WO1994009178A1 - Depot a basse temperature de nitrure de silicium cristallin, ameliore par addition de molybdene - Google Patents

Depot a basse temperature de nitrure de silicium cristallin, ameliore par addition de molybdene Download PDF

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Publication number
WO1994009178A1
WO1994009178A1 PCT/US1993/002140 US9302140W WO9409178A1 WO 1994009178 A1 WO1994009178 A1 WO 1994009178A1 US 9302140 W US9302140 W US 9302140W WO 9409178 A1 WO9409178 A1 WO 9409178A1
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Prior art keywords
molybdenum
silicon
crystalline
composite material
coating
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PCT/US1993/002140
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English (en)
Inventor
Richard A. Lowden
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Martin Marietta Energy Systems, Inc.
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Filing date
Publication date
Application filed by Martin Marietta Energy Systems, Inc. filed Critical Martin Marietta Energy Systems, Inc.
Priority to KR1019950700552A priority Critical patent/KR950703073A/ko
Priority to AU37993/93A priority patent/AU3799393A/en
Publication of WO1994009178A1 publication Critical patent/WO1994009178A1/fr

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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
    • 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
    • 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
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S427/00—Coating processes
    • Y10S427/10—Chemical vapor infiltration, i.e. CVI

Definitions

  • the invention relates to processes for chemical vapor deposition (CVD) of crystalline silicon nitride (usually Si 3 N 4 ), and more particularly to such processes which can operate at relatively low temperatures and involve the addition of molybdenum.
  • CVD chemical vapor deposition
  • the invention also relates to compositions containing crystalline silicon nitride and molybdenum suicide.
  • Si 3 N 4 Silicon nitride can exist in alpha or beta hexagonal structures, the properties of the two differing somewhat. Beta-Si 3 N ( ⁇ -Si 3 N 4 ) is preferred because it generally exhibits higher strength, modulus, and hardness. Si 3 N 4 has high strength at high temperatures, good thermal stress resistance due to its low coefficient of thermal expansion, and high resistance to oxidation when compared to other non-oxides.- These properties thus allow Si 3 N 4 components to be used to higher operating temperatures.
  • Si 3 N 4 materials are abundant, including use in combustion system components such as high temperature turbines, combustion chamber liners, rocket nozzles, and thrust deflectors.
  • the low thermal conductivity of Si 3 N 4 makes it attractive as a thermal barrier, either as a coating or stand-alone component. Its low density allows it to replace superalloys with a 40% weight savings.
  • Silicon nitride's dielectric properties are of interest for use in low observable (stealth) technology.
  • the conventional method for producing Si 3 N 4 is via the hot-pressing of powder. Generally, this requires the addition of a sintering aid which lowers the melting temperature at the grain boundaries to permit consolidation. Thus the ultimate utilization temperature of the component is reduced to well below that of pure Si 3 N 4 , preventing full use of the material's advantages.
  • Hot pressing of Si 3 N 4 with sintering aids such as mixtures of yttria and alumina is typically conducted at temperatures ranging from 1600° C to 2000° C, usually above 1700° C.
  • CND chemical vapor deposition
  • a difficulty in the CVD of Si 3 N 4 is that only amorphous material is deposited below about 1200° C, and near 1200° C crystalline material is deposited at only very low deposition rates (5 um/h). Increasing the deposition rate via increased reactant flow quickly causes the deposit to be amorphous. The only exception is the deposition from highly dilute silane and ammonia, which deposits polycrystalline Si 3 N 4 at 1100 ⁇ C at relatively low rates ( ⁇ 10 um h). Attempts to crystallize deposited amorphous coatings at 1500° C results in the coating disintegrating to a fine powder.
  • amorphous Si 3 N 4 is not desirable for most engineering applications. Deposited amorphous coatings greater than 1 urn in thickness are heavily microcracked. Amorphous material also tends to retain contaminants that result from processing (e.g., HC1).
  • CVI chemical vapor infiltration
  • Raising the CVI processing temperature to at least 1300° C could form crystalline Si 3 N 4 .
  • this is not feasible for CVI.
  • the rate of deposition which is governed by the exponential Arrhenius relation, is too high for effective infiltration to occur.
  • Deposition tends to occur at the outer surface, eventually sealing the porosity thereof and creating a steep density gradient between the entrance surface and the center of the preform.
  • many of the types of ceramic fibers used for CVI processing suffer substantial degradation at temperatures much in excess of 1100 ⁇ C,
  • the deposition temperature for crystalline Si 3 N 4 has been reduced, and/or the physical, chemical, and mechanical properties of the deposit have been altered by the addition of dopants or contaminants.
  • One approach was the addition of titanium in the form of titanium nitride. Titanium tetrachloride was added to a SiCl 4 -NH 3 -H 2 reaction to produce a crystalline Si 3 N 4 coating with a dispersed TiN second phase.
  • the deposition temperatures for the crystalline material were at least 1250° C. At 1250° C, alpha-type Si 3 N 4 was deposited, and at temperatures greater than 1400° C, ⁇ -Si 3 N 4 was produced. The materials were developed for improved thermal and electrical conductivity.
  • the deposition temperature for the preferred ⁇ -Si 3 N 4 is still above the decomposition temperature of many otherwise suitable substrates such as silicon, nickel, nickel-based alloys, and many ceramic fibers.
  • ceramic fibers are: Nicalon, a trade name for a Si-C-O manufactured by Nippon Carbon Co., Tokyo, Japan; Nextel, a trade name for Al-Si-B-O manufactured by 3M Corp., St. Paul, Minnesota; and HPZ, a trade name for Si-N-C-O manufactured by Dow-Corning, Midland, Michigan.
  • a process for chemical vapor deposition of crystalline silicon nitride which comprises the steps of: introducing a mixture of a silicon source, a molybdenum source, a nitrogen source, and a hydrogen source into a vessel containing a suitable substrate; and, thermally decomposing the mixture to deposit onto the substrate a coating comprising a crystalline nitride of silicon containing a dispersion of a suicide of molybdenum.
  • a composition of matter comprises a crystalline nitride of silicon containing a dispersion of a silicide of molybdenum.
  • a coated article comprises a substrate having thereon a coating which comprises a crystalline nitride of silicon containing a dispersion of a silicide of molybdenum.
  • a composite material comprises a porous ceramic material having deposited within the pores thereof a crystalline nitride of silicon having a silicide of molybdenum dispersed therein.
  • Fig. 1 is a schematic cutaway view of a suitable CVD chamber for carrying out a process according to the invention.
  • Fig.2 is a graph showing an X-ray diffraction pattern for amorphous Si 3 N 4 deposited from a gas mixture comprised of 40 cm 3 /min. SiCl 4 , 160 cm 3 /min. NH 3 , and ⁇ 1000 cm 3 /min. H 2 , with no MoCl s additions.
  • Fig. 3 is a graph showing an X-ray diffraction pattern for Si 3 N 4 deposited, according to the subject process, from a gas mixture comprised of 40 cm 3 /min. SiCl 4 , 160 cm 3 /min. NH 3 , and ⁇ 1000 cm 3 /min. H 2 , and 5 cm 3 /min. MoCl 5 .
  • Fig. 4 is a graph showing an X-ray diffraction pattern for Si 3 N deposited, according to the subject process, from a gas mixture comprised of 40 cm 3 /min. SiCl 4 , 160 cm 3 /min. NH 3 , and ⁇ 1000 cm 3 /min. H j , and 10 cm 3 /min. MoCl 5 .
  • Fig. 5 is a transmission electron micrograph showing a coating deposited by the subject process. Small molybdenum silicide particles dispersed in a crystalline ⁇ -Si 3 N 4 matrix are indicated by arrows.
  • molybdenum silicide is usually comprised of at least one of: MoSi- ⁇ , Mo s Si 3 , and Mo 3 Si, the most common form being MoSi 2
  • Preferred silicon sources include silanes such as SiH 4 , chlorosilanes such as SiH-Cl 4 . and silicon chlorides, especially silicon tetrachloride (SiQ 4 ).
  • Preferred molybdenum sources include Molybdenum-containing organometallic compositions, molybdenum halides such as molybdenum hexafluoride (MoF 6 ), and especially molybdenum pentachloride (MoCl 5 ).
  • Preferred nitrogen sources include nitrogen gas (N- ⁇ , and especially ammonia (NH 3 ).
  • the preferred hydrogen source is hydrogen gas (H- j ).
  • source defines compositions that are introduced in gas or vapor form into a CVD process for participation therein.
  • Molybdenum pentachloride MoCl 5
  • the preferred Mo-source is a solid at room temperature and can generally be sublimated at temperatures of » 265° C at reduced pressure.
  • direct chlorination of molybdenum is used to produce MoCl 5 within the CVD apparatus.
  • a quartz, nickel, or stainless steel cold- wall reactor vessel 1 is utilized for the preferred process.
  • Two heating means 2, 3 control the temperature of the reaction region 4 and the deposition region 5, respectively.
  • the first heating means 2, for heating the reaction region 4 is a resistance furnace
  • the second heating means 3, for heating the deposition region 5 is an RF heating coil
  • a suitable substrate 6 is supported in the deposition region 5.
  • a halide generator 7, comprised of a chamber having a perforated end 8, and made of quartz, nickel, or stainless steel, is located in the reaction region 4. Molybdenum metal in the form of chips, pellets, wire, foil, shot, etc. is contained inside the generator. Molybdenum shot of a nominal 2-5 mm diameter is usually quite suitable.
  • a suitable source of gaseous halogen is connected to the generator 7 through a tubing inlet 9.
  • the preferred halogen source is Cl 2 or HC1. Fluorine, HF, and other similar halide containing gasses are also suitable.
  • the reaction region 4 and the halide generator 7 are heated to a sufficient temperature for the molybdenum particles to react with the halogen, usually about 300° C.
  • the temperature and halogen flow are controlled in order to produce the molybdenum halide at the desired rate.
  • Other gas inlets 10 are provided for introducing gaseous or vaporous silicon, nitrogen, and hydrogen sources.
  • An outlet 11 is provided for exhaust.
  • a typical CVD system usually has connected thereto conventional devices for controlling various parameters. Devices such as plumbing, valves, pressure regulators, mass flow controllers, gas filters and scrubbers, power supplies, and the like are well known, and can be employed herein as necessary, in any convenient configuration.
  • EXAMPLE I In a CVD system as described above, MoCl 5 was introduced during an otherwise typical Si 3 N 4 deposition onto a graphite substrate, at a temperature of about 1200° C and a pressure of 3.3 kPa.
  • the gas mixture in the deposition region was comprised of 40 cm 3 /min. SiCl 4 , 160 cm 3 /min. NH 3 , and ⁇ 1000 cmVmin. H ⁇ and 5 cm 2 /min. MoCl 5 .
  • a control substrate was coated under the same conditions, but with no MoCl 5 being introduced thereto.
  • X-ray diffraction analysis of the coatings that were produced showed the deposit on the control substrate to be amorphous silicon nitride, and the deposit on the experimental substrate to be predominantly crystalline ⁇ -Si 3 N 4 with a MoSi 2 second phase dispersed therein. -These results are shown graphically in Figs. 2 and 3.
  • EXAMPLE ⁇ A coating was deposited onto a graphite substrate as described in Example I, with an increased amount of molybdenum (10 cm /min. MoCl 5 ) added to the process.
  • X-ray diffraction analysis (Fig. 4) and transmission electron microscopic analysis (Fig. 5) of the coating that was produced showed the deposit to be predominantly crystalline ⁇ -Si 3 N 4 with a greater amount of the MoSi 2 second phase.
  • EXAMPLE m Coatings were produced, as described above, on substrates such as graphite, carbon/carbon composite, silicon carbide, and other material.
  • the composition of the coating was found to be highly controllable by varying the flows these reactants into the system. Coatings were deposited at temperatures ranging from about 1000° C to 1200° C and at pressures in the range of 2 kPa to 10 kPa. Higher concentrations of MoCl 5 resulted in an increase in the relative quantity of MoSi 2 phase. As more Mo containing reactant was added, a point was reached where only molybdenum suicides were deposited, with no evidence of Si 3 N 4 .
  • Table I shows the various compositions of coatings produced in 28 CVD operations, carried out at a temperature of about 1150°C and at a pressure of about 3.3 kPa, wherein the flow of reactants were varied widely.
  • Samples 1 - 22 were coated onto graphite substrates, and samples 23 - 28 were coated onto carbon-carbon composite substrates. Deposition times were generally adjusted to produce a nominal layer thickness of 100-150 ⁇ m.
  • Example I A CVD coating was prepared as in Example I, with molybdenum hexafluoride (MoF 6 ) used as the molybdenum source. Additional SiCl 4 was needed to overcome the formation of SiF 4 . The resulting coating was similar to that of Example I.
  • MoF 6 molybdenum hexafluoride
  • Example I A CVD coating was prepared as in Example I, with silane (SiH 4 ) used as the silicon source. The resulting coating was similar to that of Example I.
  • coatings may be fabricated using alternate reactant sources such as metal organic sources for the metals.
  • Other vapor deposition techniques such as plasma- or microwave-enhanced CVD may also be employed to fabricate the materials.
  • An advantage derived from the subject process is that quality, crack-free, crystalline material can be deposited at much lower temperatures, broadening the applicable range of substrate materials.
  • the oxidation resistance properties of the coating materials are also enhanced by the MoSi 2 additions.
  • Molybdenum disilicide possesses exceptional oxidation resistance properties, and Si 3 N 4 deposits with a dispersed MoSi 2 phase performed well in oxidation tests as shown in Example VI below.
  • EXAMPLE VI An oxidation test comprising 12 to 15 cycles, simulating hypervelocity aircraft leading edge temperatures from about 900° C to about 1400° C in air, were performed on coated substrates prepared in accordance with the invention. The comparative results are shown in Tahje -X
  • the new compositions described herein are useful for various applications, such as protective coatings for carbonaceous or other materials prone to oxidation/corrosion at elevated temperatures, coatings for ceramic or metal components, and certain military applications.
  • the invention is also useful in chemical vapor infiltration (CVI) processes and compositions.
  • CVI chemical vapor infiltration
  • U.S. Patent No. 4,580,524, Lackey, et al. describes a CVI process suitably adaptable to the present invention.
  • the silicon nitride/molybdenum silicide composition is deposited on and about the fibers of a fibrous substrate, or on and about the external and internal surfaces of a porous, preformed substrate. Substrates need only withstand temperatures of about
  • a porous, preformed article comprising Nicalon (tradename for a silicon/carbon/oxygen fiber available from Dow Corning, Midland, Michigan) is subjected to a silicon nitride CVI process wherein MoCl s is introduced at a rate in the range of less than 1% to about 5% of the total reactant flow. Crystalline silicon nitride/molybdenum silicide is infiltrated and deposited throughout the interstices of the article, resulting in a dense composite material having useful ambient and elevated temperature strength and modulus and greater toughness than typical monolithic ceramics.
  • a major advantage derived from the invention is that high quality, crack free, crystalline material can be deposited at much lower temperatures, broadening the applicable range of substrate materials.
  • the invention is useful for various applications, such as protective coatings for carbonaceous or other materials prone to oxidation/corrosion at elevated temperatures, coatings for ceramic or metal components.
  • CVI composites prepared in accordance with the invention are useful for high temperature and stress applications such as jet engine components and high- temperature heat exchangers.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne un procédé de dépôt chimique par vapeur de nitrure de silicium cristallin, qui comprend les étapes suivantes: introduction d'un mélange de silicium, de molybdène, d'azote et d'hydrogène dans une enceinte contenant un substrat adéquat; décomposition thermique du mélange pour déposer sur le substrat une couche comprenant du nitrure de silicium cristallin comportant une dispersion de siliciure de molybdène.
PCT/US1993/002140 1992-03-10 1993-03-10 Depot a basse temperature de nitrure de silicium cristallin, ameliore par addition de molybdene WO1994009178A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1019950700552A KR950703073A (ko) 1992-03-10 1993-03-10 결정성 질화규소의 저온 화학적 증기증착 방법(molybdenum enhanced lowtemperature deposition of crystalline silicon nitride)
AU37993/93A AU3799393A (en) 1992-03-10 1993-03-10 Molybdenum enhanced low-temperature deposition of crystalline silicon nitride

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/849,542 US5300322A (en) 1992-03-10 1992-03-10 Molybdenum enhanced low-temperature deposition of crystalline silicon nitride
US07/849,542 1992-10-10

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WO1994009178A1 true WO1994009178A1 (fr) 1994-04-28

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US (1) US5300322A (fr)
KR (1) KR950703073A (fr)
AU (1) AU3799393A (fr)
CA (1) CA2130335A1 (fr)
WO (1) WO1994009178A1 (fr)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19646094C2 (de) * 1996-11-08 1999-03-18 Sintec Keramik Gmbh Verfahren zur chemischen Gasphaseninfiltration von refraktären Stoffen, insbesondere Kohlenstoff und Siliziumkarbid, sowie Verwendung des Verfahrens
US6124635A (en) * 1997-03-21 2000-09-26 Honda Giken Kogyo Kabushiki Kaisha Functionally gradient integrated metal-ceramic member and semiconductor circuit substrate application thereof
US6200691B1 (en) * 1998-04-20 2001-03-13 Colorado School Of Mines Oxidation resistance coating system for refractory metals
US6015464A (en) * 1998-04-29 2000-01-18 Ball Semiconductor, Inc. Film growth system and method for spherical-shaped semiconductor integrated circuits
EP1208897A1 (fr) * 2000-11-21 2002-05-29 Epcon Norge AS Réservoir pour flottation et dégazage combiné
US6528430B2 (en) * 2001-05-01 2003-03-04 Samsung Electronics Co., Ltd. Method of forming silicon containing thin films by atomic layer deposition utilizing Si2C16 and NH3
KR100454715B1 (ko) * 2002-03-14 2004-11-05 한국과학기술연구원 ＭｏＳｉ₂―Ｓｉ₃Ｎ₄복합피복층 및 그 제조방법
US20050109276A1 (en) * 2003-11-25 2005-05-26 Applied Materials, Inc. Thermal chemical vapor deposition of silicon nitride using BTBAS bis(tertiary-butylamino silane) in a single wafer chamber
US7628863B2 (en) * 2004-08-03 2009-12-08 Applied Materials, Inc. Heated gas box for PECVD applications
US20060084283A1 (en) * 2004-10-20 2006-04-20 Paranjpe Ajit P Low temperature sin deposition methods
US20070082507A1 (en) * 2005-10-06 2007-04-12 Applied Materials, Inc. Method and apparatus for the low temperature deposition of doped silicon nitride films
US7501355B2 (en) * 2006-06-29 2009-03-10 Applied Materials, Inc. Decreasing the etch rate of silicon nitride by carbon addition
US20080145536A1 (en) * 2006-12-13 2008-06-19 Applied Materials, Inc. METHOD AND APPARATUS FOR LOW TEMPERATURE AND LOW K SiBN DEPOSITION
US8105649B1 (en) 2007-08-09 2012-01-31 Imaging Systems Technology Fabrication of silicon carbide shell
DE102012100176B4 (de) 2012-01-10 2016-11-17 Cvt Gmbh & Co. Kg Verfahren zur chemischen Gasphaseninfiltration von wenigstens einem refraktären Stoff
US10093810B2 (en) 2013-03-15 2018-10-09 General Electric Company Composite coatings and methods therefor
DE102017204257A1 (de) * 2017-03-14 2018-09-20 Schunk Kohlenstofftechnik Gmbh Beschichtetes Produkt und Verfahren zur Herstellung
DE102017204258B4 (de) 2017-03-14 2023-08-17 Schunk Kohlenstofftechnik Gmbh Verfahren zur Herstellung eines porösen Körpers
CN110760816A (zh) * 2019-12-02 2020-02-07 长沙新材料产业研究院有限公司 金刚石在线检测生长装置及生长缺陷处理方法
US20220195606A1 (en) * 2020-12-23 2022-06-23 Raytheon Technologies Corporation Method for metal vapor infiltration of cmc parts and articles containing the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58176109A (ja) * 1982-04-09 1983-10-15 Shin Etsu Chem Co Ltd α型窒化けい素の製造方法
US4598024A (en) * 1984-09-28 1986-07-01 The United States Of America As Represented By The United States Department Of Energy Dispersion toughened ceramic composites and method for making same
US4888142A (en) * 1985-04-11 1989-12-19 Toshiba Ceramics Co., Ltd. Process for producing β-form Si3 N4

Family Cites Families (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2920006A (en) * 1957-12-13 1960-01-05 Leonard F Yntema Highly refractive molybdenum bodies and method of preparing same
US3117846A (en) * 1960-01-28 1964-01-14 Pfaudler Permutit Inc Multi layer difusion coatings and method of applying the same
GB1060925A (en) * 1964-04-27 1967-03-08 Westinghouse Electric Corp Growth of insulating films such as for semiconductor devices
US3477872A (en) * 1966-09-21 1969-11-11 Rca Corp Method of depositing refractory metals
GB1326769A (en) * 1970-10-08 1973-08-15 Fulmer Res Inst Ltd Formulation of tungsten and molybdenum carbides
US3982048A (en) * 1975-11-03 1976-09-21 General Electric Company Method of making an insulator with a non-linear resistivity coating of glass bonded silicon carbide
US4279947A (en) * 1975-11-25 1981-07-21 Motorola, Inc. Deposition of silicon nitride
US4162345A (en) * 1976-07-06 1979-07-24 Chemetal Corporation Deposition method and products
US4180596A (en) * 1977-06-30 1979-12-25 International Business Machines Corporation Method for providing a metal silicide layer on a substrate
NL7807798A (nl) * 1978-07-21 1980-01-23 Elbar Bv Werkwijze voor het aanbrengen van een beschermende silicium houdende deklaag op voorwerpen die vervaardigd zijn uit superlegeringen.
US4431708A (en) * 1979-12-19 1984-02-14 The United States Of America As Represented By The United States Department Of Energy Annealed CVD molybdenum thin film surface
US4794019A (en) * 1980-09-04 1988-12-27 Applied Materials, Inc. Refractory metal deposition process
US4404235A (en) * 1981-02-23 1983-09-13 Rca Corporation Method for improving adhesion of metal film on a dielectric surface
US4359490A (en) * 1981-07-13 1982-11-16 Fairchild Camera & Instrument Corp. Method for LPCVD co-deposition of metal and silicon to form metal silicide
DE3211752C2 (de) * 1982-03-30 1985-09-26 Siemens AG, 1000 Berlin und 8000 München Verfahren zum selektiven Abscheiden von aus Siliziden hochschmelzender Metalle bestehenden Schichtstrukturen auf im wesentlichen aus Silizium bestehenden Substraten und deren Verwendung
US4524718A (en) * 1982-11-22 1985-06-25 Gordon Roy G Reactor for continuous coating of glass
US4803127A (en) * 1983-02-25 1989-02-07 Liburdi Engineering Limited Vapor deposition of metal compound coating utilizing metal sub-halides and coated metal article
WO1984004110A1 (fr) * 1983-04-18 1984-10-25 Battelle Development Corp COUCHE DURE FORMEE PAR L'INCORPORATION D'AZOTE DANS DU Mo OU DU W METALLIQUE ET PROCEDE DE PREPARATION D'UNE TELLE COUCHE
JPS59203784A (ja) * 1983-04-28 1984-11-17 株式会社東芝 非酸化物系セラミックス焼結体のモリブデンシリサイド被膜の形成方法
US4605566A (en) * 1983-08-22 1986-08-12 Nec Corporation Method for forming thin films by absorption
US4617237A (en) * 1984-05-14 1986-10-14 Allied Corporation Production of conductive metal silicide films from ultrafine powders
US4780372A (en) * 1984-07-20 1988-10-25 The United States Of America As Represented By The United States Department Of Energy Silicon nitride protective coatings for silvered glass mirrors
US4580524A (en) * 1984-09-07 1986-04-08 The United States Of America As Represented By The United States Department Of Energy Process for the preparation of fiber-reinforced ceramic composites by chemical vapor deposition
JPS61117841A (ja) * 1984-11-14 1986-06-05 Hitachi Ltd シリコン窒化膜の形成方法
JPS61158877A (ja) * 1984-12-27 1986-07-18 小宮山　宏 セラミツクス多孔質膜の製造方法
US4610896A (en) * 1985-04-08 1986-09-09 United Technologies Corporation Method for repairing a multilayer coating on a carbon-carbon composite
DE3516078A1 (de) * 1985-05-04 1986-11-06 Philips Patentverwaltung Gmbh, 2000 Hamburg Verfahren zur glimmentladungsaktivierten reaktiven abscheidung von elektrisch leitendem material aus einer gasphase
US4695517A (en) * 1985-05-31 1987-09-22 Ngk Spark Plug Co., Ltd. Composite layer aluminum nitride base sintered body
KR890003856B1 (ko) * 1985-09-10 1989-10-05 가부시끼 가이샤 도시바 세라믹스 소결체용 금속화 조성물
JPH0645885B2 (ja) * 1985-12-16 1994-06-15 キヤノン株式会社 堆積膜形成法
JPS62142778A (ja) * 1985-12-18 1987-06-26 Canon Inc 堆積膜形成法
DE3544975C1 (de) * 1985-12-19 1992-09-24 Krupp Gmbh Verfahren zur Herstellung eines beschichteten Formkoerpers
JPS62197370A (ja) * 1986-02-20 1987-09-01 日本碍子株式会社 窒化珪素焼結体
US4756927A (en) * 1986-05-29 1988-07-12 Massachusetts Institute Of Technology Method and apparatus for refractory metal deposition
US4810530A (en) * 1986-08-25 1989-03-07 Gte Laboratories Incorporated Method of coating metal carbide nitride, and carbonitride whiskers with metal carbides, nitrides, carbonitrides, or oxides
US4720395A (en) * 1986-08-25 1988-01-19 Anicon, Inc. Low temperature silicon nitride CVD process
DE3630066C1 (de) * 1986-09-04 1988-02-04 Heraeus Gmbh W C Verfahren zur Herstellung von gesinterten metallisierten Aluminiumnitrid-Keramikkoerpern
JPH0772351B2 (ja) * 1986-12-01 1995-08-02 株式会社日立製作所 金属薄膜選択成長方法
US4822697A (en) * 1986-12-03 1989-04-18 Dow Corning Corporation Platinum and rhodium catalysis of low temperature formation multilayer ceramics
US4911992A (en) * 1986-12-04 1990-03-27 Dow Corning Corporation Platinum or rhodium catalyzed multilayer ceramic coatings from hydrogen silsesquioxane resin and metal oxides
DE3861032D1 (de) * 1987-03-13 1990-12-20 Toshiba Kawasaki Kk Verfahren zur metallisierung eines nitrid-keramischen gegenstandes.
US4741925A (en) * 1987-09-14 1988-05-03 Gte Products Corporation Method of forming silicon nitride coating
US4892792A (en) * 1987-10-01 1990-01-09 Gte Laboratories Incorporated A1N coated silicon nitride based cutting tools

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58176109A (ja) * 1982-04-09 1983-10-15 Shin Etsu Chem Co Ltd α型窒化けい素の製造方法
US4598024A (en) * 1984-09-28 1986-07-01 The United States Of America As Represented By The United States Department Of Energy Dispersion toughened ceramic composites and method for making same
US4888142A (en) * 1985-04-11 1989-12-19 Toshiba Ceramics Co., Ltd. Process for producing β-form Si3 N4

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US5300322A (en) 1994-04-05
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CA2130335A1 (fr) 1994-04-28

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