WO2005015621A1 - High-k dielectric film, method of forming the same and related semiconductor device - Google Patents
High-k dielectric film, method of forming the same and related semiconductor device Download PDFInfo
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- WO2005015621A1 WO2005015621A1 PCT/EP2003/050352 EP0350352W WO2005015621A1 WO 2005015621 A1 WO2005015621 A1 WO 2005015621A1 EP 0350352 W EP0350352 W EP 0350352W WO 2005015621 A1 WO2005015621 A1 WO 2005015621A1
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000004065 semiconductor Substances 0.000 title claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 135
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 74
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 72
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000010703 silicon Substances 0.000 claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 16
- 239000003990 capacitor Substances 0.000 claims description 9
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims description 9
- 238000009832 plasma treatment Methods 0.000 claims description 9
- 230000005669 field effect Effects 0.000 claims description 7
- 238000005240 physical vapour deposition Methods 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 229910005697 GdSix Inorganic materials 0.000 claims description 3
- 229910020781 SixOy Inorganic materials 0.000 claims 2
- 239000010408 film Substances 0.000 description 52
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 229910000311 lanthanide oxide Inorganic materials 0.000 description 5
- -1 Hf02 Chemical compound 0.000 description 4
- 229910020286 SiOxNy Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229910015861 MSix Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000005641 tunneling Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 235000013382 Morus laevigata Nutrition 0.000 description 1
- 244000278455 Morus laevigata Species 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910007264 Si2H6 Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910000326 transition metal silicate Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28185—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation with a treatment, e.g. annealing, after the formation of the gate insulator and before the formation of the definitive gate conductor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28202—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation in a nitrogen-containing ambient, e.g. nitride deposition, growth, oxynitridation, NH3 nitridation, N2O oxidation, thermal nitridation, RTN, plasma nitridation, RPN
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/511—Insulating materials associated therewith with a compositional variation, e.g. multilayer structures
- H01L29/513—Insulating materials associated therewith with a compositional variation, e.g. multilayer structures the variation being perpendicular to the channel plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/518—Insulating materials associated therewith the insulating material containing nitrogen, e.g. nitride, oxynitride, nitrogen-doped material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28194—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S257/00—Active solid-state devices, e.g. transistors, solid-state diodes
- Y10S257/914—Polysilicon containing oxygen, nitrogen, or carbon, e.g. sipos
Definitions
- High-k dielectric film method of forming the same and related semiconductor device
- the present invention relates to a high-k dielectric film, a method of forming the same and related semiconductor devices, and in particular to high-k dielectric films related to a gate dielectric for field effect semiconductor devices or a capacitor dielectric for trench capacitors in integrated circuits .
- CMOS devices Complementary Metal Oxide Semiconductor
- MOSFET devices Metal Ox- ide Semiconductor Field Effect Transistor
- high memory devices such as DRAMs (Dynamic Random Access Memories)
- CMOS devices Complementary Metal Oxide Semiconductor
- MOSFET devices Metal Ox- ide Semiconductor Field Effect Transistor
- DRAMs Dynamic Random Access Memories
- gate dielectric layers have been formed using silicon dioxide.
- the scaling down of the above described devices has increased the demand for gate dielec- tries with a higher dielectric constant than silicon dioxide. This is necessary to reach ultra thin oxide equivalent thicknesses (EOT, Equivalent Oxide Thickness) without compromising gate leakage current.
- EOT Equivalent Oxide Thickness
- transition metal oxide and silicate such as Hf0 2 , Zr0 2 , Hf -aluminate , Zr-aluminate, Zr-silicate, Hf-silicate and a lanthanide oxide like La 2 0 3 , Pr 2 0 3 , and Gd 2 0 3 .
- lanthanide oxides For lanthanide oxides, leakage current results have indicated that lanthanide oxides may be possible candidates of future dielectrics. However, according to H. IWAI , et al . , "Advanced gate dielectric materials for Sub-lOOnm CMOS", Tech. Dig. IEDM 2002, it is reported that these lanthanide oxides also form interfacial layers on Si substrates after subsequent thermal annealing, which may indicate thermal instability of these lanthanide oxides .
- an impurity penetration such as boron penetration from e.g. a gate layer to a Si substrate is a further problem to be solved by these high-k dielectric films.
- nitrogen incorporation on HfSi x O y has been known to suppress such a e.g. boron penetration and improve thermal stability, it was also reported that the very high Si content of Si/ [Si+Hf] ratio of over 80 % in HfSi x O y N z is required to pre- vent flat band voltage shift, resulting in seriously reducing dielectric constant of the film even with a high nitrogen content of 30 atomic percent (see M. KOYAMA, et al .
- a high-k dielectric film for a semiconductor device being formed on a substrate comprises at least a bottom layer of metal -silicon-oxynitride having a first nitrogen content and a first silicon content, and a top layer of metal-silicon-oxynitride having a second nitrogen content and a second silicon content, wherein said second nitrogen content of the top layer is higher than said first nitrogen content of the bottom layer and said second silicon content of the top layer is higher than said first silicon content of the bottom layer.
- the high-k dielectric film con- stitutes a multilayer stack comprising at least one middle layer of metal-silicon-oxynitride being formed between said bottom layer and said top layer having a further nitrogen content and a further silicon content wherein the respective further nitrogen and silicon contents are between said respective first and second nitrogen and silicon contents.
- a thickness of the top layer is equal to or lower than the sum of thicknesses of the remaining layers in the high-k dielectric film.
- the method of forming a high-k dielectric film comprises the steps of forming a bottom layer of metal-silicon-oxynitride having a first nitrogen content and a first silicon content on a substrate, and forming a top layer of metal-silicon- oxynitride having a second nitrogen content and a second silicon content, wherein said second nitrogen content is higher than said first nitrogen content and said second silicon content is higher than said first silicon content of the respective layers.
- the method further includes the step of forming a substrate interface layer of silicon-oxide on the substrate before forming the bottom layer.
- At least one middle layer of metal-silicon-oxynitride having a further nitrogen content and a further silicon content is formed on the bottom layer, wherein the respective further nitrogen content and the further silicon content is higher than that of the preceding layer.
- the method of forming a high-k dielectric film comprises the steps of forming a pre-bottom layer of metal-silicon-oxide having a first silicon content on a substrate, forming a pre-top layer of metal-silicon- oxide having a second silicon content, wherein the second silicon content is higher than the first silicon content, and performing N 2 plasma treatment to convert said pre-bottom layer to a metal-silicon-oxynitride bottom layer having a first nitrogen content and said pre-top layer to a metal- silicon-oxynitride top layer having a second nitrogen con- tent, wherein said second nitrogen content is higher than said first nitrogen content.
- At least one pre-middle layer of metal -silicon-oxide having a further silicon content is formed, wherein the respective further silicon content is higher than that of the preceding layer, and wherein during the N 2 plasma treatment at least one pre-middle layer is converted to at least one metal-silicon-oxynitride middle layer having a further nitrogen content, wherein the respective further nitrogen content is higher than that of the preceding layer .
- Figures 1A and IB are partial cross-sectional views showing essential steps for producing a high-k dielectric film according to a first embodiment
- Figure 2 is a partial cross-sectional view of the high-k dielectric film according to a second embodiment
- Figures 3A to 3D are partial cross-sectional views showing essential steps for producing a high-k dielectric film according to a third embodiment
- Figure 4 is a partial cross-sectional view of a field effect semiconductor device using the high-k dielectric film.
- Figure 5 is a partial cross-sectional view of a trench capacitor using the high-k dielectric film. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be de- scribed in detail. It should be understood, however, that the drawings and detailed description thereto are not intended to limit the invention to the particular form disclosed. On the contrary, the intention is to cover all modification, equivalents and alternatives falling within the spirit and scope of the present invention.
- Figures 1A and IB show partial cross-sections illustrating essential steps for producing a high-k dielectric film according to a first embodiment of the present invention.
- a monocrystalline Si substrate 1 is used as semiconductor substrate, on the surface of which a bottom layer B of metal-silicon-oxynitride (MSi xB O yB N Z B) is formed by layer deposition methods.
- MSi xB O yB N Z B metal-silicon-oxynitride
- a top layer T is formed by the same metal-silicon-oxynitride, however, having different silicon content and nitrogen content.
- the deposited top layer T constitutes MSi x _ ⁇ O y N zT having a second nitrogen content zT and a second silicon content xT .
- the first and second nitrogen contents of the bottom and top layer B and T as well as the first and second silicon contents xB and xT are selected in such a way that the second nitrogen content zT of the top layer T is higher than the first nitrogen content zB of the bottom layer and the second silicon content xT of the top layer T is higher than the first silicon content xB of the bottom layer.
- the indices x, y and z or xB, yB and zB or xT, yT and zT in the MSi x O y N z layers are real positive values indicating atomic percentage in a molecular. Nitrogen atomic percentage in respective layer is calculated by ( z/ ( 1+x+y+z ) ) X100. Usually, Si and M (metal) concentrations are presented by (x/(l+x)) X100 and (1/ (1+x) ) X100 , respectively.
- the shown bilayer stack according to Figure IB consti- tutes a new high-k dielectric film 2 having improved characteristics.
- the high-nitrogen-content top layer T of the bilayer stack plays a key role to effectively prevent diffusion of e.g. boron from a boron-doped poly-Si electrode (not shown) into the field effect device channel, whereas the low-nitrogen-content bottom layer B is helpful against mobility degradation within this channel and/or the substrate 1. •
- a decrease of Si since a decrease of Si.
- metal-silicon- oxynitrides is related to an increase of the metal content and, in turn, an increase of the dielectric constant the bi- layer stack according to the first embodiment provides a higher dielectric constant than the prior art of the similar high-Si-content metal-silicon-oxynitride.
- EOT effective oxide thickness
- Si and N concentrations in the top layer T need to be higher than those in the bottom layer B, e.g. xT > xB, zT > zB .
- a ratio of N and Si in the top layer T with respect to the bottom layer B depends further on what metal-silicon-oxides are considered.
- the metal M in the metal-silicon-oxynitride layer is Hf, which is HfSi x O y N z
- the Si/(Hf+Si) ratio of HfSi x O y N z needs to be in the range of 70 % to 95 % with N concentration of as high as 30 atomic percentage.
- N and Si contents of the bottom layer B need to be lower than those of the top layer T, with N atomic percentage in the range from 15 % to 25 % and a Si/(Hf+Si) ratio in the range from 20 % to 60 %.
- the top layer T should have a lower thickness than the thickness of the sum of the other layers within the high-k dielectric film 2 or the same. That is, the top layer T according to the bilayer structure of the first embodiment should be thinner or equal to the bottom layer B.
- an anneal process (at a temperature of over 600°C in N 2 or other gas) is helpful to density the layer stack and to reduce defects in order to improve the quality of the high-k dielectric film 2 (particularly to improve the leakage current characteristics) .
- Figure 2 shows a partial cross-sectional view of the high-k dielectric film according to a second embodiment, wherein same reference numbers refer to same or corresponding layers and a repeated description of these layers is omitted.
- a substrate interface layer I is formed on the surface of the substrate 1 while the respective further layers of the high-k dielectric film 2 are formed on the surface of this substrate interface layer I .
- this substrate interface layer constitutes preferably a silicon oxide, which further increases the mobility within the substrate and reduces defects at the surface of the substrate 1.
- the bilayer MSi x O y N z stack according to the first and second embodiment having a bottom layer and a top layer of metal-silicon-oxynitride
- at least a further metal layer of metal-silicon-oxynitride could be formed between said bottom layer B and said top layer T having a further nitrogen content and a further silicon content, wherein a respective further nitrogen content and a further silicon content is between said first and second nitrogen and silicon contents of the bottom layer B and top layer T.
- the further nitrogen content and the further silicon content of a respectively formed middle layer is higher than the respective nitrogen and silicon contents of a metal- silicon-oxynitride layer formed in a preceding step.
- the thickness of the top layer T is again equal to or lower than the sum of thicknesses of the remaining layers in the high-k dielectric film or multilayer stack, i.e. the bottom layer and the further middle layers.
- PVD physical vapor deposition
- metal such as Hf, Zr, La, Pr, Gd and other lanthanide metals
- silicon in an Ar/N 2 /0 2 ambient is considered to form metal-silicon-oxynitride films.
- Nitrogen concentration and silicon concentration in these metal-silicon-oxynitrides can be controlled by N 2 flow and silicon sputtering rate. High nitrogen content metal-silicon-oxynitride with a small amount of silicon can be obtained using high-nitrogen flow during the co-sputtering of Si.
- a high nitrogen content and high silicon content metal- silicon-oxynitride at the top part of the high-k dielectric film 2 and a lower nitrogen content and a lower silicon content at the bottom part of the high-k dielectric film 2 can be formed to keep the interface of the high-k dielectric film 2 and (a not shown) poly-Si electrode formed usually on the top of the high-k dielectric film 2 thermally stable.
- Poly-Si electrode deposition usually is performed using SiH 4 or Si 2 Hg which may induce reduction of metal-0 and metal-N bonds by hydrogen coming from SiH 4 or Si 2 H 6 , probably generating defects and, in turn, resulting in high leakage current.
- High nitrogen concentrations and high silicon concentrations in metal-silicon-oxynitride suppress reaction between hydrogen and the high-k dielectric film during a respective poly-Si deposition due to a number of Si-N and Si-0 bonds in the place of metal -0 and metal -N bonds. Similar advantages result when using a metallic material instead of poly-Si as an electrode formed on the surface of the high-k dielectric film 2.
- DySi x O y N z , and other nitrogen incorporated lanthanide-sili- cates can be formed as high-k dielectric films.
- Figures 3A to 3D show partial cross-sectional views illus- trating essential steps for producing a high-k dielectric film according to a third embodiment of the present invention, wherein same reference numbers refer to same or corresponding layers as in Figures 1 and 2, and, therefore, a repeated description of these layers is omitted in the follow- ing .
- a triple layer stack is formed by an alternative method to provide the high-k dielectric film 2.
- a substrate interface layer I is formed directly on the surface of the substrate 1 preferably by a thermal process.
- a Si0 2 -substrate interface layer I is formed on the Si substrate 1.
- a pre-bottom layer Bl of metal - silicon-oxide having a low first silicon content xB is formed preferably by deposition on the substrate interface layer I .
- a pre-middle layer Ml of metal- silicon-oxide having a further silicon content xM is deposited on the pre-bottom layer Bl having the first silicon content xB .
- the further silicon content xM of the further layer or the pre-middle layer Ml is higher than that of the bottom layer Bl or (if a plurality of middle layers are to be used) is higher than that of the preceding layer.
- a pre-top layer Tl of metal-silicon- oxide having a second silicon content xT is formed on the at least one pre-middle layer Ml.
- the second silicon content xT of the pre-top layer Tl is higher than the that of the pre-middle layer Ml which is higher than that of the pre- bottom layer Bl .
- an N 2 plasma treatment is made to the metal - silicon-oxide layers forming SiN bond rather than metal-N bond so that, as Si content in the different layer is different, also nitrogen contents after N plasma treatment is different, respectively.
- HfSi x O y can be formed by various deposition methods, such as MOCVD (Metal Organic
- HfSi x O y Chemical Vapor Deposition
- PVD Physical Vapor Deposition
- ALD Advanced Layer Deposition
- HfSi x O y two precursors, Hf [N (C 2 H 5 ) 2 ] 4 for Hf and Si[N(CH 3 ) 2 - 4 for Si, flow into a reactor together with 0 2 to deposit HfSi x O y .
- Si0 2 mole fraction in HfSi x O y can be controlled by process parameters, such as temperature, pressure and both precursor flow rates, during the silicate deposition.
- the third embodiment of this invention uses MOCVD HfSi x O y as sequence for depositing low Si0 2 content HfSi xB O yB and high Si0 2 content HfSi x iOyr are deposited at the bottom part and at the top part of the high-k dielectric film 2 and then followed by N 2 plasma treatment. After N 2 plasma nitration, the top layer T of the film 2 shows a high nitrogen content and the bottom layer B a low nitrogen content.
- MOCVD Zr silicate instead of MOCVD Hf silicate, precursors are requested to simply change to Zr [N (C 2 H 5 ) 2 ] 4 and Si[N(CH 3 ) 2 -4 for Zr silicate.
- This embodiment of the Hf or Zr silicon-oxynitride stack using MOCVD Hf silicate or Zr silicate can be extended to for MOCVD lanthanide silicates even though various lanthanide MOCVD processes are possible.
- the pre-bottom layer Bl, the pre-middle layer Ml and the pre-top layer Tl are converted to a respective metal- silicon-oxynitride bottom layer B, middle layer M and top layer T.
- an annealing process after N 2 plasma treatment can be considered to release the damage of plasma on the high-k dielectric film 2, to density the high-k dielectric film and to reduce defects as well as impurities in the high-k film stack .
- Figure 4 shows a partial cross-sectional view of a semiconductor device comprising a field effect transistor using the high-k dielectric film as a gate dielectric.
- a source region S, a drain region D and a channel region between the source and drain region are provided in a semiconductor substrate 1.
- the high-k dielectric film 2, according to the present invention, is used as gate dielectric and formed on the channel region while a gate layer is formed on said gate dielectric 2.
- spacer SP at the side walls of the gate stack could be provided to form the source and drain regions S and D.
- the gate layer 3 preferably comprises a poly-Si, it could also constitute a metal gate, thereby improving the electrical characteristics of the semiconductor device.
- Figure 5 shows a partial cross-sectional view of a semiconductor device wherein the high-k dielectric film is used as a capacitor dielectric.
- a deep trench or hole is provided within the silicon substrate 1.
- the high-k dielectric film 2 is provided after forming a second electrode 5 in the substrate 1 in the vicinity of the lower part of the trench.
- a filling material 4 is used as a first electrode of the resulting capacitor which is usually highly doped poly-Si or a deposited metal.
- the new high-k dielectric film essentially improves the electric characteristics of semiconductor devices thereby enabling further integration densities.
- this invention is believed to provide a high-k dielectric film, a method for forming the same as well as related semiconductor devices having an improved leakage current by reduced tunneling currents as well as improved diffusion barrier characteristics. Further modifications and alternative embodiments of various aspects of the invention will be apparent to those skilled in the art in view of this description.
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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CNB038268728A CN100431103C (en) | 2003-07-30 | 2003-07-30 | High-K dielectric film, method for forming it, and related semiconductor device |
DE60311016T DE60311016T2 (en) | 2003-07-30 | 2003-07-30 | HIGH-K DIELECTRIC FILM, METHOD OF MANUFACTURING THEREOF AND THIS SEMICONDUCTOR ELEMENT |
EP03817953A EP1649501B1 (en) | 2003-07-30 | 2003-07-30 | High-k dielectric film, method of forming the same and related semiconductor device |
AU2003266410A AU2003266410A1 (en) | 2003-07-30 | 2003-07-30 | High-k dielectric film, method of forming the same and related semiconductor device |
PCT/EP2003/050352 WO2005015621A1 (en) | 2003-07-30 | 2003-07-30 | High-k dielectric film, method of forming the same and related semiconductor device |
US11/342,370 US7405482B2 (en) | 2003-07-30 | 2006-01-27 | High-k dielectric film, method of forming the same and related semiconductor device |
US12/117,274 US7655099B2 (en) | 2003-07-30 | 2008-05-08 | High-k dielectric film, method of forming the same and related semiconductor device |
US12/609,670 US7923336B2 (en) | 2003-07-30 | 2009-10-30 | High-k dielectric film, method of forming the same and related semiconductor device |
Applications Claiming Priority (1)
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PCT/EP2003/050352 WO2005015621A1 (en) | 2003-07-30 | 2003-07-30 | High-k dielectric film, method of forming the same and related semiconductor device |
Related Child Applications (1)
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US11/342,370 Continuation US7405482B2 (en) | 2003-07-30 | 2006-01-27 | High-k dielectric film, method of forming the same and related semiconductor device |
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WO2005015621A1 true WO2005015621A1 (en) | 2005-02-17 |
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PCT/EP2003/050352 WO2005015621A1 (en) | 2003-07-30 | 2003-07-30 | High-k dielectric film, method of forming the same and related semiconductor device |
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US (3) | US7405482B2 (en) |
EP (1) | EP1649501B1 (en) |
CN (1) | CN100431103C (en) |
AU (1) | AU2003266410A1 (en) |
DE (1) | DE60311016T2 (en) |
WO (1) | WO2005015621A1 (en) |
Cited By (1)
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US7521324B2 (en) * | 2003-04-03 | 2009-04-21 | Tadahiro Ohmi | Semiconductor device and method for manufacturing the same |
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US7799669B2 (en) * | 2007-04-27 | 2010-09-21 | Texas Instruments Incorporated | Method of forming a high-k gate dielectric layer |
DE102007002962B3 (en) * | 2007-01-19 | 2008-07-31 | Qimonda Ag | Method for producing a dielectric layer and for producing a capacitor |
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US7671394B2 (en) * | 2007-10-17 | 2010-03-02 | International Business Machines Corporation | Embedded trench capacitor having a high-k node dielectric and a metallic inner electrode |
US20120001179A1 (en) * | 2010-07-02 | 2012-01-05 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device |
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US8614478B2 (en) | 2010-07-26 | 2013-12-24 | Infineon Technologies Austria Ag | Method for protecting a semiconductor device against degradation, a semiconductor device protected against hot charge carriers and a manufacturing method therefor |
US8779838B2 (en) | 2011-10-25 | 2014-07-15 | International Business Machines Corporation | Methodology and apparatus for tuning driving current of semiconductor transistors |
US9595593B2 (en) | 2015-06-29 | 2017-03-14 | Taiwan Semiconductor Manufacturing Co., Ltd. | Semiconductor structure with interfacial layer and method for manufacturing the same |
JP6640762B2 (en) * | 2017-01-26 | 2020-02-05 | 株式会社東芝 | Semiconductor device |
TWI634468B (en) * | 2017-08-18 | 2018-09-01 | 財團法人工業技術研究院 | Transparent display device |
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Also Published As
Publication number | Publication date |
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US20080246100A1 (en) | 2008-10-09 |
EP1649501B1 (en) | 2007-01-03 |
EP1649501A1 (en) | 2006-04-26 |
US20060194451A1 (en) | 2006-08-31 |
DE60311016D1 (en) | 2007-02-15 |
AU2003266410A1 (en) | 2005-02-25 |
DE60311016T2 (en) | 2007-08-02 |
US7923336B2 (en) | 2011-04-12 |
CN100431103C (en) | 2008-11-05 |
US7405482B2 (en) | 2008-07-29 |
US7655099B2 (en) | 2010-02-02 |
US20100047991A1 (en) | 2010-02-25 |
CN1820355A (en) | 2006-08-16 |
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