EP0295272A1 - Production de carbure de silicium - Google Patents

Production de carbure de silicium

Info

Publication number
EP0295272A1
EP0295272A1 EP87907809A EP87907809A EP0295272A1 EP 0295272 A1 EP0295272 A1 EP 0295272A1 EP 87907809 A EP87907809 A EP 87907809A EP 87907809 A EP87907809 A EP 87907809A EP 0295272 A1 EP0295272 A1 EP 0295272A1
Authority
EP
European Patent Office
Prior art keywords
process according
silicon
substrate
hydrocarbon
silane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP87907809A
Other languages
German (de)
English (en)
Inventor
Michael John Thwaites
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BP PLC
Original Assignee
BP PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BP PLC filed Critical BP PLC
Publication of EP0295272A1 publication Critical patent/EP0295272A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • 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
    • C23C16/32—Carbides
    • C23C16/325—Silicon carbide
    • 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
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/36—Carbides

Definitions

  • the present invention relates to the production of beta silicon carbide.
  • Beta silicon carbide is a potentially valuable semiconductive material. The virtues of beta silicon carbide are discussed by J.D. Parsons et al in Solid State Technology, November 1985 pages 133 - 138. However, Parson et al point out that the problem with beta silicon carbide is how to grow satisfactory material. Beta silicon carbide has been made by vapour phase epitaxy. However, difficulties have been found in depositing beta silicon carbide particularly on substrates other than beta silicon carbide itself. Parsons et al disclose the chemical vapour deposition of SiC on TiC using ion plating with Si which has been evaporated by an electron beam, and acetylene gas as a source of carbon. Substrate temperatures in excess of 1250°C were required and good quality layers W ⁇ only obtained at temperatures over 1400°C. The necessity to use these high temperatures and a special substrate namely TiC is an undesirable restriction of the process.
  • Beta silicon carbide is a crystalline material. It is possible to produce amorphous alloys of silicon and carbon.
  • US 4 459 163 (McDiarmid and Kiss) disclose the production of amorphous silicon by pyrolitic decomposition of silanes on a substrate at a temperature of 390°C. It is stated that methane may be added to the silane to produce the carbon containing alloy.
  • EP 115 125 discloses the production of an amorphous silicon carbon alloy by subjecting a mixture of silane, methane, and hydrogen to a glow discharge in a chamber at 10 -2 torr and with a substrate at 270oC.
  • amorphous silicon carbon alloys can be deposited at much lower temperatures than are required to make crystalline silicon carbide the resulting alloys do not have the advantageous electronic properties of the crystalline material.
  • FR 2 159 592 states that a monocrystalline layer of beta-silicon carbide may be deposited on monocrystalline silicon by heating a silicon substrate in a mixture of hydrocarbon, silane, and hydrogen fed over the silicon. No details are given of the temperature or pressure conditions used. We have not found it possible to deposit monocrystalline beta-silicon carbide directly on monocrystalline silicon at the relatively low temperatures which are desirable for a commercial process.
  • DE 34 15 799 discloses the deposition of polycrystalline SiC on monocrystalline silicon by chemical vapour deposition followed by deposition of single crystal SiC.
  • the first deposition step is carried out at 800-1200oC, preferably 1000-1100°C atmospheric pressure and the second stage is at 1200-1400°C atmospheric pressure.
  • reduced pressures e.g. 0.01-100 torr (corresponding to a minimum of 1.33 Pa) is mentioned but no examples are given.
  • Chemical vapour deposition has the disadvantage that it is necessary to use high temperatures to obtain satisfactory levels of deposition. At high temperatures close to the melting, point of silicon there will be a greater tendency for contaminants in the substrate to be released and to adversely affect the properties of the silicon carbide layer. The difference in thermal expansion coefficients between the silicon substrate and the SiC layer will also be larger leading to poorer quality. We have now found an improved process for making crystalline beta silicon carbide.
  • a process for the deposition of crystalline beta silicon carbide on a compatible substrate comprises subjecting a mixture of hydrocarbon vapour and a silane to a glow discharge at a partial pressure of hydrocarbon vapour and silane of not more than 1 Pa while maintaining the substrate at a temperature in the range 600 to 1000oC.
  • the substrate is a compatible substrate, ie it must be capable of surviving the conditions used and its lattice structure must be compatible with that of beta silicon carbide.
  • a suitable compatible substrate is TiC. Crystalline silicon is not a compatible substrate.
  • a compatible substrate can be produced by producing a layer on the surface of the crystalline silicon with a composition varying from pure silicon to a composition corresponding to SiC. This may be done in two ways.
  • One method is to introduce carbon into the upper layer of a crystalline silicon substrate by bringing the heated substrate into contact with a hydrocarbon gas while subjecting the gas to a glow discharge.
  • Another method is to deposit an epitaxial silicon layer on the crystalline silicon substrate by glow discharge in a gas mixture containing silane while progressively introducing a hydrocarbon into the reactor to raise the Si:C ratio in successive portions in the layer deposited on the crystalline silicon until it reaches a value corresponding to SiC.
  • the glow discharge process of the present invention is a PECVD process (Plasma Enhanced Chemical Vapour Deposition).
  • An alternative method is to bring the silicon substrate into contact with a hydrocarbon vapour at elevated temperatures e.g. 800°C-1000°C in the absence of a glow discharge and at low pressures e.g. 10 -4 Pa to 10 -2 Pa.
  • the substrate is preferably thoroughly cleaned before use. If the substrate has any tendency to form an oxide film on its surface, which would tend to adversely effect the deposition of the crystalline layer, then the oxide may be removed by heating the substrate in the presence of hydrogen subjected to a glow discharge before any buffer layer, and then the silicon carbide, is deposited.
  • the hydrocarbon vapour is preferably provided by hydrocarbon containing 1 to 7 carbon atoms in the molecule for example methane or ethylene.
  • the silane may for example be SiH 4 .
  • the silicon carbide deposition process may be carried out in the presence of hydrogen.
  • the carbon:silicon ratio of the hydrocarbon/silane mixture are preferably maintained at a value very slightly greater than 1:1 preferably at a value corresponding to a C:(C+Si) ratio in the range 0.5 to 0.7, during the deposition in order to give the desired 1:1 atomic ratio in the SiC.
  • the substrate temperature is preferably in the range 800oC to 1000oC.
  • the total partial pressure of the silane and hydrocarbon must be below 1 Pa, preferably below 0.5 Pa.
  • the total pressure must not of course be sufficiently high to inhibit the initiation of a glow discharge, and is preferably not greater than 1000 Pa.
  • the glow discharge is produced by the application of radio frequency energy. Relatively low frequency radio frequency energy (e.g. about 100 kHz) is used to produce induction heating of substrate holders in some techniques of preparing semi-conductor materials. The frequencies required to produce glow discharges will generally be considerably higher than those used for induction heating e.g. above 1 MHz, preferably above 10 MHz.
  • the duration of the deposition step is dependent on the thickness of the layer required. The invention will now be described with reference to the following examples.
  • Example 1 A pre-cleaned single crystal silicon substrate was clamped on a substrate heater (capable of reaching 1000°C) inside a vertical tube vacuum chamber. The sample was de-gassed at pressures below 10 -6 torr (1.3 x 10 -4 Pa) and at a silicon surface temperature approximately 850°C for 45 minutes. Hydrogen was then introduced into the chamber, bringing the pressure up to 8 x 10 -1 torr (106 Pa). A glow discharge was initiated within the chamber for approximately 30 minutes, to remove the native oxide from the silicon surface. The glow discharge was initiated using high frequency radio frequency energy at a frequency of 13.56 MHz and a power of 30 watts. With the hydrogen discharge still operating the hydrogen flow rate was reduced and a low flow rate of C 2 H 4 was introduced into the reactor.
  • Example 2 The material deposited on the silicon was shown by X-ray diffraction to be crystalline beta silicon carbide with a preferred orientation.
  • Example 2 The material deposited on the silicon was shown by X-ray diffraction to be crystalline beta silicon carbide with a preferred orientation.
  • Example 1 An experiment was carried out as in Example 1 but using methane in place of ethylene. Crystalline beta silicon carbide was produced as in Example 1.
  • Example 3 An experiment was carried out as in Example 1 but with the following differences.
  • the hydrogen discharge was terminated after the oxide removal step.
  • the ethylene vapour was then introduced into the chamber at a pressure of 2 x 10 -4 Pa and the silicon maintained at a temperature of 900oC for 10 minutes.
  • a mixture of ethylene, silane vapour and hydrogen was then introduced into the chamber at a total pressure of 20 Pa (the ratio of ethylene to silane was such as to give a carbonrsilicon atom ratio of 1:0.9.
  • the total partial pressure of ethylene and silane was 0.5 Pa.
  • the discharge was continued for at least 100 minutes as in Example 1.
  • the material deposited on the silicon was shown to be crystalline beta silicon carbide with a preferred orientation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Vapour Deposition (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Du carbure de silicium crystallin sous forme beta est déposé sur un substrat compatible en soumettant un mélange de vapeur d'un carbure d'hydrogène et d'un silane à une décharge sous vide sous une pression partielle de vapeur de carbure d'hydrogène et de silane n'excédant pas 1 Pa, tout en maintenant le substrat à une température de 600° à 1000°C.
EP87907809A 1986-12-10 1987-12-04 Production de carbure de silicium Withdrawn EP0295272A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB868629496A GB8629496D0 (en) 1986-12-10 1986-12-10 Silicon carbide
GB8629496 1986-12-10

Publications (1)

Publication Number Publication Date
EP0295272A1 true EP0295272A1 (fr) 1988-12-21

Family

ID=10608765

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87907809A Withdrawn EP0295272A1 (fr) 1986-12-10 1987-12-04 Production de carbure de silicium

Country Status (5)

Country Link
EP (1) EP0295272A1 (fr)
JP (1) JPH01502182A (fr)
KR (1) KR890700175A (fr)
GB (1) GB8629496D0 (fr)
WO (1) WO1988004333A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2382265C2 (ru) * 2005-03-21 2010-02-20 Оттмар ДИЛЬ Установка для натяжения труб

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69023478T2 (de) * 1990-03-05 1996-06-20 Ibm Verfahren zum Herstellen von Siliziumkarbidschichten mit vorherbestimmter Spannungskraft.
DE4121798A1 (de) * 1991-07-02 1993-01-14 Daimler Benz Ag Mehrschichtige, monokristallines siliziumkarbid enthaltene zusammensetzung
DE4135076A1 (de) * 1991-10-24 1993-04-29 Daimler Benz Ag Mehrschichtige, monokristallines siliziumkarbid enthaltende zusammensetzung
GB2267291B (en) * 1992-05-27 1995-02-01 Northern Telecom Ltd Plasma deposition process
US5465680A (en) * 1993-07-01 1995-11-14 Dow Corning Corporation Method of forming crystalline silicon carbide coatings
KR960012710B1 (ko) * 1993-10-11 1996-09-24 한국화학연구소 단일 유기규소 화합물을 이용한 탄화규소 막의 제조
JPWO2015137389A1 (ja) * 2014-03-11 2017-04-06 コニカミノルタ株式会社 ガスバリアーフィルムの製造方法
JP6488607B2 (ja) * 2014-09-22 2019-03-27 株式会社Sumco 単結晶ＳｉＣウェーハの製造方法
DE102016203324A1 (de) * 2016-03-01 2017-09-07 Evonik Degussa Gmbh Verfahren zur Herstellung eines Silicium-Kohlenstoff-Komposites

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3011912A (en) * 1959-12-22 1961-12-05 Union Carbide Corp Process for depositing beta silicon carbide
JPH0635323B2 (ja) * 1982-06-25 1994-05-11 株式会社日立製作所 表面処理方法
EP0106637B1 (fr) * 1982-10-12 1988-02-17 National Research Development Corporation Eléments optiques transparents aux rayons infrarouges
GB2162862B (en) * 1984-07-26 1988-10-19 Japan Res Dev Corp A method of growing a thin film single crystalline semiconductor
NL8500645A (nl) * 1985-03-07 1986-10-01 Philips Nv Werkwijze voor het afzetten van een laag, die in hoofdzaak uit siliciumcarbide bestaat op een substraat.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8804333A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2382265C2 (ru) * 2005-03-21 2010-02-20 Оттмар ДИЛЬ Установка для натяжения труб

Also Published As

Publication number Publication date
GB8629496D0 (en) 1987-01-21
KR890700175A (ko) 1989-03-10
JPH01502182A (ja) 1989-08-03
WO1988004333A1 (fr) 1988-06-16

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