WO1998043286A1 - Tunable dielectric constant oxide and method of manufacture - Google Patents

Tunable dielectric constant oxide and method of manufacture Download PDF

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Publication number
WO1998043286A1
WO1998043286A1 PCT/US1998/005231 US9805231W WO9843286A1 WO 1998043286 A1 WO1998043286 A1 WO 1998043286A1 US 9805231 W US9805231 W US 9805231W WO 9843286 A1 WO9843286 A1 WO 9843286A1
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Prior art keywords
dielectric constant
silicon
film
oxide film
nitrogen
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PCT/US1998/005231
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French (fr)
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Derryl D. J. Allman
Dim Lee Kwong
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Symbios, Inc.
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Priority to AU64698/98A priority Critical patent/AU6469898A/en
Publication of WO1998043286A1 publication Critical patent/WO1998043286A1/en

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    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H01L21/02131—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being halogen doped silicon oxides, e.g. FSG
    • H—ELECTRICITY
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    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02142—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
    • H01L21/02153—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing titanium, e.g. TiSiOx
    • H—ELECTRICITY
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    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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    • 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
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/3143—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
    • H01L21/3144—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers on silicon
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    • 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
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
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    • 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
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31604—Deposition from a gas or vapour
    • H01L21/31608—Deposition of SiO2
    • H—ELECTRICITY
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    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H01L23/5329—Insulating materials
    • H—ELECTRICITY
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    • 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

Definitions

  • the present invention relates generally to a method of manufacturing semiconductor devices and, specifically, to a method of forming films such as silicon oxide films used in the manufacture of such devices, the films having a tunable dielectric constant.
  • Chemical vapor deposition is a commonly used technique for forming thin films and has been widely used as a manufacturing technique in the semiconductor device industry.
  • CVD methods using an organic or inorganic silicon compound gas and an oxidizing gas are well known as methods for forming thin films of silicon oxide.
  • an insulating film is typically utilized for electrically isolating element wiring.
  • the typical insulating film used in the past was a Si0 2 film formed by the thermal oxidation of a silicon substrate or a Si0 2 film formed by chemical vapor deposition under a reduced pressure or atmospheric pressure using gaseous materials such as silane and tetraethoxy silicate (TEOS).
  • TEOS tetraethoxy silicate
  • Si0 2 films are preferred for insulation and are formed by CVD techniques using either TEOS or silane and 0 2 because such Si0 2 films can be formed under temperatures as low as about 400°C.
  • the interconnect spacing between wiring is reduced so that electromagnetic coupling of adjacent metal lines is possible causing errors, noise and, in the extreme case, a non-functioning device.
  • the space between two adjacent metal lines is shortened in accordance with the miniaturization of the semiconductor circuitry, increased capacitance occurs between the metal lines tending to obstruct the higher operating speed of the semiconductor device, thereby inhibiting the performance improvement offered by the miniaturization of the device.
  • the Si0 2 film formed by conventional plasma CVD methods typically has a dielectric constant in the range from about 4.0 to 5.0.
  • two interconnect lines can be placed closer in proximity, thus lowering the operating voltage of the transistor because the noise margin thereof can be reduced. It is desirable, therefore, in some instances to reduce the dielectric constant of such films from approximately 4.5 to about 3.0 or lower.
  • dielectric constant of the oxide film being formed in semiconductor devices such as capacitors.
  • the higher dielectric constant materials can be used to form regions of capacitance within the integrated circuit.
  • the higher the dielectric constant of the material the smaller the capacitance region required, resulting in a smaller capacitor, thereby equating to an area savings.
  • the dielectric constant of oxides can be lowered by the addition of carbon or fluorine into the oxide. While this general principle has been stated in the prior art, the previous attempts to provide a film having a lowered dielectric constant have exhibited various deficiencies. For example, in Japanese Patent Application No. 2-77127, fluorine is introduced into SiO z by means of ion implantation. However, it is necessary to apply a heat treatment at a temperature of at least about 600 °C within the Si0 2 layer. Thus, the Si0 2 layer formed by this method cannot be used for isolation of aluminum wirings within semiconductor devices.
  • TEOS high density plasma
  • APCVD atmospheric pressure chemical vapor deposition
  • Another object of the invention is to provide a method for manufacturing a semiconductor device in which a silicon oxide film containing fluorine and carbon is produced, the film acting as an insulating film for electrically isolating conductive layers included in the semiconductor device, the film being formed by plasma CVD technique using an organic silicon gas as a starting material.
  • Another object of the invention is to provide basic nitrogen incorporation to act as a moisture and OH barrier for the activating film.
  • Another object of the invention is to provide a lower dielectric constant film which is stable with higher concentrations of fluorine incorporated into the film.
  • Another object of the invention is to provide a method of manufacturing semiconductor devices in which the conductive layers on the silicon oxide films so produced have improved reliability.
  • a method for manufacturing a semiconductor device is shown in which a silicon oxide film acts as an insulating film for electrically isolating conductive layers included in the semiconductor device.
  • a silicon oxide film is formed containing fluorine and having a given dielectric constant by CVD method using a source gas containing at least silicon, nitrogen, carbon, oxygen and fluorine contributors.
  • the ratio of nitrogen to oxygen in the source gases used in the CVD method is controlled in order to control the ultimate carbon and fluorine concentrations and hence the dielectric constant of the silicon oxide film so produced.
  • the addition of nitrogen to the film also acts as a barrier to the diffusion of H 2 0 or OH into the film in subsequent processing steps.
  • the source gases, in addition to a silicon contributor include N 2 0, 0 2 and C 2 F 6 .
  • the given dielectric constant and moisture barrier properties of the silicon oxide film are determined by controlling the relative ratios of N 2 0:0 2 :C 2 F 6 and high frequency to low frequency power applied, with silane SH X or NH X as the source gases in the CVD method.
  • the silicon source can be a conventional TEOS.
  • N 2 0 can be used as the nitrogen contributor in the source gas to add nitrogen to the silicon oxide film which is formed in order to improve reliability of the film when used in a semiconductor device.
  • a silicon oxide film can be formed containing fluorine and having a given dielectric constant value by plasma CVD method using a source gas containing at least silicon, nitrogen, carbon, oxygen and fluorine contributors introduced within a reaction chamber.
  • a high dielectric compound can also be introduced into the reaction chamber to form the relatively high dielectric constant silicon oxide film.
  • the high dielectric compound is preferably selected from the group consisting of either a single source or mixtures of alkoxy compounds of the general formula MOR, or titanate compounds of the general formula MTi0 3 and M 2 Ti0 5 , where M is an alkali or alkaline earth metal, or ferroelectric materials.
  • the high dielectric compound can be added to the reaction chamber by liquid or vapor injection into the CVD reaction chamber.
  • the high dielectric compounds added to the reaction chamber typically have dielectric constants between 15 and 12,000.
  • Figure 1 is a simplified, schematic view of a plasma CVD chamber of the type used in the method of the present invention
  • Figures 2-4 are simplified, cross-sectional views showing the steps employed in manufacturing a semiconductor device of the invention.
  • Figures 5-6 are graphs of the carbon, fluorine and nitrogen concentrations of Si0 2 films formed by conventional methods and formed with the tunable dielectric constants of the invention, respectively.
  • Figure 1 shows a parallel plate type plasma CVD apparatus of the type which can be used in practicing the method of the invention.
  • a gas within the chamber interior 13 is discharged to the exterior thereof by means of a suitable pump 15.
  • Appropriately selected source gases are introduced into the chamber interior 13 by means of a plurality of quartz nozzles 17, 19, 21.
  • a set of parallel plate electrodes 23, 25 are mounted within the chamber interior 13.
  • a variable frequency power source 27 is connected to the top electrode 23 with the bottom electrode 25 being connected to a ground potential point 29.
  • a Si substrate 31 is mounted on the lower electrode 25.
  • the dielectric constant of the oxide films produced according to the present method can be "tuned” by the selective addition of carbon, nitrogen or fluorine or all of the aforementioned to the oxide film.
  • the process of the invention allows the deposition of a conformal TEOS film which has been doped using carbon, nitrogen and fluorine. The process controls the percentage of carbon and fluorine that is added to the film in order to selectively "tune” the resulting dielectric constant of the film.
  • the film doped only with carbon, fluorine and nitrogen has shown improved transistor reliability performance over standard ⁇ ox.de films.
  • One advantage of the present method is that the starting gases can employ TEOS as the silicon source, thereby allowing conformal step coverage.
  • the process can be run using any plasma enhanced chemical vapor deposition (PECVD) deposition system, such as the radio frequency plasma assisted CVD system shown in Figure 1. Atmospheric or high density plasma systems may also be used to apply this film.
  • PECVD plasma enhanced chemical vapor deposition
  • the process of the invention preferably utilizes tetraethoxy silicate (TEOS) as the silicon source, although other silicon sources could be utilized besides TEOS.
  • TEOS tetraethoxy silicate
  • Other silicon sources include, for example, HSi(N(CH 2 ) 2 ) 3 ; Si(N(CH 3 ) 2 ) 4 ; (CH 3 ) 3 SiN 3 ; and SiH 4 or mixtures thereof.
  • the preferred oxidizing source gases are N 2 0 and although other sources of oxidizing gas could be utilized, as well, including NO, NH 3 , 0 2 , or a combination of these gases.
  • a preferred fluorine source gas is C 2 F &
  • Other fluorine source gases which could be used include SiF 4 , CF 4 and mixtures thereof, or any other fluorine gaseous source conveniently available.
  • N 2 0 alone or as one of the oxidizing source gases
  • TEOS is not fully oxidized, leaving carbon behind in the film being produced.
  • N 2 0 and 0 2 within selected percentages with TEOS, different percentages of carbon can be left behind in the film.
  • the percentage of fluorine and carbon added to the film is controlled by the flow rate (partial pressure) of the C 2 F 6 gas source introduced to the process.
  • the use of N 2 0 as the oxidizing gas source also leaves behind nitrogen in the film being produced.
  • the addition of nitrogen to the film changes the doped silicon dioxide film to a doped oxynitride film.
  • the oxynitride film provides a barrier to water and hydroxyl diffusion, thus allowing a more stable, lower dielectric constant film to be formed. Higher concentrations of fluorine can be added to the oxynitride film above that of a standard fluorine doped silicon dioxide film to produce a final film with a lower dielectric constant.
  • Figure 2-4 illustrate, in simplified fashion, the steps of the method of the invention.
  • a silicon oxide film containing fluorine, carbon and nitrogen having a given dielectric constant is formed by CVD method using a source gas containing at least silicon, nitrogen, oxygen, carbon and fluorine contributors.
  • the Si substrate 31 is mounted on the electrode 25, followed by heating the substrate 31 to between 300°C-500°C with a resistance heater.
  • a tetraethoxy silicate (TEOS) gas, N 2 0 as an oxidizing source gas and C 2 F 6 as a fluorine source gas are simultaneously introduced into the chamber interior 13 at flow rates in the range of 4 to 10 L/min for C 2 F 6) 5 to 12 L/min for N 2 0, 0.8 to 3 L min for TEOS and 0.01 to 5 L/min for 0 2 , respectively so as to set up a pressure of 10 microTorr to 1 atmosphere within the chamber.
  • Particularly preferred gas flow rates are 6 L ⁇ nin for C 2 F 6 , 10 L/min for N 2 0, 2.8 L/min for TEOS and 0.05 L/min fo ⁇ O at a low relative pressure of about 2.6 Torr within the chamber interior 13.
  • the ratio of N 2 0 to 0 2 in the source gases can be in the range of 1 :1 to 1200:1 with a preferable setting of 200:1.
  • the total RF power supplied to the electrode 23 can be in the range of 0.1 to 2.5 KWatt with a preferred setting of 0.5 KWatts in order to cause a discharge and, thus, to form a doped oxynitride, Si0 2 like, film 33 ( Figure 2) on the St substrate 35.
  • the ratio of the low frequency power, at 300 KHz, to high frequency power at 13.56 MHz was in the range of 6:1 to 1 :1 with a preferable setting of 1.5:1.
  • an aluminum film is formed by any convenient means, for example by physical vapor deposition followed by patterning the aluminum film to form a first aluminum wiring 37 (see Figure 3).
  • a Si0 2 film 39 is formed in the same manner that the film 33 was formed.
  • an aluminum film is formed to cover the second Si0 2 film 39 followed by patterning the aluminum film to form a second aluminum wiring 41 , as in the formation of the first aluminum wiring 37.
  • a Si0 2 film 43 is formed to cover the second aluminum wiring 41.
  • Conventional gap fill processes such as SOG fill, can be used to locally planarize the space between adjacent metal lines. The use of the SOG local gap fill process will require the deposition of two doped oxynitride films to encapsulate the SOG film.
  • a semiconductor device in which a silicon oxide film acts as an insulating film for electrically isolating conductive layers included in the semiconductor device.
  • the silicon oxide film is formed containing fluorine, carbon and nitrogen and having a given dielectric constant value by the CVD method using a source gas which contains at least silicon, nitrogen, carbon, oxygen and fluorine contributors.
  • a source gas which contains at least silicon, nitrogen, carbon, oxygen and fluorine contributors.
  • the given dielectric constant is determined by controlling the relative ratios of N 2 0:0 2 :C 2 F 6 and TEOS as the source gases in the CVD method.
  • the method of the invention also allows silicon oxide films to be produced which have increased dielectric constants to thereby provide a "tunable" dielectric constant oxide.
  • a semiconductor device is manufactured in which a silicon oxide film is formed with regions having a relatively high dielectric constant. The regions of relatively high dielectric constant are used to form capacitors within the semiconductor device.
  • a silicon oxide film is formed containing metal oxides and having a given dielectric constant value by CVD method using a source gas which contains at least silicon, nitrogen and oxygen contributors which are introduced within a reaction chamber.
  • a high dielectric compound is also introduced into the reaction chamber which is preferably selected from the group consisting of either single source or mixtures of alkoxy compounds of the general formula MOR, or titanate compounds of the general formula MTi0 3 and , where M is a alkali or alkaline earth metal, or ferroelectric materials to form a relatively high dielectric constant silicon oxide film.
  • the high dielectric compound can be added to the reaction chamber by liquid or vapor injection into the CVD reaction chamber.
  • the high dielectric compounds added to the reaction chamber have a dielectric constant between about 15 and 12,000.
  • Alkoxy (MOR) or titanate (MTi0 3 or M 2 Ti0 5 ) compounds (where M is an alkali or alkaline earth metal, Ba, Sr, Ca, Mg) or ferroelectric compounds can be used in PECVD or CVD operations to form high dielectric constant oxide or ceramic films. Titanates in the pure form have dielectric constants between 15 to 12,000. The addition of these compounds to an oxynitride or silicon dioxide film will effectively form a composite film with an increased dielectric constant. The final film can be homogeneous, graded or layered.
  • Some typical sources for the high dielectric constant compound are:
  • Strontium Strontium Hexafluoropentanedionate
  • Oxoalkoxides have been formed by thermal condensation of heteralkoxides, alkoxide, titanate or organic salts. The addition of these compounds either by liquid or vapor injection into a CVD or PECVD reactor would produce the desired increase in the dielectric constant of deposited film.
  • an Si substrate is again mounted to an electrode, such as electrode 25 in Figure 1, followed by heating the substrate 31 to between 100°C-900°C, where 500°C is the highest temperature possible for aluminum capacitor electrodes.
  • a tetraethoxy silicate (TEOS) gas, N 2 0 and 0 2 as the oxidizing source gas, and titanium isopropoxide are simultaneously introduced into the chamber interior 13 at flow rates in the range of 0.8 to 2 L/min for TEOS, .01 to 12 Umin for N 2 0, 0.01 to 12 L/min for 0 2 , and 0.01 to 10 L/min for titanium isopropoxide, receptively, so as to set up a pressure of 10 microTorr to 1 atmosphere within the chamber.
  • TEOS tetraethoxy silicate
  • the ratio of N 2 0 to 0 2 in the source gases can be in the range of 0.000008:1 to 1200:1 with a preferable setting of 0.3:1.
  • the total RF power supplied to the electrode 23 can be in the range of 0.1 to 2.5 KWatt with a preferred setting of 0.8 KWatts in order to cause a discharge and, thus, to form a high dielectric constant oxide film 33 (Figure 2) on the Si substrate 35.
  • the ratio of the low frequency power, at 300 KHz, to high frequency power at 13.56 MHz was in the range of 6:1 to 0.1 :1 with a preferable setting of 1 :1.
  • the method of the invention provides a convenient means for tuning the dielectric constant of an oxide film of the type used in the manufacture of semiconductor devices.
  • the dielectric constant of the oxide film can be lowered by doping the film with carbon or fluorine atoms. By lowering the dielectric constant of the oxide film below about 4.0, cross talk between adjacent conductive lines can be minimized.
  • the method of the invention can employ a conventional TEOS as the silicon source gas which allows conformal step coverage. Also, the process can be run on any conventional CVD deposition system.
  • two interconnect lines can be spaced in closer proximity, thereby lowering the operating voltage of the circuit.
  • the use of a PECVD environment is advantageous because of the relatively low temperatures required for metal interconnect lines.
  • a convenient carbon and fluorine source gas is C 2 F 6 . Using this gas, it is possible to reduce the dielectric constant of the silicon oxide film from approximately 4.5 to about 3.5 or lower according to the teaching of the invention.
  • the dielectric constant of the silicon oxide film can be raised to form capacitors within the semiconductor devices.

Abstract

A method is shown for manufacturing a semiconductor device in which a silicon oxide film (33) acts as an insulating film for electrically isolating conductive layers included in the semiconductor device. An oxynitride silicon-oxide-like film (33) is formed containing fluorine, carbon and nitrogen and having a given dielectric constant by CVD method using a source gas which contains at least silicon, nitrogen, carbon, oxygen and fluorine contributors. By controlling the ratio of nitrogen to oxygen in the source gas as used in the CVD method, the ultimate nitrogen, carbon and fluorine concentrations in the film can be controlled and hence the dielectric constant of the film so produced. Similarly a silicon oxide film with high dielectric constant may be formed by adding a high dielectric compound in the CVD chamber.

Description

TUNABLE DIELECTRIC CONSTANT OXIDE AND METHOD OF MANUFACTURE
1. Technical Field
The present invention relates generally to a method of manufacturing semiconductor devices and, specifically, to a method of forming films such as silicon oxide films used in the manufacture of such devices, the films having a tunable dielectric constant.
2. Description of the Related Art
Chemical vapor deposition (CVD) is a commonly used technique for forming thin films and has been widely used as a manufacturing technique in the semiconductor device industry. CVD methods using an organic or inorganic silicon compound gas and an oxidizing gas are well known as methods for forming thin films of silicon oxide. In such semiconductor devices, an insulating film is typically utilized for electrically isolating element wiring. The typical insulating film used in the past was a Si02 film formed by the thermal oxidation of a silicon substrate or a Si02 film formed by chemical vapor deposition under a reduced pressure or atmospheric pressure using gaseous materials such as silane and tetraethoxy silicate (TEOS). Particularly in the case of aluminum wirings, ,Si02 films are preferred for insulation and are formed by CVD techniques using either TEOS or silane and 02 because such Si02 films can be formed under temperatures as low as about 400°C.
As transistors are scaled into the submicron regions in such semiconductor devices, the interconnect spacing between wiring is reduced so that electromagnetic coupling of adjacent metal lines is possible causing errors, noise and, in the extreme case, a non-functioning device. As the space between two adjacent metal lines is shortened in accordance with the miniaturization of the semiconductor circuitry, increased capacitance occurs between the metal lines tending to obstruct the higher operating speed of the semiconductor device, thereby inhibiting the performance improvement offered by the miniaturization of the device. As a result of these shortcomings, it is often important to decrease the dielectric constant of the insulating film which is interposed between two adjacent lines in a semiconductor device. The Si02 film formed by conventional plasma CVD methods typically has a dielectric constant in the range from about 4.0 to 5.0. The higher the dielectric constant of the oxide film, the further the electromagnetic field can penetrate into the dielectric media. By reducing the dielectric constant of the oxide, two interconnect lines can be placed closer in proximity, thus lowering the operating voltage of the transistor because the noise margin thereof can be reduced. It is desirable, therefore, in some instances to reduce the dielectric constant of such films from approximately 4.5 to about 3.0 or lower.
Contrarily, it is sometimes desirable to increase the dielectric constant of the oxide film being formed in semiconductor devices such as capacitors. The higher dielectric constant materials can be used to form regions of capacitance within the integrated circuit. The higher the dielectric constant of the material, the smaller the capacitance region required, resulting in a smaller capacitor, thereby equating to an area savings.
The dielectric constant of oxides can be lowered by the addition of carbon or fluorine into the oxide. While this general principle has been stated in the prior art, the previous attempts to provide a film having a lowered dielectric constant have exhibited various deficiencies. For example, in Japanese Patent Application No. 2-77127, fluorine is introduced into SiOz by means of ion implantation. However, it is necessary to apply a heat treatment at a temperature of at least about 600 °C within the Si02 layer. Thus, the Si02 layer formed by this method cannot be used for isolation of aluminum wirings within semiconductor devices.
In United States Patent No. 5,429,995, issued July 4, 1995 and assigned to Kabushiki Kaisha Toshiba, a method is shown for manufacturing a semiconductor device with a film which exhibits a low dielectric constant which uses FSi(OC2H5)3 as the silicon source gas. A particular object of the invention was to provide an insulating film having low hygroscopicity. It would be desirable, however, to use as the organic silicon source gas a conventional TEOS to allow conformal coverage and to provide a process which can be run on any of the conventional PECVD type deposition systems.
Additionally, in certain of the prior art techniques, it has been difficult to control accurately the fluorine concentration in the Si02 film.
Accordingly, it is an object of the present invention to provide a method for forming a Si02 film which has a tunable dielectric constant and which is formed by conventional plasma CVD methods using TEOS as the silicon source gas or which is formed by either HDP (high density plasma) or atmospheric pressure chemical vapor deposition (APCVD) methods using a silane as the source gas.
Another object of the invention is to provide a method for manufacturing a semiconductor device in which a silicon oxide film containing fluorine and carbon is produced, the film acting as an insulating film for electrically isolating conductive layers included in the semiconductor device, the film being formed by plasma CVD technique using an organic silicon gas as a starting material.
Another object of the invention is to provide basic nitrogen incorporation to act as a moisture and OH barrier for the activating film.
Another object of the invention is to provide a lower dielectric constant film which is stable with higher concentrations of fluorine incorporated into the film.
Another object of the invention is to provide a method of manufacturing semiconductor devices in which the conductive layers on the silicon oxide films so produced have improved reliability.
3. Summary of the Invention
A method for manufacturing a semiconductor device is shown in which a silicon oxide film acts as an insulating film for electrically isolating conductive layers included in the semiconductor device. A silicon oxide film is formed containing fluorine and having a given dielectric constant by CVD method using a source gas containing at least silicon, nitrogen, carbon, oxygen and fluorine contributors. The ratio of nitrogen to oxygen in the source gases used in the CVD method is controlled in order to control the ultimate carbon and fluorine concentrations and hence the dielectric constant of the silicon oxide film so produced. The addition of nitrogen to the film also acts as a barrier to the diffusion of H20 or OH into the film in subsequent processing steps. Preferably, the source gases, in addition to a silicon contributor include N20, 02 and C2F6. The given dielectric constant and moisture barrier properties of the silicon oxide film are determined by controlling the relative ratios of N20:02:C2F6 and high frequency to low frequency power applied, with silane SHX or NHX as the source gases in the CVD method. The silicon source can be a conventional TEOS. N20 can be used as the nitrogen contributor in the source gas to add nitrogen to the silicon oxide film which is formed in order to improve reliability of the film when used in a semiconductor device.
A method is also shown for manufacturing a semiconductor device in which a silicon oxide film is formed with regions having a relatively high dielectric constant, the regions of relatively high dielectric constant being used to form capacitors within the semiconductor device. In this aspect of the invention, a silicon oxide film can be formed containing fluorine and having a given dielectric constant value by plasma CVD method using a source gas containing at least silicon, nitrogen, carbon, oxygen and fluorine contributors introduced within a reaction chamber. A high dielectric compound can also be introduced into the reaction chamber to form the relatively high dielectric constant silicon oxide film. The high dielectric compound is preferably selected from the group consisting of either a single source or mixtures of alkoxy compounds of the general formula MOR, or titanate compounds of the general formula MTi03 and M2Ti05, where M is an alkali or alkaline earth metal, or ferroelectric materials. The high dielectric compound can be added to the reaction chamber by liquid or vapor injection into the CVD reaction chamber. The high dielectric compounds added to the reaction chamber typically have dielectric constants between 15 and 12,000.
The above as well as additional objectives, features, and advantages of the present invention will become apparent in the following detailed written description.
4. Brief Description of the Drawings The novel features believed characteristic of the invention are set forth in the appended claims. The invention itself, however, as well as a preferred mode of use, further objectives and advantages thereof, will best be understood by reference to the following detailed description of an illustrative embodiment when read in conjunction with the accompanying drawings, wherein: Figure 1 is a simplified, schematic view of a plasma CVD chamber of the type used in the method of the present invention;
Figures 2-4 are simplified, cross-sectional views showing the steps employed in manufacturing a semiconductor device of the invention; and
Figures 5-6 are graphs of the carbon, fluorine and nitrogen concentrations of Si02 films formed by conventional methods and formed with the tunable dielectric constants of the invention, respectively.
5. Detailed Description of the Preferred Embodiment
Figure 1 shows a parallel plate type plasma CVD apparatus of the type which can be used in practicing the method of the invention. A gas within the chamber interior 13 is discharged to the exterior thereof by means of a suitable pump 15. Appropriately selected source gases are introduced into the chamber interior 13 by means of a plurality of quartz nozzles 17, 19, 21. A set of parallel plate electrodes 23, 25 are mounted within the chamber interior 13. A variable frequency power source 27 is connected to the top electrode 23 with the bottom electrode 25 being connected to a ground potential point 29. A Si substrate 31 is mounted on the lower electrode 25.
The dielectric constant of the oxide films produced according to the present method can be "tuned" by the selective addition of carbon, nitrogen or fluorine or all of the aforementioned to the oxide film. The process of the invention allows the deposition of a conformal TEOS film which has been doped using carbon, nitrogen and fluorine. The process controls the percentage of carbon and fluorine that is added to the film in order to selectively "tune" the resulting dielectric constant of the film. The film doped only with carbon, fluorine and nitrogen has shown improved transistor reliability performance over standard~ox.de films. One advantage of the present method is that the starting gases can employ TEOS as the silicon source, thereby allowing conformal step coverage. The process can be run using any plasma enhanced chemical vapor deposition (PECVD) deposition system, such as the radio frequency plasma assisted CVD system shown in Figure 1. Atmospheric or high density plasma systems may also be used to apply this film.
The process of the invention preferably utilizes tetraethoxy silicate (TEOS) as the silicon source, although other silicon sources could be utilized besides TEOS. Other silicon sources include, for example, HSi(N(CH2)2)3; Si(N(CH3)2)4; (CH3)3SiN3; and SiH4 or mixtures thereof. The preferred oxidizing source gases are N20 and although other sources of oxidizing gas could be utilized, as well, including NO, NH3, 02, or a combination of these gases.
A preferred fluorine source gas is C2F& Other fluorine source gases which could be used include SiF4, CF4 and mixtures thereof, or any other fluorine gaseous source conveniently available.
By using N20 alone or as one of the oxidizing source gases, TEOS is not fully oxidized, leaving carbon behind in the film being produced. By reacting N20 and 02 within selected percentages with TEOS, different percentages of carbon can be left behind in the film. The percentage of fluorine and carbon added to the film is controlled by the flow rate (partial pressure) of the C2F6 gas source introduced to the process. The use of N20 as the oxidizing gas source also leaves behind nitrogen in the film being produced. Using the techniques of the invention, it is possible to reduce the dielectric constant of the silicon film being produced from around 4.5 to about 3.5, or lower. The addition of nitrogen to the film changes the doped silicon dioxide film to a doped oxynitride film. The oxynitride film provides a barrier to water and hydroxyl diffusion, thus allowing a more stable, lower dielectric constant film to be formed. Higher concentrations of fluorine can be added to the oxynitride film above that of a standard fluorine doped silicon dioxide film to produce a final film with a lower dielectric constant. Figure 2-4 illustrate, in simplified fashion, the steps of the method of the invention. A silicon oxide film containing fluorine, carbon and nitrogen having a given dielectric constant is formed by CVD method using a source gas containing at least silicon, nitrogen, oxygen, carbon and fluorine contributors. With reference to Figure 1, the Si substrate 31 is mounted on the electrode 25, followed by heating the substrate 31 to between 300°C-500°C with a resistance heater. Under these conditions, a tetraethoxy silicate (TEOS) gas, N20 as an oxidizing source gas and C2F6 as a fluorine source gas are simultaneously introduced into the chamber interior 13 at flow rates in the range of 4 to 10 L/min for C2F6) 5 to 12 L/min for N20, 0.8 to 3 L min for TEOS and 0.01 to 5 L/min for 02, respectively so as to set up a pressure of 10 microTorr to 1 atmosphere within the chamber. Particularly preferred gas flow rates are 6 LΛnin for C2F6, 10 L/min for N20, 2.8 L/min for TEOS and 0.05 L/min foζ O at a low relative pressure of about 2.6 Torr within the chamber interior 13. The ratio of N20 to 02 in the source gases can be in the range of 1 :1 to 1200:1 with a preferable setting of 200:1. Also, the total RF power supplied to the electrode 23 can be in the range of 0.1 to 2.5 KWatt with a preferred setting of 0.5 KWatts in order to cause a discharge and, thus, to form a doped oxynitride, Si02 like, film 33 (Figure 2) on the St substrate 35. The ratio of the low frequency power, at 300 KHz, to high frequency power at 13.56 MHz was in the range of 6:1 to 1 :1 with a preferable setting of 1.5:1. In succeeding step, an aluminum film is formed by any convenient means, for example by physical vapor deposition followed by patterning the aluminum film to form a first aluminum wiring 37 (see Figure 3). Next, a Si02 film 39 is formed in the same manner that the film 33 was formed. Additionally, an aluminum film is formed to cover the second Si02 film 39 followed by patterning the aluminum film to form a second aluminum wiring 41 , as in the formation of the first aluminum wiring 37. Finally, a Si02 film 43 is formed to cover the second aluminum wiring 41. Conventional gap fill processes, such as SOG fill, can be used to locally planarize the space between adjacent metal lines. The use of the SOG local gap fill process will require the deposition of two doped oxynitride films to encapsulate the SOG film. Thus, in the method of the invention, a semiconductor device can be manufactured in which a silicon oxide film acts as an insulating film for electrically isolating conductive layers included in the semiconductor device. The silicon oxide film is formed containing fluorine, carbon and nitrogen and having a given dielectric constant value by the CVD method using a source gas which contains at least silicon, nitrogen, carbon, oxygen and fluorine contributors. By controlling the ratio of nitrogen to oxygen in the source gases used in the CVD method, the ultimate carbon and fluorine concentrations and hence the dielectric constant of the silicon oxide film can be controlled. Figures 5 and 6.are graphical representations of the carbon, fluorine and nitrogen concentrations versus the depth in microns of the films formed using TEOS and a conventional source gas mixture and formed using the controlled source gas mixture of the invention, respectively.
Preferably, the given dielectric constant is determined by controlling the relative ratios of N20:02:C2F6 and TEOS as the source gases in the CVD method.
The method of the invention also allows silicon oxide films to be produced which have increased dielectric constants to thereby provide a "tunable" dielectric constant oxide. In this aspect of the invention, a semiconductor device is manufactured in which a silicon oxide film is formed with regions having a relatively high dielectric constant. The regions of relatively high dielectric constant are used to form capacitors within the semiconductor device. A silicon oxide film is formed containing metal oxides and having a given dielectric constant value by CVD method using a source gas which contains at least silicon, nitrogen and oxygen contributors which are introduced within a reaction chamber. A high dielectric compound is also introduced into the reaction chamber which is preferably selected from the group consisting of either single source or mixtures of alkoxy compounds of the general formula MOR, or titanate compounds of the general formula MTi03 and
Figure imgf000011_0001
, where M is a alkali or alkaline earth metal, or ferroelectric materials to form a relatively high dielectric constant silicon oxide film. The high dielectric compound can be added to the reaction chamber by liquid or vapor injection into the CVD reaction chamber. The high dielectric compounds added to the reaction chamber have a dielectric constant between about 15 and 12,000.
Alkoxy (MOR) or titanate (MTi03 or M2Ti05) compounds (where M is an alkali or alkaline earth metal, Ba, Sr, Ca, Mg) or ferroelectric compounds can be used in PECVD or CVD operations to form high dielectric constant oxide or ceramic films. Titanates in the pure form have dielectric constants between 15 to 12,000. The addition of these compounds to an oxynitride or silicon dioxide film will effectively form a composite film with an increased dielectric constant. The final film can be homogeneous, graded or layered. Some typical sources for the high dielectric constant compound are:
Barium:
Barium hexafluoropentane-Dionate
Barium Isopropoxide
Barium Isopropoxide Barium II Methoxypropoxide
Barium 2,4-Pentanedionate
Barium II 2,2,6,6-Tetramethyl-3,5-Heptanedionate
Barium II 2,2,6,6-Tetramethyl-3,5-heptanedionate
Calcium:
Calcium ethoxide
Calcium Hexafluoropentanedionate Calcium Methoxide Calcium Methoxyethoxide
Calcium 2,4-Pentanedionate
Calcium 2,2,6, 6-Tetramethyl-3,5-Heptanedionate
Magnesium: Magnesium Ethoxide
Magnesium Hexafluoropentanedionate
Magnesium Methoxide
Magnesium Methoxypropoxide
Magnesium Methyl Carbonate Magnesium 2,4-Pentanedionate
Magnesium n-Propoxide
Magnesium trifluopentanedionate
Strontium: Strontium Hexafluoropentanedionate
Strontium Isopropoxide Strontium Methoxypropoxide Strontium 2,4-Pentanedionate Strontium 2, 2, 6,6-Tetramethyl-3,5-Heptanedionate
Titanium:
Poly(Dibutyltitanate) Diethoxysiloxane-Ethyltitanate Poly (Octylenegylcoltitanate)
Heterometallic or Double Metal Alkoxides: Barium Titanium, BaTi(OR)x Magnesium Titanium, MgTi(OR)x Strontium Titanium, SrTi(OR)x
Oxoalkoxides have been formed by thermal condensation of heteralkoxides, alkoxide, titanate or organic salts. The addition of these compounds either by liquid or vapor injection into a CVD or PECVD reactor would produce the desired increase in the dielectric constant of deposited film.
In the second embodiment of the invention, in which the dielectric constant of the resultant film is increased, an Si substrate is again mounted to an electrode, such as electrode 25 in Figure 1, followed by heating the substrate 31 to between 100°C-900°C, where 500°C is the highest temperature possible for aluminum capacitor electrodes. Under these conditions, a tetraethoxy silicate (TEOS) gas, N20 and 02 as the oxidizing source gas, and titanium isopropoxide are simultaneously introduced into the chamber interior 13 at flow rates in the range of 0.8 to 2 L/min for TEOS, .01 to 12 Umin for N20, 0.01 to 12 L/min for 02, and 0.01 to 10 L/min for titanium isopropoxide, receptively, so as to set up a pressure of 10 microTorr to 1 atmosphere within the chamber. The preferable gas flow rates 0.8 L min for TEOS, 2 L/min for N20, 6 Umin for O^ and 0.5 L/min for titanium isopropoxide, at a low relative pressure of about 1.8 Torr within the chamber interior 13. The ratio of N20 to 02 in the source gases can be in the range of 0.000008:1 to 1200:1 with a preferable setting of 0.3:1. Also, the total RF power supplied to the electrode 23 can be in the range of 0.1 to 2.5 KWatt with a preferred setting of 0.8 KWatts in order to cause a discharge and, thus, to form a high dielectric constant oxide film 33 (Figure 2) on the Si substrate 35. The ratio of the low frequency power, at 300 KHz, to high frequency power at 13.56 MHz was in the range of 6:1 to 0.1 :1 with a preferable setting of 1 :1.
An invention has been shown with several advantages. The method of the invention provides a convenient means for tuning the dielectric constant of an oxide film of the type used in the manufacture of semiconductor devices. The dielectric constant of the oxide film can be lowered by doping the film with carbon or fluorine atoms. By lowering the dielectric constant of the oxide film below about 4.0, cross talk between adjacent conductive lines can be minimized. The method of the invention can employ a conventional TEOS as the silicon source gas which allows conformal step coverage. Also, the process can be run on any conventional CVD deposition system.
By reducing the dielectric constant of the oxide film, two interconnect lines can be spaced in closer proximity, thereby lowering the operating voltage of the circuit. The use of a PECVD environment is advantageous because of the relatively low temperatures required for metal interconnect lines. A convenient carbon and fluorine source gas is C2F6. Using this gas, it is possible to reduce the dielectric constant of the silicon oxide film from approximately 4.5 to about 3.5 or lower according to the teaching of the invention. By adding an appropriate high dielectric constant compound to the reaction chamber, the dielectric constant of the silicon oxide film can be raised to form capacitors within the semiconductor devices.
While the invention has been shown in only two of its forms, it is not thus limited but is susceptible to various changes and modifications without departing from the spirit thereof.

Claims

CLAIMS:What is claimed is:
1. A method for manufacturing a semiconductor device in which a silicon oxide film acts as an insulating film for electrically isolating conductive layers included in the semiconductor device, the method comprising the steps of:
forming a silicon oxide film containing fluorine, carbon and nitrogen and having a given dielectric constant by CVD method using a source gas containing at least silicon, nitrogen, carbon, oxygen and fluorine contributors; and
controlling the ratio of nitrogen to oxygen in the source gases used in the CVD method to control the ultimate carbon and fluorine concentrations and hence the dielectric constant, final film stability and transistor reliability of the 5 final oxynitride, silicon-oxide-like film so produced.
2. The method of claim 1 , wherein the source gases, in addition to a silicon contributor, include N20, 02 and C2F6 and wherein the given dielectric constant is determined by controlling the relative ratios of N20:02:C2F6 as the source 0 gases in the CVD method.
3. The method of claim 2, wherein the silicon source is selected from the group consisting of conventional TEOS and silane.
5 4. The method of claim 3, wherein the film deposition methods is selected from the group consisting of plasma enhanced, atmospheric or HPD deposition methods.
5. A method for manufacturing a semiconductor device in which a silicon o oxide film acts as an insulating film for electrically isolating conductive layers included in the semiconductor device, the method comprising the steps of: forming a silicon oxide film containing fluorine by plasma CVD method using a source gas containing at least silicon, nitrogen, carbon, oxygen and fluorine contributors; and
wherein N20 is used as the nitrogen contributor in the source gas to add nitrogen to the silicon oxide film which is formed in order to improve reliability or the film when used in a semiconductor device.
6. The method of claim 5, wherein the silicon oxide film which is formed has a given dielectric constant and wherein the source gases, in addition to a silicon source, include N20, 02 and C2F6, the dielectric constant of the silicon oxide film being determined by controlling the relative ratios of N20:02:C2F6 and the silicon source gas in the CVD method.
7. A method for manufacturing a semiconductor device in which a silicon oxide film is formed with regions having a relatively high dielectric constant, the regions of relatively high dielectric constant being used to form capacitors within the semiconductor device, the method comprising the steps of:
forming a silicon oxide film containing a metal oxide and having a given dielectric constant by plasma CVD method using a source gas containing at least silicon, nitrogen and oxygen contributors introduced within a reaction chamber; and
further introducing to the reaction chamber a high dielectric compound selected from the group consisting of alkoxy compounds of the general formula MOR and titanate compounds of the general formula MTi03 and M2Ti05, where M is an alkali or alkaline earth metal, and ferroelectric compounds, to form a relatively- high dielectric constant silicon oxide film.
8. The method of claim 7, wherein the high dielectric compound added to the reaction chamber is added by liquid or vapor injection to the CVD reaction chamber.
9. The method of claim 8, wherein the high dielectric compounds added to the reaction chamber have dielectric constants between 15 and 12,000.
10. A product made in accordance with the method of claim 1.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1037271A2 (en) * 1999-03-17 2000-09-20 Canon Sales Co., Inc. Method for forming an interlayer insulating film, and semiconductor device
DE10085212B4 (en) * 1999-11-30 2008-11-20 Intel Corporation, Santa Clara Dielectric layer, integrated circuit and method of making the same

Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6627532B1 (en) * 1998-02-11 2003-09-30 Applied Materials, Inc. Method of decreasing the K value in SiOC layer deposited by chemical vapor deposition
US6426233B1 (en) * 1999-08-03 2002-07-30 Micron Technology, Inc. Uniform emitter array for display devices, etch mask for the same, and methods for making the same
US6943392B2 (en) * 1999-08-30 2005-09-13 Micron Technology, Inc. Capacitors having a capacitor dielectric layer comprising a metal oxide having multiple different metals bonded with oxygen
US6592980B1 (en) * 1999-12-07 2003-07-15 Air Products And Chemicals, Inc. Mesoporous films having reduced dielectric constants
US6365266B1 (en) * 1999-12-07 2002-04-02 Air Products And Chemicals, Inc. Mesoporous films having reduced dielectric constants
US6693033B2 (en) 2000-02-10 2004-02-17 Motorola, Inc. Method of removing an amorphous oxide from a monocrystalline surface
US6558517B2 (en) * 2000-05-26 2003-05-06 Micron Technology, Inc. Physical vapor deposition methods
WO2002003437A1 (en) * 2000-06-30 2002-01-10 Motorola, Inc., A Corporation Of The State Of Delaware Hybrid semiconductor structure and device
US6555946B1 (en) 2000-07-24 2003-04-29 Motorola, Inc. Acoustic wave device and process for forming the same
US6590236B1 (en) 2000-07-24 2003-07-08 Motorola, Inc. Semiconductor structure for use with high-frequency signals
US6638838B1 (en) 2000-10-02 2003-10-28 Motorola, Inc. Semiconductor structure including a partially annealed layer and method of forming the same
US6501121B1 (en) * 2000-11-15 2002-12-31 Motorola, Inc. Semiconductor structure
US6673646B2 (en) 2001-02-28 2004-01-06 Motorola, Inc. Growth of compound semiconductor structures on patterned oxide films and process for fabricating same
US6472333B2 (en) 2001-03-28 2002-10-29 Applied Materials, Inc. Silicon carbide cap layers for low dielectric constant silicon oxide layers
US6482754B1 (en) * 2001-05-29 2002-11-19 Intel Corporation Method of forming a carbon doped oxide layer on a substrate
US6709989B2 (en) 2001-06-21 2004-03-23 Motorola, Inc. Method for fabricating a semiconductor structure including a metal oxide interface with silicon
US20030017266A1 (en) * 2001-07-13 2003-01-23 Cem Basceri Chemical vapor deposition methods of forming barium strontium titanate comprising dielectric layers, including such layers having a varied concentration of barium and strontium within the layer
US6838122B2 (en) 2001-07-13 2005-01-04 Micron Technology, Inc. Chemical vapor deposition methods of forming barium strontium titanate comprising dielectric layers
US6646293B2 (en) 2001-07-18 2003-11-11 Motorola, Inc. Structure for fabricating high electron mobility transistors utilizing the formation of complaint substrates
US6693298B2 (en) 2001-07-20 2004-02-17 Motorola, Inc. Structure and method for fabricating epitaxial semiconductor on insulator (SOI) structures and devices utilizing the formation of a compliant substrate for materials used to form same
US6667196B2 (en) 2001-07-25 2003-12-23 Motorola, Inc. Method for real-time monitoring and controlling perovskite oxide film growth and semiconductor structure formed using the method
US6589856B2 (en) 2001-08-06 2003-07-08 Motorola, Inc. Method and apparatus for controlling anti-phase domains in semiconductor structures and devices
US6639249B2 (en) 2001-08-06 2003-10-28 Motorola, Inc. Structure and method for fabrication for a solid-state lighting device
US6673667B2 (en) 2001-08-15 2004-01-06 Motorola, Inc. Method for manufacturing a substantially integral monolithic apparatus including a plurality of semiconductor materials
US7011978B2 (en) 2001-08-17 2006-03-14 Micron Technology, Inc. Methods of forming capacitor constructions comprising perovskite-type dielectric materials with different amount of crystallinity regions
US6887780B2 (en) 2001-08-31 2005-05-03 Intel Corporation Concentration graded carbon doped oxide
US6677253B2 (en) 2001-10-05 2004-01-13 Intel Corporation Carbon doped oxide deposition
JP3749162B2 (en) * 2001-12-05 2006-02-22 キヤノン販売株式会社 Manufacturing method of semiconductor device
JP2003273325A (en) * 2002-03-15 2003-09-26 Oki Electric Ind Co Ltd Semiconductor device and its manufacturing method
US6916717B2 (en) * 2002-05-03 2005-07-12 Motorola, Inc. Method for growing a monocrystalline oxide layer and for fabricating a semiconductor device on a monocrystalline substrate
US6885345B2 (en) * 2002-11-14 2005-04-26 The Penn State Research Foundation Actively reconfigurable pixelized antenna systems
US20050214457A1 (en) * 2004-03-29 2005-09-29 Applied Materials, Inc. Deposition of low dielectric constant films by N2O addition
CN101473064B (en) * 2006-06-16 2012-08-29 东丽工程株式会社 Silicon thin-film and method of forming silicon thin-film
DE102007004844B4 (en) * 2007-01-31 2011-05-05 Infineon Technologies Ag Method for producing a component and component
US7955994B2 (en) * 2007-10-18 2011-06-07 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing semiconductor device, semiconductor device, and electronic appliance
US20090175378A1 (en) * 2008-01-08 2009-07-09 Robert Bogdan Staszewski System and Method for Impedance Mismatch Compensation in Digital Communications Systems
WO2012128044A1 (en) * 2011-03-23 2012-09-27 株式会社日立国際電気 Semiconductor device manufacturing method, substrate processing method, and substrate processing device
JP2019057634A (en) * 2017-09-21 2019-04-11 東芝メモリ株式会社 Manufacturing method for semiconductor device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0677145A (en) * 1992-08-27 1994-03-18 Toshiba Corp Thin film formation
US5429995A (en) * 1992-07-17 1995-07-04 Kabushiki Kaisha Toshiba Method of manufacturing silicon oxide film containing fluorine
US5470398A (en) * 1990-09-25 1995-11-28 Matsushita Electric Industrial Co., Ltd. Dielectric thin film and method of manufacturing same
JPH08213386A (en) * 1995-02-08 1996-08-20 Fujitsu Ltd Manufacture of semiconductor device

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6235562A (en) * 1985-08-08 1987-02-16 Nec Corp Semiconductor device
US5145711A (en) 1987-08-10 1992-09-08 Semiconductor Energy Laboratory Co., Ltd. Cyclotron resonance chemical vapor deposition method of forming a halogen-containing diamond on a substrate
US5275850A (en) 1988-04-20 1994-01-04 Hitachi, Ltd. Process for producing a magnetic disk having a metal containing hard carbon coating by plasma chemical vapor deposition under a negative self bias
WO1989011556A1 (en) 1988-05-28 1989-11-30 Sumitomo Electric Industries, Ltd. Process for vapor-phase synthesis of diamond
JPH04261439A (en) 1991-02-14 1992-09-17 Semiconductor Energy Lab Co Ltd Organic composite material
US5198263A (en) 1991-03-15 1993-03-30 The United States Of America As Represented By The United States Department Of Energy High rate chemical vapor deposition of carbon films using fluorinated gases
JPH04341568A (en) 1991-05-16 1992-11-27 Toshiba Corp Method for forming thin film and device therefor
JP2699695B2 (en) * 1991-06-07 1998-01-19 日本電気株式会社 Chemical vapor deposition
CA2072384A1 (en) 1991-08-29 1993-03-01 Clifford L. Spiro Carbon fluoride compositions
US5423945A (en) 1992-09-08 1995-06-13 Applied Materials, Inc. Selectivity for etching an oxide over a nitride
US5296258A (en) 1992-09-30 1994-03-22 Northern Telecom Limited Method of forming silicon carbide
US5324690A (en) 1993-02-01 1994-06-28 Motorola Inc. Semiconductor device having a ternary boron nitride film and a method for forming the same
JP3152859B2 (en) * 1994-09-16 2001-04-03 株式会社東芝 Method for manufacturing semiconductor device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5470398A (en) * 1990-09-25 1995-11-28 Matsushita Electric Industrial Co., Ltd. Dielectric thin film and method of manufacturing same
US5429995A (en) * 1992-07-17 1995-07-04 Kabushiki Kaisha Toshiba Method of manufacturing silicon oxide film containing fluorine
JPH0677145A (en) * 1992-08-27 1994-03-18 Toshiba Corp Thin film formation
JPH08213386A (en) * 1995-02-08 1996-08-20 Fujitsu Ltd Manufacture of semiconductor device

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 018, no. 324 (E - 1564) 20 June 1994 (1994-06-20) *
PATENT ABSTRACTS OF JAPAN vol. 096, no. 012 26 December 1996 (1996-12-26) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1037271A2 (en) * 1999-03-17 2000-09-20 Canon Sales Co., Inc. Method for forming an interlayer insulating film, and semiconductor device
EP1037271A3 (en) * 1999-03-17 2001-06-20 Canon Sales Co., Inc. Method for forming an interlayer insulating film, and semiconductor device
US6281113B1 (en) 1999-03-17 2001-08-28 Canon Sales Co., Inc. Method for forming an interplayer insulating film and semiconductor device
DE10085212B4 (en) * 1999-11-30 2008-11-20 Intel Corporation, Santa Clara Dielectric layer, integrated circuit and method of making the same

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