US3911194A - Method for forming pure metal or non-metal deposits - Google Patents

Method for forming pure metal or non-metal deposits Download PDF

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Publication number
US3911194A
US3911194A US41201673A US3911194A US 3911194 A US3911194 A US 3911194A US 41201673 A US41201673 A US 41201673A US 3911194 A US3911194 A US 3911194A
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United States
Prior art keywords
metal
source
substratum
fluoride
vapour
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Expired - Lifetime
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English (en)
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Jacques Dejachy
Jacques Gillardeau
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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    • 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
    • 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
    • C23C16/06—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 metallic material
    • C23C16/08—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 metallic material from metal halides
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the present invention relates to a method for obtaining metal or metal-like coatings in the pure state from the high-valence corresponding fluorides.
  • the positioning of the metal atom in the surface lattice of the receiver metal occurs very quickly.
  • the adsorbed two fluorine atoms are capable of moving under the conditions of the experiment, and the desorption thereof, which proves to be one of the main factors governing the kinetics of the deposition, allows the metal surface to be permanently uncovered.
  • Another method consists in reducing a fluoride by 1 means of hydrogen, and it also leads to good coatings,
  • the excess hydrogen may alter the hydrogen/- gaseous fluoride ratio to the point of deteriorating the metal deposit, or even causing the vapour-deposition to stop.
  • Too great a concentration of hydrofluoric gas in the vicinity of the substratum may, quite undesirably, lead to a reaction opposite to the desired one, viz. the recombination of the metal deposited in the fluoride state.
  • the reduction method has therefore to be rejected whenever the geometry of the objects to be coated is complicated, or whenever it is desired to form deposits inside parts comprising many branches or, e.g., inside long and narrow tubes.
  • the invention relates to a method for forming pure metal or non-metal deposits, said method consisting in introducing, in the vapour state, at least one metal or non-metal fluoride of higher valence into an enclosure containing at least one substratum to be coated and a source for providing the metal or non-metal to be deposited, heating said source in order that the higher valence fluoride is transformed, when contacting said source, into at least one sub-fluoride which evaporates, is condensed on the substratum and is transformed into fluorine and into the metal, or the non-metal, which constitutes the desired deposit.
  • the fluorides of higher valence are fluoridizing and cannot be thermally decomposed until the metal is obtained. It is only by means of the reduction of these fluorides with hydrogen that a total chemical decomposition can be obtained.
  • the sub-fluorides are not fluoridizing in general, and they can be thermally decomposed on a hot substratum in order to provide the metal directly.
  • subfluorides and the thermal decomposition of same occur simultaneously.
  • the formation of a sub-fluoride, having the general formula MF froma higher fluoride, having the general formula MF,,, and the metal M is carried out as follows:
  • n and m being the valences of the elements and n being higher than m.
  • the following compounds can be mentioned as fluorides of higher valence capable of providing a thermally decomposable sub-fluoride: wF6, MoF6, ReF6, PtF6, TaFS, NbFS, BFS, TiF4, CF4, SiF4
  • the higher valence fluoride is caused to react on the corresponding metal or non-metal, heated to the appropriate temperature.
  • the generating metal or non-metal can be very easily located in the vicinity of the part to be coated, which permits to form the subfluoride in the vicinity of the surface on which the de- MFm MFm- M mF- M F adsorbed adsorbed adsorbed solid desorbed gas metal
  • a gaseous molecule of sub-fluoride MF inpinges on the substratum to be coated, heated to the appropriate temperature, the impact is efficient and the MF, molecule is activated to a sufficient extent to be quickly absorbed by the substratum.
  • the chemical adsorption being of a dissociating nature, the sub-fluoride adsorbed decomposes into metal M and into fluorine atoms.
  • the metal obtained is inserted into the surface cristalline lattice, and fluorine is desorbed, which permits further molecules of sub-fluorides to be introduced and the vapour deposition to proceed.
  • the method according to the invention can be illustrated, for example, by the vapour deposition of tungsten (W). Hexafluoride WF reacts on tungsten metal W as follows:
  • the tungsten hexafluoride used at the beginning of the reaction is re-generated at the end of that reaction; it thus acts as a catalyst. It is therefore possible to introduce the gas into the enclosure and to carry out the reaction under constant pressure.
  • the metal fluoride MF or MP thus formed is then decomposed on the suitably heated part to be coated, thus freeing the metal which is deposited:
  • the fluorine provided by the thermal decomposition of MP or MP recombines with Wlto give back fluoride WF i.e. the gaseous catalyst which is thus regenerated.
  • a great many metal deposits can be obtained in this way.
  • the copper deposits from CuF and CuF and the nickel deposits from NiF and NiF.
  • the following metals are transfered and vapour-deposited according to that method: iron, cobalt, zinc, silver, gold, cadmium, and aluminum, to mention only the most frequently used metals.
  • the above reaction has the advantage of permitting the vapour-deposition of metals such as, e.g., nickel, copper, aluminum, zinc, cadmium, zirconium, the fluorides of which, which are not volatile enough, cannot be validly used in the other vapour-metallurgy methods.
  • metals such as, e.g., nickel, copper, aluminum, zinc, cadmium, zirconium, the fluorides of which, which are not volatile enough, cannot be validly used in the other vapour-metallurgy methods.
  • the method according to the invention has many others advantages.
  • the deposits obtained by means of the method according to the invention are compact, even, adhesive and epitaxic,:whenever allowed by the nature of the substratum and of the deposit. a
  • a remarkable vapour-deposition technology can be developed, taking account of the fact that the fluoride (MF or MP useful to thevapour-deposition, can be generated in the. vicinity of the surface to be coated, whatever be the shape of the latter; one has only to put the metal source near the substratum.
  • MF or MP useful to thevapour-deposition
  • This is of considerable advantage for carrying out depositions inside parts of various shapes such as tubes, valves and containers.
  • the shape of the part to be coated by no means impairs .the very good penetration power associated to the method.
  • the metal generating member may be a wire or a bar, heated by Joule effect.
  • the generatingsource may also be a rod, indirectly heated by means of a non-consumable thermal member, the shape of that rod being adapted to each particular instance.
  • That rod may either be coated with the metal obtained by sin'tering, or consist in a tank containing fragments of the metal to be vapour-deposited.
  • the part to be coated is preferably directly heated by the metal member which generates metal M, and in this case a heat insulating member must surround said part.
  • the shape of the devices for carrying out the method according to the invention varies according to the shape, the nature and the number of the articles to be coated.
  • FIG. 1 is a section through a device for coating the inside of a tube
  • FIG. 2 is a section through a device for coating both the inner portion and the outer portion of a tube; as can be seen in FIG. 1, tube 1, made of any metal alloy, the inside portion of which is to be metal coated, is introduced into a heat insulated sleeve 2, with a view to avoiding as best as possible, heat-losses by radiation.
  • a metal or non-metal rod 3 is held by the ends thereof inside the tube at the level of plugs 4 and 5.
  • Plug 4 has an opening for conduct 6 through which a higher valence fluoride is introduced. For operating that device, the rod must be heated to a predetermined temperature before introducing, through conduct 6, the fluoride which, by contacting bar 3, generates a sub-fluoride that forms a deposit of the inner wall of tube 1.
  • Tube 1 is held within an enclosure 7 by means of brackets (not shown).
  • the arrangement as shown permits, as in the previous instance, to coat the innerportion of tube 1 with metal, and also permits to coat the outer portion of that tube, through the addition of bars 3 and 3" which are metal canon-metal generating sources like bar 3, and of conducts-5' and 5" for the introduction of fluorine.
  • bars 3 and 3" which are metal canon-metal generating sources like bar 3, and of conducts-5' and 5" for the introduction of fluorine.
  • the inner wall of enclosure 7 is of a material which is not likely to retain a metal deposit. 1 Y v r
  • the method according to the invention permits to.
  • the vapour-deposit is necessarily good. This is even the case with deposits carried out at temperatures which would prove much too low for the reduction method. It follows that the method according to the invention permits to coat materials likely to be definitively altered at higher temperatures,. O ine can mention, for instance, the case of deposits made on metals subjected to allotropic transformations at high temperatures and for which there is a risk of deteriorating the deposit-substratum interface, at the moment of passing the allotropic transformation point, during the cooling step.
  • thedep osits obtained carrying out themethodaccording to,,th e invention are both adhesive, compact and even, and that their growth is carried out epitaxically, viz. the cristalline lattice 'develops atom per atom in agreement with the surface cristalline lattice, which permits to obtain as desired monocristals having agiven orientation.
  • tungsten deposits were obtained, from WP on the following substrata, given merely as examples: tungsten, molybdenum copper, nickel, monel-metal, inconel, iron, graphite, silicon, alumina.
  • vapour-deposits with alloys. It is indeed possible to carry out the co-deposition of two metals, by taking advantage of the respective chemical natures of the generating metal and of the gaseous fluoride of higher valence.
  • a remarkable vapour-deposition technology can be developed taking into account the fact that sub-fluoride useful for the vapour-deposition can be generated in the vicinity of the surface to be coated whatever be the shape of the latter. It is only sufficient to put the metal or non-metal source near the substratum. This is of considerable advantage for making deposits e.g. inside tubes, even very long and narrow tubes, inside valve bodies, complicated tubing, containers, etc. The shape of the member to be coated by no means impairs the excellent penetrating power associated to the method.
  • the metal or non-metal source can be a wire or a bar, heated by Joule effect. That source can also be a rod directly heated by means of a non-consumable thermal member. The shape of that rod may be adapted to each particular instance.
  • the rod either can be coated with the metal obtained by sintering or according to any vapour-deposition method, or consists in a tank containing metal fragments to be vapour-deposited.
  • the part to be coated is preferably heated directly by the generating metal member, said part being surrounded by a heat-insulating member.
  • the invention may have quite a number of applications in the field of electronics, in particular for the manufacture of the transmitters of electronic-tungsten converters, and for the manufacture of X-ray tubes anticathodes and in particular, in the field of space research, for manufacturing titanium thermal shields.
  • the following applications can also be mentioned:
  • refractory metal e.g. of tungsten, tantalum, molybdenum
  • refractory substrata such as ruby or corundum
  • the deposition of refractory metals on various types of glass in view of the possibility of making the deposition at a low temperature
  • the deposition of various metals on substrata sensitive to hydrogen in view of the possibility of making the deposition at a low temperature
  • catalysts by depositing metals having a high specific area.
  • a method for forming pure metal deposits consisting in introducing, in the vapour state, at least one metal or metalloid fluoride of higher valence selected from the group consisting of: WF MF ReF PtF TaF NbF BF TiF SiF CF, into an enclosure containing at least one substratum to be metal-coated and a source of the metal to be deposited selected from the group consisting of nickel, copper, aluminum, zinc, cadmium, molybdenum, tungsten and zirconium, heating said source in order that the higher valence fluoride is transformed, when contacting said source, into at least one sub-fluoride of the source metal which coats the substratum and is transformed into fluorine and into the metal, which constitutes the desired deposit.
  • the substratum is a material selected from the group consisting of tungsten, molybdenum, copper, nickel, monel metal, inconel, iron, graphite, silicon and alumina.
  • a method according to claim 1, wherein the source is selected from the group consisting of an electrically heated wire or a hollow rod.

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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)
  • Surface Treatment Of Glass (AREA)
  • Physical Vapour Deposition (AREA)
US41201673 1972-11-07 1973-11-01 Method for forming pure metal or non-metal deposits Expired - Lifetime US3911194A (en)

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FR7239334A FR2205583B1 (sv) 1972-11-07 1972-11-07

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US (1) US3911194A (sv)
JP (1) JPS4995832A (sv)
DE (1) DE2355531A1 (sv)
FR (1) FR2205583B1 (sv)
GB (1) GB1406394A (sv)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4196230A (en) * 1978-09-15 1980-04-01 Gibson James O Production of carbon fiber-tantalum carbide composites
EP0040092A1 (en) * 1980-05-14 1981-11-18 Permelec Electrode Ltd Method for forming an anticorrosive coating on a metal substrate
US4343963A (en) * 1979-03-02 1982-08-10 Westinghouse Electric Corp. Substrate for silicon solar cells
US4386137A (en) * 1981-09-10 1983-05-31 Nobuatsu Watanabe Process for producing a graphite fluoride type film on the surface of an aluminum substrate
US4387962A (en) * 1981-10-06 1983-06-14 The United States Of America As Represented By The Secretary Of The Air Force Corrosion resistant laser mirror heat exchanger
US4402771A (en) * 1979-03-02 1983-09-06 Westinghouse Electric Corp. Substrate for silicon solar cells
US4411861A (en) * 1977-08-19 1983-10-25 Kraftwerk Union Aktiengesellschaft Method for protecting the casing tubes of nuclear reactor fuel rods
US4540607A (en) * 1983-08-08 1985-09-10 Gould, Inc. Selective LPCVD tungsten deposition by the silicon reduction method
US4681652A (en) * 1980-06-05 1987-07-21 Rogers Leo C Manufacture of polycrystalline silicon
US4741928A (en) * 1985-12-27 1988-05-03 General Electric Company Method for selective deposition of tungsten by chemical vapor deposition onto metal and semiconductor surfaces
US4751044A (en) * 1985-08-15 1988-06-14 Westinghouse Electric Corp. Composite nuclear fuel cladding tubing and other core internal structures with improved corrosion resistance
US4842891A (en) * 1987-02-20 1989-06-27 Hitachi, Ltd. Method of forming a copper film by chemical vapor deposition

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55134170A (en) * 1979-04-04 1980-10-18 Oyo Kagaku Kenkyusho Manufacture of deformed tungusten structure
DE3025680A1 (de) * 1980-07-07 1982-02-04 Siemens AG, 1000 Berlin und 8000 München Heizkoerper fuer einen hochtemperaturofen
FR2527226B1 (fr) * 1982-05-19 1986-02-21 Creusot Loire Procede de revetement en phase gazeuse de petits orifices menages dans des pieces en aciers
DE3300449A1 (de) * 1983-01-08 1984-07-12 Philips Patentverwaltung Gmbh, 2000 Hamburg Verfahren zur herstellung einer elektrode fuer eine hochdruckgasentladungslampe
FR2629839B1 (fr) * 1988-04-07 1991-03-22 Pauleau Yves Procede de depot de metaux refractaires
GB9203394D0 (en) * 1992-02-18 1992-04-01 Johnson Matthey Plc Coated article

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2887407A (en) * 1957-08-05 1959-05-19 Manufacturers Chemical Corp Preparation of diffusion coatings on metals
US3658577A (en) * 1969-10-01 1972-04-25 Gene F Wakefield Vapor phase deposition of silicide refractory coatings

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2856312A (en) * 1953-07-03 1958-10-14 Nowak Rudolf Treating metal surfaces
US3414428A (en) * 1964-10-20 1968-12-03 Allied Chem Chromizing compositions and methods and continuous production of chromium halides for chromizing
US3373018A (en) * 1965-02-17 1968-03-12 Allied Chem Production of rigid shapes of refractory metals by decomposition of the metal hexafluoride in the interstices of a green compact
US3516850A (en) * 1966-09-16 1970-06-23 Texas Instruments Inc Process for metal coating a hydrogen permeable material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2887407A (en) * 1957-08-05 1959-05-19 Manufacturers Chemical Corp Preparation of diffusion coatings on metals
US3658577A (en) * 1969-10-01 1972-04-25 Gene F Wakefield Vapor phase deposition of silicide refractory coatings

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4411861A (en) * 1977-08-19 1983-10-25 Kraftwerk Union Aktiengesellschaft Method for protecting the casing tubes of nuclear reactor fuel rods
US4196230A (en) * 1978-09-15 1980-04-01 Gibson James O Production of carbon fiber-tantalum carbide composites
US4343963A (en) * 1979-03-02 1982-08-10 Westinghouse Electric Corp. Substrate for silicon solar cells
US4402771A (en) * 1979-03-02 1983-09-06 Westinghouse Electric Corp. Substrate for silicon solar cells
EP0040092A1 (en) * 1980-05-14 1981-11-18 Permelec Electrode Ltd Method for forming an anticorrosive coating on a metal substrate
US4681652A (en) * 1980-06-05 1987-07-21 Rogers Leo C Manufacture of polycrystalline silicon
US4386137A (en) * 1981-09-10 1983-05-31 Nobuatsu Watanabe Process for producing a graphite fluoride type film on the surface of an aluminum substrate
US4387962A (en) * 1981-10-06 1983-06-14 The United States Of America As Represented By The Secretary Of The Air Force Corrosion resistant laser mirror heat exchanger
US4540607A (en) * 1983-08-08 1985-09-10 Gould, Inc. Selective LPCVD tungsten deposition by the silicon reduction method
US4751044A (en) * 1985-08-15 1988-06-14 Westinghouse Electric Corp. Composite nuclear fuel cladding tubing and other core internal structures with improved corrosion resistance
US4741928A (en) * 1985-12-27 1988-05-03 General Electric Company Method for selective deposition of tungsten by chemical vapor deposition onto metal and semiconductor surfaces
US4842891A (en) * 1987-02-20 1989-06-27 Hitachi, Ltd. Method of forming a copper film by chemical vapor deposition

Also Published As

Publication number Publication date
DE2355531A1 (de) 1974-05-09
FR2205583B1 (sv) 1975-09-12
JPS4995832A (sv) 1974-09-11
FR2205583A1 (sv) 1974-05-31
GB1406394A (en) 1975-09-17

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