WO2005121399A1 - Precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides - Google Patents

Precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides Download PDF

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WO2005121399A1
WO2005121399A1 PCT/GB2005/002095 GB2005002095W WO2005121399A1 WO 2005121399 A1 WO2005121399 A1 WO 2005121399A1 GB 2005002095 W GB2005002095 W GB 2005002095W WO 2005121399 A1 WO2005121399 A1 WO 2005121399A1
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precursor
metal
deposition
silicon oxynitride
hnnme
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Anthony Copeland Jones
Megan Ravetz
Paul Williams
Ravi Kanjolia
Rajesh Odedra
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Epichem Limited
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    • 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
    • H01L21/02205—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 the layer being characterised by the precursor material for deposition
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/308—Oxynitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
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    • 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
    • H01L21/0214—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 a silicon oxynitride, e.g. SiON or SiON:H
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    • 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
    • H01L21/02148—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 hafnium, e.g. HfSiOx or HfSiON
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    • 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
    • H01L21/02159—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 zirconium, e.g. ZrSiOx
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    • 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
    • H01L21/0217—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 being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
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    • 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
    • H01L21/02205—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 the layer being characterised by the precursor material for deposition
    • H01L21/02208—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02214—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H01L21/02216—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
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    • 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

Definitions

  • This invention concerns precursors for deposition, of silicon nitride, silicon oxynitride, and metal silicon oxynitrides, such as hafnium silicon oxynitride, methods of making precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides, and methods of depositing silicon nitride, silicon oxynitride and metal silicon oxynitrides.
  • Silicon nitride has a number of attractive properties, such as high electrical resistivity, high dielectric breakdown field, high chemical stability, good diffusion barrier characteristics and superior mechanical strength. These properties render silicon nitride films useful in a wide range of applications, especially in the field of microelectronics.
  • Silicon nitride is also used as a mask for selective oxidation of Si. Silicon nitride has applications in FRONT-END-OF-LINE (FEOL applications) as an advanced gate dielectric (k > 3.8) in metal-nitride-oxide-silicon (MNOS) structures, and as sidewall spacers. Silicon oxynitride, Si x O y N z , films have potential applications in microelectronics, for instance in shallow trench isolation (STI), antireflective coatings (ARCs) and DRA capacitors. Hafnium silicon oxynitride is a promising alternative to Si0 2 as the
  • CMOS complementary metal-oxide-semiconductor
  • LPCVD low pressure chemical vapour deposition techniques
  • Silane and ammonia a hot wall reactor
  • plasma enhanced CVD and jet vapour CVD R.F. Bundish, ed.
  • An object of this invention is to provide alternative precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides, such as hafnium silicon oxynitride at low temperatures.
  • Another object of the present invention is to provide a method for making alternative precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides, such as hafnium silicon oxynitride at low temperatures.
  • a further object of the invention is to provide methods for depositing silicon nitride, silicon oxynitride and metal silicon oxynitrides, such as hafnium silicon oxynitride at low temperatures using alternative precursors.
  • precursors suitable for use in low temperature deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides have the following general formula:
  • R 3 R 5 wherein R 1 , R 2 , R 3 , R 4 and R 5 are selected from H and alkyl groups having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms.
  • R , R , R , R and R are selected from H and alkyl groups having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms comprising reacting a dichlorosilane of the formula R 1 R 2 SiCI 2 with a hydrazine of the formula R 3 HNNR 4 R 5 in appropriate molar quantities, R 1 to R 5 being as defined above.
  • the reaction is preferably carried in a hydrocarbon solvent, such as hexane.
  • R 1 , R 2 , R 3 , R 4 , R 5 are selected from H and alkyl groups having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms.
  • the precursors of the invention may be used alone or with the addition of another nitrogen source, such as ammonia, 1 ,1- dimethylhydrazine (Me 2 NNH 2 ) or tert-butylhydrazine (Bu t NHNH 2 ) for the deposition of silicon nitride.
  • Another nitrogen source such as ammonia, 1 ,1- dimethylhydrazine (Me 2 NNH 2 ) or tert-butylhydrazine (Bu t NHNH 2 ) for the deposition of silicon nitride.
  • the main effects of adding the other nitrogen source are to increase the amount of nitrogen incorporated in the deposited films and to reduce the level of oxygen and carbon contamination.
  • an oxygen source needs to be present, such as oxygen or nitrous oxide, N 2 0.
  • an oxygen and metal source needs to be present.
  • a precursor according to the first aspect of the invention is combined with a suitable metal-oxide precursor.
  • the precursors of the invention it is believed that deposition of SiN and SiON layers may be achieved at growth temperatures in the range of 400 to 600°C.
  • R 1 to R 5 be selected from H, Me, Et, 'Pr and l Bu groups.
  • Preferred precursors according to the invention have R 3 as H and have both R4 and R 5 as Me or R 4 as'Bu and R 5 as H. Examples of preferred precursors according to the invention include
  • the invention is suitable for deposition of a number of metal silicon oxynitrides, such as hafnium silicon oxynitride, HfSiON, and Zirconium silicon oxynitride, ZrSiON.
  • the precursors of the invention may be used in any type of CVD process but they are believed to be particularly suitable for liquid injection chemical vapour deposition.
  • This invention will now be further described by means of the following Examples and with reference to the accompanying drawing, which shows a reactor used in the deposition of silicon nitride and silicon oxynitride described in Example 2 below.
  • Example 1 Preparation of bis(2,2-dimethylhydrazino)ethylsilane The following procedure assumes that all solvents and starting materials have been dried.
  • This reaction may be carried out in other solvents.
  • the precursor/solvent vapour is then carried by argon or argon/oxygen mixture over the heated substrate (20) in the reactor chamber.
  • Oxygen can be added to the argon flow as required.
  • a single supply of high purity argon acts as the carrier gas while safety purges at the exhaust are nitrogen. The same supply of nitrogen is used to control the vacuum level. Nitrogen is also used continuously to purge the exhaust line from the
  • the argon flows to the reactor through the injector assembly via two mass flow controllers (MFC1 0-11/min range or MFC2 0-5lmin range).
  • the argon is used as a carrier gas, to purge the reactor and to bring the reactor up to argon when the vacuum processes are complete.
  • the oxygen flow cannot be obtained unless the argon is flowing.
  • Oxygen when in use, also flows through the injector assembly and is controlled by a single MFC (0- 0.51/min range).
  • Deposition chamber The deposition chamber (16) consists of a horizontal quartz tube with stainless steel door assembly and exhaust outlet.
  • the reactor substrate susceptor (22) is heated using IR radiation (24) and can achieve
  • reactor tube is sized for one IR lamp, however, two lamps can be used either alongside each other to allow increased susceptor size or above and below to increase the temperature.
  • the reactor tube is connected to the injector assembly via a heated gas line (26) to prevent the possible condensation of the precursor or solvent.
  • injector assembly The method used to introduce precursor into the deposition chamber is to dissolve the precursor in a compatible solvent and inject this solution into a hot zone immediately before the reactor. This results in both solvent and precursor vaporising and being carried by the carrier gas (argon and oxygen when required) into the reactor chamber.
  • the injector assembly comprises a reservoir (30), where the precursor/solvent mixture is stored at room temperature prior to injection, a liquid flow meter, so the actual flow of precursor/solvent to the injector can be measured, a BOSCH car fuel injector, through which the precursor/solvent mixture flows, a hot zone, heated by four cartridge heaters, where the precursor/solvent mixture is vaporised and mixed with the carrier gas and oxygen and a gas preheat to heat the carrier gas and oxygen before the injection zone.
  • the fuel injector is also water cooled to prevent premature solvent vaporisation in the fuel injector.
  • Oxygen levels found in the above samples are probably due to residual oxygen either in the precursor or the reactor.
  • HfSiON hafnium silicon oxynitride
  • Typical growth conditions are given in Table 3, and Auger Electron Spectroscopic (AES) data for the HfSiON films are given in Table 4.

Abstract

Precursors for the deposition of silicon nitride, silicon oxynitride and metal silicon oxynitride films, the precursors having the general formula (I) wherein R1, R2, R3, R4, R5 are selected from H and alkyl groups having (1 to 6) carbon atoms.

Description

Title: Precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides
Description
This invention concerns precursors for deposition, of silicon nitride, silicon oxynitride, and metal silicon oxynitrides, such as hafnium silicon oxynitride, methods of making precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides, and methods of depositing silicon nitride, silicon oxynitride and metal silicon oxynitrides. Silicon nitride has a number of attractive properties, such as high electrical resistivity, high dielectric breakdown field, high chemical stability, good diffusion barrier characteristics and superior mechanical strength. These properties render silicon nitride films useful in a wide range of applications, especially in the field of microelectronics. These applications include the chemical passivation and encapsulation of Si bipolar and MOS devices, as it is an extremely good barrier to diffusion of H20 and Na+ ions. Silicon nitride is also used as a mask for selective oxidation of Si. Silicon nitride has applications in FRONT-END-OF-LINE (FEOL applications) as an advanced gate dielectric (k > 3.8) in metal-nitride-oxide-silicon (MNOS) structures, and as sidewall spacers. Silicon oxynitride, SixOyNz, films have potential applications in microelectronics, for instance in shallow trench isolation (STI), antireflective coatings (ARCs) and DRA capacitors. Hafnium silicon oxynitride is a promising alternative to Si02 as the
gate dielectric material in sub-0.1 μm complementary metal-oxide-
semiconductor (CMOS) technology. Currently silicon nitride is deposited by low pressure chemical vapour deposition techniques (LPCVD) in a hot wall reactor at deposition temperatures > 750°C using dichlorosilane and ammonia, G.E. McGuire, Semiconductor and Process Technology Handbook, Noyes Publication, NJ, pp. 289-301 , 1988. The process suffers from the problems of a high deposition temperature and the formation of ammonium chloride leading to particulate contamination. Alternative deposition methods include LPCVD using silane and ammonia, plasma enhanced CVD and jet vapour CVD, R.F. Bundish, ed. Handbook of Deposition Technologies for Films and Coatings, Noyes Publication, pp 446-458, 827-837,1994. However, LPCVD batch processes using silane results in poor uniformity films, and PECVD processes are not favoured in FEOL applications due to plasma damage to the active device regions. Jet vapour deposition techniques are also not favoured due to very low deposition rates. In an effort to solve these problems, a number of precursors, which already contain a silicon nitrogen bond in the molecule, have been investigated. These include bis(tertiary-butyIamino)silane,
Figure imgf000003_0001
R.K. Laxman, T.D. Anderson, J.A. Mestermacher, Solid State Technology, 2000, tris(dimethlyamino)silane, (Me2N)3SiH, R.A.Levy et al. J. Mate. Res., 1996, 11 ,1483, hexamethyl disilazane, (Me2Si)2NH, O.N.Mittov et al., Russ. Microelectronics, 2002, 31 , 13, and methylsilazane, (MeSiHNMe)n, H.Du et al. J. Am. Ceram. Soc, 1990, 73, 764. These precursors are generally used with added NH3 and allow a reduction in growth temperature down to 550°C. An object of this invention is to provide alternative precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides, such as hafnium silicon oxynitride at low temperatures. Another object of the present invention is to provide a method for making alternative precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides, such as hafnium silicon oxynitride at low temperatures. A further object of the invention is to provide methods for depositing silicon nitride, silicon oxynitride and metal silicon oxynitrides, such as hafnium silicon oxynitride at low temperatures using alternative precursors. According to a first aspect of the invention precursors suitable for use in low temperature deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides have the following general formula:
Figure imgf000004_0001
R3 R5 wherein R1, R2, R3, R4 and R5 are selected from H and alkyl groups having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms. According to a second aspect of the invention there is provided a method of preparing precursors of the following general formula:
Figure imgf000005_0001
wherein R , R , R , R and R are selected from H and alkyl groups having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms comprising reacting a dichlorosilane of the formula R1R2SiCI2 with a hydrazine of the formula R3HNNR4R5 in appropriate molar quantities, R1 to R5 being as defined above. The reaction is preferably carried in a hydrocarbon solvent, such as hexane. According to a third aspect of the invention there is provided a method of depositing silicon nitride, silicon oxynitride or a metal silicon oxynitride by chemical vapour deposition (CVD) using a precursor having the following general formula:
R3 . R4 R1 N N'
Figure imgf000005_0002
wherein R1, R2, R3, R4, R5 are selected from H and alkyl groups having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms. The precursors of the invention may be used alone or with the addition of another nitrogen source, such as ammonia, 1 ,1- dimethylhydrazine (Me2NNH2) or tert-butylhydrazine (ButNHNH2) for the deposition of silicon nitride. The main effects of adding the other nitrogen source are to increase the amount of nitrogen incorporated in the deposited films and to reduce the level of oxygen and carbon contamination. For the deposition of silicon oxynitride films, SixOyNz, an oxygen source needs to be present, such as oxygen or nitrous oxide, N20. For the deposition of metal silicon oxynitride films, an oxygen and metal source needs to be present. Preferably, deposition of a metal silicon oxynitride film, a precursor according to the first aspect of the invention is combined with a suitable metal-oxide precursor. With the precursors of the invention it is believed that deposition of SiN and SiON layers may be achieved at growth temperatures in the range of 400 to 600°C. It is preferred that R1 to R5 be selected from H, Me, Et, 'Pr and lBu groups. Preferred precursors according to the invention have R3 as H and have both R4 and R5 as Me or R4 as'Bu and R5 as H. Examples of preferred precursors according to the invention include
bis(dimethylhydrazino)ethyl silane (EtSiH(HNNMe2)2, EtSiH(HNNHBut)2,
H2Si(HNNMe2)2, ButSiH(HNNMe2)2; H2Si(HNNHBut)2 and ButSiH(HNNHBut)2. The invention is suitable for deposition of a number of metal silicon oxynitrides, such as hafnium silicon oxynitride, HfSiON, and Zirconium silicon oxynitride, ZrSiON. Preferably, [EtSiH(HNNMe2)2] is combined with a suitable metal-oxide precursor, such as X(mmp) , X(OBu')2 (mmp)2, where X is a metal and mmp = 1-methoxy-2-methyl-2-propanolate, OCMe2CH2OMe), X(OR)4 (X is a metal, R = alkyl, such as Bu1) or X(NR1R2)4 (X is a metal, R = Me, Et; R2 = Me, Et etc;), with or without a suitable oxidant. The precursors of the invention may be used in any type of CVD process but they are believed to be particularly suitable for liquid injection chemical vapour deposition. This invention will now be further described by means of the following Examples and with reference to the accompanying drawing, which shows a reactor used in the deposition of silicon nitride and silicon oxynitride described in Example 2 below. Example 1 Preparation of bis(2,2-dimethylhydrazino)ethylsilane The following procedure assumes that all solvents and starting materials have been dried.
To ethyldichlorosilane (20g) in hexane (300mls) in a reactor with an overhead stirrer was added 1 ,1-dimethylhydrazine (30g) slowly. As the material was added a reaction was observed with the formation of white solid, 1 ,1-dimethylhdrazonium chloride. After the addition of all the hydrazine the mixture was stirred for a further 1 hour, after which the solution was filtered using a frit. The solvent was removed to give a white solid with clear liquid. To this was added a further 10g of 1 ,1-dimethylhydrazine, during which time the mixture became clear with a single white solid lump. The clear liquid was separated and pumped on to give the final product. Yield of the product was 70-80%.
This reaction may be carried out in other solvents.
Analysis details
MP - -31C
Density - Around 1 Example 2 Growth of Si3N4 using bis(2,2-dimethylhydrazino)ethylsilane using a reactor of the type shown in the accompanying drawing. General Reactor Description The equipment is designed to carry out MOCVD processes at either atmospheric pressure or under vacuum conditions. The precursor under test is dissolved in a suitable solvent (10) and injected into the system where it is transported by an argon or argon/oxygen gas flow (12, 14), usually at low pressure, to a reactor (16) where a film is deposited. The gas system, deposition chamber and injector assembly are briefly described below. Gas system The carrier gas is argon and is passed through the precursor solvent injection assembly (18) where the precursor solution is injected using a car fuel injector. The precursor/solvent vapour is then carried by argon or argon/oxygen mixture over the heated substrate (20) in the reactor chamber. Oxygen can be added to the argon flow as required. A single supply of high purity argon acts as the carrier gas while safety purges at the exhaust are nitrogen. The same supply of nitrogen is used to control the vacuum level. Nitrogen is also used continuously to purge the exhaust line from the
vacuum pump. The argon flows to the reactor through the injector assembly via two mass flow controllers (MFC1 0-11/min range or MFC2 0-5lmin range). The argon is used as a carrier gas, to purge the reactor and to bring the reactor up to argon when the vacuum processes are complete. The oxygen flow cannot be obtained unless the argon is flowing. Oxygen, when in use, also flows through the injector assembly and is controlled by a single MFC (0- 0.51/min range). Deposition chamber The deposition chamber (16) consists of a horizontal quartz tube with stainless steel door assembly and exhaust outlet. The reactor substrate susceptor (22) is heated using IR radiation (24) and can achieve
temperatures of up to 750°C. The paddle assembly/susceptor (22) within the
reactor tube is sized for one IR lamp, however, two lamps can be used either alongside each other to allow increased susceptor size or above and below to increase the temperature. The reactor tube is connected to the injector assembly via a heated gas line (26) to prevent the possible condensation of the precursor or solvent. Injector assembly The method used to introduce precursor into the deposition chamber is to dissolve the precursor in a compatible solvent and inject this solution into a hot zone immediately before the reactor. This results in both solvent and precursor vaporising and being carried by the carrier gas (argon and oxygen when required) into the reactor chamber. The injector assembly comprises a reservoir (30), where the precursor/solvent mixture is stored at room temperature prior to injection, a liquid flow meter, so the actual flow of precursor/solvent to the injector can be measured, a BOSCH car fuel injector, through which the precursor/solvent mixture flows, a hot zone, heated by four cartridge heaters, where the precursor/solvent mixture is vaporised and mixed with the carrier gas and oxygen and a gas preheat to heat the carrier gas and oxygen before the injection zone. The fuel injector is also water cooled to prevent premature solvent vaporisation in the fuel injector. The general growth conditions used for deposition of SiN and SiON using the above-described equipment are given in Table 1 below Table 1 Growth conditions used for deposition of SiN and SiON by liquid injection MOCVD using bis(2,2-dimethylhydrazino)ethylsi!ane, [EtSiH(HNNMe2)2] Reactor pressure ~ 200 Torr
Evaporator temperature 110 - 160°C
Si precursor injection rate 0.5 - 2 cm3 hr"1
Argon carrier gas flow 450 - 500 cm3 min"1
Me2NNH2 bubbler gas flow rate(a) 50 cm3 min"1
Me2NNH2 bubbler temperature ' 10°C
Substrates Single crystal silicon
Substrate temperature 425 - 600°C
NH3 flow rate(b) 500 cm3 min"1 (a) Some growth runs carried out in the presence of Me2NNH2 vapour supplied from a stainless steel bubbler using a separate inlet line. ( ) Some growth runs carried out using NH3 as a carrier gas instead of argon.
Growth of SiN and SiON with various precursor samples under various conditions within the ranges given in the Table and the results are given below in Table 2
Table 2
Sample Precursor Ratio Evaporator Growth Si N C O
No. temperature temp. (°C) (°C)
INT 09 Me2NNH2 / 100:1 110 600 52.0 29.2 6.9 11.9 [EtSiH(HNNMe2)2]
INT 10 Me2NNH2 / 50:1 110 600 54.1 27.9 7.1 10.9 [EtSiH(HNNMe2)2]
INT 12 Me2NNH2 / 100:1 110 550 39.3 21.6 7.0 32.2 [EtSiH(HNNMe2)2]
INT 11 e2NNH2 / 50:1 110 550 39.2 24.1 7.1 29.6 [EtSiH(HNNMe2)2]
INT 17 Me2NNH2 / 50:1 110 500 36.2 18.1 6.1 39.5 [EtSiH(HNNMe2)2]
INT 13 [EtSiH(HNNMe2)2] — 110 600 45.8 20.2 10.1 23.9
INT 15 [EtSiH(HNNMe2)2] — 110 550 43.5 21.8 11.2 23.5
INT 18 [EtSiH(HNNMe2)2] — 140 550 38.9 19.9 11.5 28.5
INT 16 [EtSiH(HNNMe2)2] — 110 500 39.4 20.8 11.2 23.5
INT 19 [EtSiH(HNNMe2)2] — 140 500 37.2 19.7 8.0 33.1
INT 22 [EtSiH(HNNMe2)2] — 160 500 35.8 15.1 7.9 38.9
INT 23 [EtSiH(HNNMe2)2] — 160 475 33.8 15.8 9.7 36.3
INT 24 [EtSiH(HNNMe2)2] — 160 450 37.0 12.4 10.0 39.0 INT 25 [EtSiH(HNNMe2)2] NH3 160 500 48.9 34.6 5.1 11.4 / NH3 Carrier gas
The SiN and SiON films grown by liquid injection MOCVD using [EtSiH(HNNMe2)2] were analysed by Auger electron spectroscopic (AES) (see Table 2) Elemental compositions are given in atomic % (Hydrogen was not analysed for).
Certain conclusions can be made, as follows;
• With [EtSiH(HNNMe2)2] used alone, N incorporation tends to decrease with decreasing substrate temperature, O contamination increases with decreasing substrate temperature and C incorporation appears to be independent of substrate temperature (~ 10 at.-%).
• For the precursor combination, [EtSiH(HNNMe2)2] and NH3 carrier gas there is a large increase in N incorporation, a large reduction in O contamination, with some reduction in carbon levels.
• Oxygen levels found in the above samples are probably due to residual oxygen either in the precursor or the reactor.
The invention also provides a method for the deposition of hafnium silicon oxynitride (HfSiON) thin films, by combining [EtSiH(HNNMe2)2] with a suitable Hf-oxide precursor, preferably Hf(mmp) or Hf(OBut)2(mmp)2 (where mmp = 1-methoxy-2-methyl-2-propanolate, OCMe2CH2OMe), with or without an added oxidant. Other Hf-oxide precursors including Hf(OR)4 (R = alkyl such as Buf) or Hf(NR1R2)4 (R1 = Me, Et; R2 = Me, Et etc.) may also be combined with [EtSiH(HNNMe2)2], with or without an added oxidant, to produce HfSiON. Typical growth conditions are given in Table 3, and Auger Electron Spectroscopic (AES) data for the HfSiON films are given in Table 4.
The invention may also be suitable for the deposition of a number of other metal silicon oxyntrides, such as zirconium silicon oxynitride, ZrSiON, in which [EtSiH(HNNMe2)2] is used in combination with a suitable Zr-oxide precursor, such as Zr(mmp)4 or Zr(OBut)2(mmp)2, Zr(OR)4 (R = alkyl such as Bul) Zr(NR1R2)4 (R1 = Et, Me, R2 = Et, Me etc.), with or without an added oxidant.
Table 3. Typical growth conditions used for the deposition of HfSiON films by liquid injection MOCVD using [Hf(mmp)4 + [EtSiH(HNNMe2)2]
Substrate temperature 300-650°C
Evaporator temperature 160°C
Pressure 50 mbar
Injection rate 4 cm3h"1
Ratio of Hf(mmp)4 : 1 : 1
[EtSiH(HNNMe2)2]
Solvent Nonane
Concentration 0.1 M
Argon flow rate 500 cm3min"1 Oxygen flow rate 0 cm min Run time 1 h Substrates Si(100)
Figure imgf000014_0001

Claims

1. Precursor suitable for use in low temperature deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides having the following general formula:
Figure imgf000015_0001
R3 / X R5 wherein R1, R2, R3, R and R5 are selected from H and alkyl groups having 1 to 6 carbon atoms.
2. Precursor as claimed in claim 1 wherein R1, R2, R3, R4 and R5 is H or an alkyl group having 1 to 4 carbon atoms.
3. Precursor as claimed in claim 1 or claim 2 wherein R1 to R5 is selected from H, Me, Et, 'Pr, *Bu groups.
4. Precursor as claimed in claim 3 wherein R3 is H and R4 and R5 are both Me or R4 is lBu and R5 is H.
5. Precursor as claimed in claim 4 selected from the group consisting of bis(dimethylhydrazino) ethyl silane (EtSiH(HNNMe2)2, EtSiH(HNNHBut)2,
H2Si(HNNMe2)2, ButSiH(HNNMe2)2, H2Si(HNNHBut)2 and Bu'SiHOHNNHBu
6. A method of preparing precursors of the following general formula: Rd R4 \ R1 N N
Figure imgf000016_0001
R3 / R5 wherein R1, R2, R3, R4 and R5 are selected from H and alkyl groups having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms, comprising reacting a dichlorosilane of the formula R1R2SiCI2 with a hydrazine of the formula R3HNNR4R5 in appropriate molar quantities, R1 to R5 being as defined above.
7. A method as claimed in claim 6 wherein the reaction is carried out in a hydrocarbon solvent.
8. A method of depositing silicon nitride, silicon oxynitride or a metal silicon oxynitride by chemical vapour deposition (CVD) using a precursor having the following general formula:
Figure imgf000016_0002
wherei »n-. D R"! , D R2 , i R _)3 , D R4 , D R5
Figure imgf000016_0003
alkyl groups having 1 to 6 carbon atoms.
9. A method as claimed in claim 8 wherein R1, R2, R3, R4, R5 is H or an alkyl group having 1 to 4 carbon atoms.
10. A method as claimed in claim 8 or claim 9 wherein an additional nitrogen source is included for the deposition of silicon nitride.
11. A method as claimed in claim 10 wherein the additional nitrogen source is selected from ammonia, 1 , 1-dimethylhydrazine (Me2 NNH2) or tert-butylhydrazine (Bu*NHNH2).
12. A method as claimed in claim 8 or claim 9 wherein an oxygen source is provided for the deposition of silicon oxynitride.
13. A method as claimed in claim 12 wherein the oxygen source is selected from oxygen and nitrous oxide, N20.
14. A method as claimed in claim 8 or claim 9 wherein an oxygen and metal source is provided for deposition of a metal silicon oxynitride.
15. A method as claimed in claim 14 wherein a metal-oxide precursor is used.
16. A method as claimed in claim 15 wherein the metal oxide precursor is selected from X(mmp) , X(Obu')2 (mmp)2 where X is a metal and mmp = 1- methoxy-2-methyl-2-propanolate, (OCMe2CH2OMe), X(OR)4 where X is a metal, R = alkyl and X(NR1R2) where X is a metal, R1 and R2 = 4 alkyl group, with or without a suitable oxidant.
17. A method as claimed in any one of claims 14 to 16 for the preparation of hafnium silicon oxynitride or zirconium silicon oxynitride.
18. A method as claimed in any one of claims 9 to 17 wherein R1 to R5 of the first precursor is selected from the group consisting of H, M, Et, 'Pr and *Bu groups.
19. A method as claimed in claim 18 wherein R3 is H and R4 and R5 are both Me or R4 is fBu and R5 is H.
20. A method as claimed in claim 19 wherein the first precursor is selected from the group consisting of bis (dimethylhydrazino)ethyl silane,
(EtSiH(HNNMe2)2, EtSiH(HNNHBut)2, H2Si(HNNMe2)2 , ButSiH(HNNMe2)2, H2Si(HNNHBut)2 and ButSiH(HNNHBut)2.
21. A method as claimed in any one of claims 8 to 20 wherein deposition is achieved at a growth temperature in the range 400 to 600°C.
22. A method as claimed in any one of claims 8 to 21 wherein the CVD process is liquid injection chemical vapour deposition.
23. A method of depositing a silicon oxynitride by chemical vapour deposition (CVD) by combining an oxygen source with a precursor having the following general formula:
Figure imgf000018_0001
wherein R1, R2, R3, R4, R5 are selected from H and alkyl groups having 1 to 6 carbon atoms.
24. A method of depositing a metal silicon oxynitride by chemical vapour deposition (CVD) by combining a metal-oxide precursor with a precursor
having the following general formula: R R4 R1 N N
Figure imgf000019_0001
wherein R1, R2, R3, R4, R5 are selected from H and alkyl groups having 1 to 6 carbon atoms.
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GB2432363B (en) 2005-11-16 2010-06-23 Epichem Ltd Hafnocene and zirconocene precursors, and use thereof in atomic layer deposition
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US9028917B2 (en) 2009-08-07 2015-05-12 Sigma-Aldrich Co. Llc High molecular weight alkyl-allyl cobalttricarbonyl complexes and use thereof for preparing dielectric thin films
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US8927748B2 (en) 2011-08-12 2015-01-06 Sigma-Aldrich Co. Llc Alkyl-substituted allyl carbonyl metal complexes and use thereof for preparing dielectric thin films
CN104136448B (en) 2012-01-26 2015-12-02 辛格玛艾瑞契有限责任公司 Molybdenum allyl complex and its purposes in thin film deposition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020130340A1 (en) * 2000-02-11 2002-09-19 Yanjun Ma Method of forming a multilayer dielectric stack
US20030127640A1 (en) * 2002-01-08 2003-07-10 Kabushiki Kaisha Toshiba Semiconductor device and method for manufacturing semiconductor device
US20040043569A1 (en) * 2002-08-28 2004-03-04 Ahn Kie Y. Atomic layer deposited HfSiON dielectric films
EP1441042A1 (en) * 2003-01-23 2004-07-28 Air Products And Chemicals, Inc. Precursors for depositing silicon containing films and processes thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020130340A1 (en) * 2000-02-11 2002-09-19 Yanjun Ma Method of forming a multilayer dielectric stack
US20030127640A1 (en) * 2002-01-08 2003-07-10 Kabushiki Kaisha Toshiba Semiconductor device and method for manufacturing semiconductor device
US20040043569A1 (en) * 2002-08-28 2004-03-04 Ahn Kie Y. Atomic layer deposited HfSiON dielectric films
EP1441042A1 (en) * 2003-01-23 2004-07-28 Air Products And Chemicals, Inc. Precursors for depositing silicon containing films and processes thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 1963, SERGEEVA, S.I.; CHIEN, HSING-CHANG; TSITOVICH, D.D.: "Synthesis of alkyl- and dialkylbis(1,1-dialkylhydrazino)silanes", XP002278438, Database accession no. 61:4288 *
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 2003, RAKHLIN, V. I.; FOMINA, A.N.; MIRSKOV, R.G.; KANAEV, V.G.: "Organosilicon derivatives of 1,1-dimethylhydrazine: novel precursors of thin-film dielectric coatings", XP002339520, Database accession no. 2003:151746 *
DOKLADY CHEMISTRY (TRANSLATION OF THE CHEMISTRY SECTION OF DOKLADY AKADEMII NAUK), vol. 388, no. 4-6, 2003, pages 47 - 49 *
SMIRNOVA T P ET AL: "SiCN alloys obtained by remote plasma chemical vapour deposition from novel precursors", PREPARATION AND CHARACTERIZATION, ELSEVIER SEQUOIA, NL, vol. 429, no. 1-2, 1 April 2003 (2003-04-01), pages 144 - 151, XP004421425, ISSN: 0040-6090 *
ZHURNAL OBSHCHEI KHIMII FROM: CZ 1963 (11), 3947, vol. 30, no. 2, 1960, pages 694 - 695 *

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