会社 Organic electroluminescence element and display device
JP2005026121A (en) 2003-07-03 2005-01-27 Fujitsu Ltd Organic el element and manufacturing method of the same as well as organic el display
JP4396163B2 (en) 2003-07-08 2010-01-13 株式会社デンソー Organic EL device
AU2003294180A1 (en) 2003-07-09 2005-01-28 Matsushita Electric Industrial Co., Ltd. Organic electroluminescence element and an exposure unit and image-forming apparatus both using the element
CN101789497B (en) * 2003-09-26 2013-03-13 株式会社半导体能源研究所 Light-emitting device and method for manufacturing the same
JP4683829B2 (en) 2003-10-17 2011-05-18 淳二 城戸 Organic electroluminescent device and manufacturing method thereof
JP4476594B2 (en) 2003-10-17 2010-06-09 淳二 城戸 Organic electroluminescent device
JP4243237B2 (en) 2003-11-10 2009-03-25 淳二 城戸 Organic element, organic EL element, organic solar cell, organic FET structure, and organic element manufacturing method
JP4300176B2 (en) * 2003-11-13 2009-07-22 ローム株式会社 Organic electroluminescent device
EP2059094A1 (en) * 2003-12-16 2009-05-13 Panasonic Corporation Organic electroluminescent device and method for manufacturing the same
JP2005251587A (en) 2004-03-04 2005-09-15 Tdk Corp Organic el device
JP4925569B2 (en) 2004-07-08 2012-04-25 ローム株式会社 Organic electroluminescent device
WO2006101016A1 (en) * 2005-03-23 2006-09-28 Semiconductor Energy Laboratory Co., Ltd. Composite material, light emitting element and light emitting device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0963771A (en) 1995-08-25 1997-03-07 Toyota Central Res & Dev Lab Inc Organic thin film luminescent element
US20030160260A1 (en) 2002-02-28 2003-08-28 Fuji Photo Film Co., Ltd. Light-emitting element and method of producing the same
EP1351558A1 (en) 2002-03-26 2003-10-08 Junji Kido Organic electroluminescent device

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
S. TOHITO ET AL., J. PHYS.D: APPL. PHYS., vol. 29, 1996, pages 2750
See also references of EP1776846A4

Cited By (80)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1521316B1 (en) * 2003-10-03 2016-05-25 Semiconductor Energy Laboratory Co., Ltd. Manufacturing method of a light emitting element
EP2276088A3 (en) * 2003-10-03 2011-03-09 Semiconductor Energy Laboratory Co, Ltd. Light emitting element and manufacturing method thereof, and light emitting device using the light emitting element
US9461271B2 (en) 2003-10-03 2016-10-04 Semiconductor Energy Laboratory Co., Ltd. Light emitting element and manufacturing method thereof, and light emitting device using the light emitting element
EP1524706A3 (en) * 2003-10-17 2006-05-10 Junji Kido Organic electroluminescent device
US8558451B2 (en) 2003-10-17 2013-10-15 Junji Kido Organic electroluminescent device
EP1524706A2 (en) * 2003-10-17 2005-04-20 Junji Kido Organic electroluminescent device
US8643270B2 (en) 2004-05-20 2014-02-04 Semiconductor Energy Laboratory Co., Inc. Light-emitting element and display device
US8339039B2 (en) 2004-05-20 2012-12-25 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element including intermediate conductive layer having an electron-injection layer with an island-like structure
US8018152B2 (en) * 2004-05-20 2011-09-13 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element including intermediate conductive layer having a hole-injection layer with an island-like structure
US8618574B2 (en) 2004-08-04 2013-12-31 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, display device, and electronic appliance
US7462883B2 (en) 2004-08-04 2008-12-09 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element having hole generating layer
US7964891B2 (en) 2004-08-04 2011-06-21 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, display device, and electronic appliance
US7951470B2 (en) 2004-08-23 2011-05-31 Semiconductor Energy Laboratory Co., Ltd. Light emitting element, light emitting device, and lighting system
US10134996B2 (en) 2004-10-29 2018-11-20 Semicondcutor Energy Laboratory Co., Ltd. Composite material, light-emitting element, light-emitting device, and manufacturing method thereof
US7646010B2 (en) 2004-11-26 2010-01-12 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic device
US8927114B2 (en) 2004-11-30 2015-01-06 Semiconductor Energy Laboratory Co., Ltd. Light emitting element and electronic device using the same
US7989694B2 (en) 2004-12-06 2011-08-02 Semiconductor Energy Laboratory Co., Ltd. Photoelectric conversion element, solar battery, and photo sensor
US8692454B2 (en) 2004-12-06 2014-04-08 Semiconductor Energy Laboratory Co., Ltd. Electronic appliance and light-emitting device
US8569742B2 (en) 2004-12-06 2013-10-29 Semiconductor Energy Laboratory Co., Ltd. Organic field-effect transistor and semiconductor device including the same
US9257489B2 (en) 2004-12-06 2016-02-09 Semiconductor Energy Laboratory Co., Ltd. Electronic appliance and light-emitting device
US7667389B2 (en) 2004-12-06 2010-02-23 Semiconductor Energy Laboratory Co., Ltd. Light emitting element, light emitting device, and electronic device
US7999460B2 (en) 2004-12-06 2011-08-16 Semiconductor Energy Laboratory Co., Ltd. Electronic appliance and light-emitting device
US8492971B2 (en) 2004-12-06 2013-07-23 Semiconductor Energy Laboratory Co., Ltd. Electronic appliance and light-emitting device
US7521855B2 (en) 2004-12-06 2009-04-21 Semiconductor Energy Laboratory Co., Ltd. Electronic appliance and light-emitting device
US9147820B2 (en) 2004-12-28 2015-09-29 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and method for manufacturing the same
US8633473B2 (en) 2004-12-28 2014-01-21 Semiconductor Energy Laboratory Co., Ltd. High contrast light emitting device and method for manufacturing the same
US8426034B2 (en) * 2005-02-08 2013-04-23 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic appliance
US9530968B2 (en) 2005-02-15 2016-12-27 Semiconductor Energy Laboratory Co., Ltd. Light emitting element and light emitting device
JP2015092578A (en) * 2005-02-28 2015-05-14 株式会社半導体エネルギー研究所 Composite material
US7626198B2 (en) 2005-03-22 2009-12-01 Semiconductor Energy Laboratory Co., Ltd. Nonlinear element, element substrate including the nonlinear element, and display device
US8405070B2 (en) 2005-03-23 2013-03-26 Semiconductor Energy Laboratory Co., Ltd. Composite material, and light emitting element and light emitting device using the composite material
US7649197B2 (en) 2005-03-23 2010-01-19 Semiconductor Energy Laboratory Co., Ltd. Composite material, and light emitting element and light emitting device using the composite material
US8916276B2 (en) 2005-03-23 2014-12-23 Semiconductor Energy Laboratory Co., Ltd. Composite material, light emitting element and light emitting device
US8420227B2 (en) * 2005-03-23 2013-04-16 Semiconductor Energy Laboratory Co., Ltd. Composite material, light emitting element and light emitting device
US7777232B2 (en) 2005-04-11 2010-08-17 Semiconductor Energy Laboratory Co., Ltd. Display device and electronic device using the same
JP2015181189A (en) * 2005-04-21 2015-10-15 株式会社半導体エネルギー研究所 light-emitting element
US8049208B2 (en) 2005-04-22 2011-11-01 Semiconductor Energy Laboratory Co., Ltd. Organic semiconductor device having composite electrode
US20060263637A1 (en) * 2005-05-20 2006-11-23 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element and light-emitting device
US8920940B2 (en) * 2005-05-20 2014-12-30 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element and light-emitting device
US8158969B2 (en) * 2005-05-20 2012-04-17 Hitachi Displays, Ltd. Organic light emitting display device
US8269227B2 (en) 2005-06-09 2012-09-18 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and electronic device
US8461605B2 (en) 2005-06-09 2013-06-11 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and electronic device
US8252434B2 (en) 2005-06-22 2012-08-28 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and electronic appliance using the same
US8017252B2 (en) 2005-06-22 2011-09-13 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and electronic appliance using the same
JP2008021665A (en) * 2005-06-22 2008-01-31 Semiconductor Energy Lab Co Ltd Light-emitting device, and electronic equipment using the same
CN102593367A (en) * 2005-06-22 2012-07-18 株式会社半导体能源研究所 Light-emitting device, and electronic equipment using the same
CN1885585B (en) * 2005-06-22 2012-04-18 株式会社半导体能源研究所 Light emitting device and electronic appliance using the same
US8541114B2 (en) 2005-06-22 2013-09-24 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and electronic appliance using the same
US8729795B2 (en) 2005-06-30 2014-05-20 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and electronic device
US9196858B2 (en) 2005-07-04 2015-11-24 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing light emitting device
US8288180B2 (en) 2005-07-04 2012-10-16 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing light emitting device
US8901814B2 (en) 2005-07-06 2014-12-02 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic device
US8415878B2 (en) 2005-07-06 2013-04-09 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic device
US8659008B2 (en) 2005-07-08 2014-02-25 Semiconductor Energy Laboratory Co., Ltd. Composite material and light emitting element, light emitting device, and electronic device using the composite material
US9224968B2 (en) 2005-07-25 2015-12-29 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic appliance
JP2009224804A (en) * 2005-07-25 2009-10-01 Semiconductor Energy Lab Co Ltd Light emitting element
WO2007013478A1 (en) 2005-07-25 2007-02-01 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic appliance
US8227982B2 (en) 2005-07-25 2012-07-24 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic appliance
EP1911079A4 (en) * 2005-07-25 2012-05-09 Semiconductor Energy Lab Light-emitting element, light-emitting device, and electronic appliance
JP2007073932A (en) * 2005-07-25 2007-03-22 Semiconductor Energy Lab Co Ltd Light emitting element, light emitting device, and electronic apparatus
EP1911079A1 (en) * 2005-07-25 2008-04-16 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and electronic appliance
CN102163697A (en) * 2005-07-25 2011-08-24 株式会社半导体能源研究所 Light-emitting element, light-emitting device, and electronic appliance
JP2014239253A (en) * 2005-07-25 2014-12-18 株式会社半導体エネルギー研究所 Light emitting device, light emitting apparatus, lighting apparatus and electronic apparatus
KR101262068B1 (en) * 2005-07-25 2013-05-08 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Light-emitting element light-emitting device and electronic appliance
CN101263616B (en) * 2005-07-25 2011-05-11 株式会社半导体能源研究所 Light emitting element, light emitting device, and electronic apparatus
US7994711B2 (en) 2005-08-08 2011-08-09 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and manufacturing method thereof
KR101338875B1 (en) * 2005-10-18 2013-12-09 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Light emitting element, light emitting device, and electronic apparatus
EP1777758A1 (en) * 2005-10-18 2007-04-25 Semiconductor Energy Laboratory Co., Ltd. Organic light emitting device
JP2007142378A (en) * 2005-10-18 2007-06-07 Semiconductor Energy Lab Co Ltd Light emitting element, light emitting device and electronic apparatus
WO2007064009A1 (en) * 2005-11-30 2007-06-07 Semiconductor Energy Laboratory Co., Ltd. Light emitting element, light emitting device and electronic device
JP2007180526A (en) * 2005-11-30 2007-07-12 Semiconductor Energy Lab Co Ltd Light emitting element, light emitting device and electronic equipment
KR101338098B1 (en) 2006-06-30 2013-12-06 엘지디스플레이 주식회사 Organic electro luminescence display device and fabrication method thereof
US8093806B2 (en) 2007-06-20 2012-01-10 Semiconductor Energy Laboratory Co., Ltd. Light-emitting device, method for manufacturing the same, and electronic apparatus
US8368301B2 (en) 2007-06-20 2013-02-05 Semiconductor Energy Laboratory Co., Ltd. Light-emitting device, method for manufacturing the same, and electronic apparatus
US8531104B2 (en) 2007-06-20 2013-09-10 Semiconductor Energy Laboratory Co., Ltd. Light-emitting device, method for manufacturing the same, and electronic apparatus
US20110127510A1 (en) * 2009-12-01 2011-06-02 Semiconductor Energy Laboratory Co., Ltd. Light-Emitting Element, Light-Emitting Device, Electronic Device, and Lighting Device
US8486543B2 (en) * 2009-12-01 2013-07-16 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, electronic device, and lighting device
US9698354B2 (en) 2009-12-01 2017-07-04 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, electronic device, and lighting device
US10756287B2 (en) 2009-12-01 2020-08-25 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, electronic device, and lighting device
US9595678B2 (en) 2010-07-23 2017-03-14 Basf Se Dye solar cell with improved stability

Also Published As

Publication number Publication date
US8178869B2 (en) 2012-05-15
CN100596251C (en) 2010-03-24
EP1776846B1 (en) 2013-04-10
TW201342656A (en) 2013-10-16
TW200816863A (en) 2008-04-01
KR20060099511A (en) 2006-09-19
TW200518625A (en) 2005-06-01
KR20090111869A (en) 2009-10-27
KR101286221B1 (en) 2013-07-15
TWI464902B (en) 2014-12-11
TWI407830B (en) 2013-09-01
TWI407612B (en) 2013-09-01
KR20090111868A (en) 2009-10-27
CN101771135B (en) 2012-05-23
US8216875B2 (en) 2012-07-10
TW201334217A (en) 2013-08-16
KR101590148B1 (en) 2016-01-29
EP1776846A2 (en) 2007-04-25
WO2005031798A3 (en) 2005-05-26
KR20120062911A (en) 2012-06-14
CN1860829A (en) 2006-11-08
CN101771135A (en) 2010-07-07
US20100207518A1 (en) 2010-08-19
KR101286219B1 (en) 2013-07-15
US20120241812A1 (en) 2012-09-27
KR20140107696A (en) 2014-09-04
US20070200125A1 (en) 2007-08-30
TW201220527A (en) 2012-05-16
TW200814390A (en) 2008-03-16
CN101777628B (en) 2013-03-13
KR20130062367A (en) 2013-06-12
US8507903B2 (en) 2013-08-13
CN101789497A (en) 2010-07-28
CN101789497B (en) 2013-03-13
TWI422066B (en) 2014-01-01
CN101777628A (en) 2010-07-14
US7732808B2 (en) 2010-06-08
TWI407829B (en) 2013-09-01
EP1776846A4 (en) 2010-08-11
KR20120014044A (en) 2012-02-15
US20100096627A1 (en) 2010-04-22

Similar Documents

Publication Publication Date Title
US7732808B2 (en) Light-emitting device and method for manufacturing the same
EP2276088B1 (en) Light emitting element, and light emitting device using the light emitting element
KR101204289B1 (en) Light emitting device, electronic appliance and lighting appliance
JP3748110B1 (en) LIGHT EMITTING DEVICE AND ELECTRONIC DEVICE USING THE SAME
KR20070085793A (en) Light emitting element and light emitting device using the same
JP2006114477A (en) Manufacturing method of light-emitting device and electronic apparatus
JP5244456B2 (en) Light-emitting devices, electronic devices, mobile phones, lighting equipment
JP2005129500A (en) Light emitting element and its manufacturing method, and light emitting device using the light emitting element

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200480027991.7

Country of ref document: CN

AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1020067005626

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2004773500

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 10571891

Country of ref document: US

Ref document number: 2007200125

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 2004773500

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 10571891

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 1020097018993

Country of ref document: KR

Ref document number: 1020097018994

Country of ref document: KR

NENP Non-entry into the national phase

Ref country code: JP

WWE Wipo information: entry into national phase

Ref document number: 1020117030615

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1020127010680

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1020137011242

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1020147023148

Country of ref document: KR