US3607368A - Method of coating substrates by vapor deposition - Google Patents

Method of coating substrates by vapor deposition Download PDF

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Publication number
US3607368A
US3607368A US765826A US3607368DA US3607368A US 3607368 A US3607368 A US 3607368A US 765826 A US765826 A US 765826A US 3607368D A US3607368D A US 3607368DA US 3607368 A US3607368 A US 3607368A
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United States
Prior art keywords
graphite
substance
vapor
vaporizer
deposited
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US765826A
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English (en)
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Johannes Jacobus Asueru Amstel
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US Philips Corp
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US Philips Corp
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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
    • 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
    • C23C14/24—Vacuum evaporation
    • C23C14/26—Vacuum evaporation by resistance or inductive heating of the source

Definitions

  • the material to be deposited is taken up in a lacelike 117/107, 219/274, 118/491, 118/495 body built up from graphite yarn heated to the vaporization [51 Int. Cl C23c13/12 temperature by the passage of electrical current :1 I I I J 9 Z f;
  • the invention relates to the coating of substrates by vapor deposition.
  • this is generally carried out in an atmosphere which is inert relative to the substance to be deposited in which, in order to check impediment of the vapor molecules on their way to the substrate, the gas pressure is chosen to be low and the method is usually carried out in a vacuum.
  • the vaporization of the substance to be deposited is usually effected by means of a vaporizer element which is heated by the passage of current.
  • the substance is caused to vaporize on the surface of a heating element.
  • a drawback hereof is that the substance can be present only in restricted quantities and hence the vapor deposition of thick layers or the continuous vapor deposition is not possible.
  • a vaporizing element is also known already to which the substance to be vapor-deposited is applied continuously from a container during the vaporization process (American Pat. Spec. 2,665,227).
  • an approximately horizontally arranged vaporizer element in the form of a rod is used which is provided with a channellike groove extending in the longitudinal direction in which the substance is allowed to flow from the container.
  • This element is composed of a material which is readily wetted by the substance to be vapor-deposited so that it is coated with the substance, all over its surface.
  • graphite was found to be suitable, if desired, converted superficially into a high-melting-point metal carbide.
  • a drawback of such vaporizer elements is that during use they have to be arranged approximately horizontally.
  • the layer thickness of the substance to be vapor deposited in the groove is different from that on the further surface of the element. The result of this is a difference in vaporization at the area of the groove so that substrates arranged around the element are coated in different thicknesses dependent upon their position.
  • the invention is based on the recognition of the fact that the above-mentioned drawbacks can be avoided by using an electrically conducting vaporizer element which is built up from a porous material.
  • a vaporizer element is used for this purpose, which is constructed from a lacelike body of graphite yarn.
  • Such a material is commercially available and may be obtained, for example, by carbonizing rayon yarns, whether or not woven, knitted or twined, at temperatures above approximately 2000" C. for example an Article by MoLindsey in Design Engineering of 6 Apr. 1965 titled: Developments in Carbon and graphite Textiles f.e. Materials which advantageously can be used are told by Morganite Research and Development Ltd. UK. as graphite card grade 6301 G and 6303 G.
  • the invention relates to a method of coating substrates by vapor-deposition from the surface of a vaporizer element built up from graphite and heated by the passage of current, characterized in that the substance to be vapor-deposited is taken up in a vaporizer element consisting of a lace-body which is built up from graphite yarn and is then heated at a temperature at which said substance vaporizes.
  • a vaporizer element is preferably used which is built up from yarns, the elementary strands of which have a thickness of under 20 microns.
  • the substance to be vaporized may be incorporated in the vaporizer element in comparatively large quantities. If very thick layers have to be vapor-deposited, or large numbers of substrates have to be coated in a continuous process however, it is of advantage to add a further quantity of the substance to the element during the vaporization process.
  • a porous lacelike body which comprises a coaxial cavity.
  • Some substances for example, copper, germanium and tim, do not react with the graphite material of the vaporizer. If such a substance is made to melt in the vaporizer, it penetrates through the pores in the wall to the outer surface on which an even layer is then formed. In this case it is recommendable to use a hollow vaporizer element which can easily be filled with the material to be vaporized.
  • the graphite body may be converted into zirconium carbide, as a result of which an element of a very large strength is obtained, which can be used repeatedly for vapor-deposition of metals, for example, cobalt and chromium.
  • the supply to the vaporizer of the substance to be vapordeposited may be effected in a liquid and in a solid state, both prior to and during the vaporization.
  • a device for coating substrates by vapor-deposition comprises a container in which the substance to be vaporized can be molten and from which the molten substance flows into a vaporizer element consisting of a lacelike body which is built up from yarns of graphite and/or a carbide.
  • a vaporizer element consisting of a lacelike body which is built up from yarns of graphite and/or a carbide.
  • the action of gravity and/or capillary action occuring may be used.
  • a vaporizer element which is provided with a coaxial cavity.
  • the metal in the form of powder, grains or wire can easily be provided in said cavity.
  • metal in the form of a wire is most suitable. This is the case also when replenishing the molten substance which is supplied to the vaporizer element through a container.
  • FIG. 1 shows in perspective a hollow graphite lace
  • FIG. 2 I shows in perspective a hollow graphite lace
  • FIG. 3 shows a section of a device for vapor-coating according to the invention.
  • Two copper wires 2 thickness 0.5 mm., length 320 mm., are slid into a hollow graphite lace 1, length 400 mm., outside diameter approximately 2 mm., inside diameter approximately 1 mm., as shown on an exaggerated scale in FIG. 1 of the drawing, so that on either side approximately 40 mm. of the lace is free from metal.
  • This element is arranged horizontally in a vacuum and heated by a current of 13a. With an initial voltage of 20v. For maintaining this current which is necessary for maintaining a vaporization temperature of approximately 2000 C., the voltage must gradually be increased to approximately 90v.
  • the copper wires melt.
  • the molten copper does not wet the graphite element but an even vaporization of copper around the element is obtained.
  • Example 2 A graphite lace as described in example 1 is filled with 1.7 gms. of germanium grains over a length of 300 mm.
  • the germanium which does not wet the graphite lace is caused to melt and vaporize in a vacuum.
  • germanium mirrors thickness 2.2. microns, are obtained in this manner in approximately minutes on glass substrates which are arranged at a distance of 80 mm.
  • an analogous manner 3 has also been processed to mirrors.
  • Example 3 A densely braided graphite lace 3, length 444 mm., as shown in FIG. 2, is threaded through an aperture 4 in the bottom of a crucible 5 and secured there by means of a knot 6.
  • Aluminum 7 is provided in the crucible 5 and is kept in the molten state at approximately 800 C.
  • the crucible 5 is positioned in an oven 8.
  • the lace 3 is brought under a weak tensile stress by the leaf springs 14 to which the lace 3 is connected through member 11 having an aperture 15 in which lace 3 is secured by means of a knot 12 and the means 13 for holding member 11.
  • Substrate holders 10 are arranged around the lace 3.
  • spring 9 which is arranged between the crucible 5 and the inner wall of the electric oven 8 and the holding means 13.
  • the device as shown in FIG. 3 is positioned in a vacuum chamber (not shown). The chamber is evacuated.
  • the mass 7 consisting of aluminum is heated to a temperature of 800 C. by means of the oven 8.
  • the lace 3 is heated to approximately 2000 C. with a current of 27a. with an initial voltage difference of 80v. between the springs 9 and the holding member B.
  • Alu'mihum is sucked up from the crucible and reacts with the graphite while forming aluminum carbide. At the same time free aluminum is taken up in the element. With a current passage of 100a. and a voltage of 8v. a temperature of approximately 1200 C. is generated.
  • On substrates which are arranged at a distance of 40 mm. aluminum mirrors, thickness 20 ,u., are vapor-deposited in this manner in 20 minutes.
  • the aluminum in the element is replenished by a capillary sucking from the crucible.
  • the process can be Example 4
  • a rod of titanium, length 250 mm., thickness 2 mm., is slid into a hollow graphite lace as described in example 1. Heating is carried out in a vacuum by the passage of current.
  • reaction occurs while forming titanium carbide, while a part of the titanium remains in the tubular element in a free state.
  • the free titanium is deposited on glass substrates which are arranged at a distance of mm. Titanium mirrors, thickness 1 u, are then obtained in approximately 10 minutes.
  • Example 5 In a manner quite analogous to that described in example 4 a graphite lace is converted into a zirconium carbide element, the quantity of zirconium being chosen to be so that only a small excess of this metal remains.
  • the resulting hollow zirconium carbide element is filled with chromium in powder form and then heated in a vacuum to approximately 1200 C. by a current of 50a. with 20v.
  • Chromium mirrors thickness approximately 1 [.L, are then obtained in 25 minutes on substrates which are arranged at a distance of 70 mm.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
US765826A 1967-10-10 1968-10-08 Method of coating substrates by vapor deposition Expired - Lifetime US3607368A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL6713713A NL6713713A (fr) 1967-10-10 1967-10-10

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US3607368A true US3607368A (en) 1971-09-21

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Application Number Title Priority Date Filing Date
US765826A Expired - Lifetime US3607368A (en) 1967-10-10 1968-10-08 Method of coating substrates by vapor deposition
US00131793A Expired - Lifetime US3723706A (en) 1967-10-10 1971-04-06 Wick type evaporator

Family Applications After (1)

Application Number Title Priority Date Filing Date
US00131793A Expired - Lifetime US3723706A (en) 1967-10-10 1971-04-06 Wick type evaporator

Country Status (8)

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US (2) US3607368A (fr)
AT (1) AT284582B (fr)
BE (1) BE722019A (fr)
CH (1) CH531053A (fr)
FR (1) FR1589261A (fr)
GB (1) GB1229879A (fr)
NL (1) NL6713713A (fr)
SE (1) SE326874B (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3796182A (en) * 1971-12-16 1974-03-12 Applied Materials Tech Susceptor structure for chemical vapor deposition reactor
US3860443A (en) * 1973-03-22 1975-01-14 Fiber Materials Graphite composite
US3928659A (en) * 1970-02-12 1975-12-23 Alexander Samuel Baxter Methods of and means for vacuum deposition
US3931493A (en) * 1973-06-21 1976-01-06 United Technologies Corporation Apparatus and method for the production of metal vapor
US4027622A (en) * 1974-04-08 1977-06-07 Beckman Instruments G.M.B.H. Apparatus for doping semiconductors in centrifuge
US4029829A (en) * 1974-02-08 1977-06-14 Dunlop Limited Friction member
US4336277A (en) * 1980-09-29 1982-06-22 The Regents Of The University Of California Transparent electrical conducting films by activated reactive evaporation
US4803094A (en) * 1988-05-09 1989-02-07 Myers Richard A Metallized coating
US4947789A (en) * 1988-09-30 1990-08-14 Leybold Aktiengesellschaft Apparatus for vaporizing monomers that flow at room temperature
US4986212A (en) * 1989-10-11 1991-01-22 Kazuhiro Shibamoto Metallizing apparatus
US6258172B1 (en) * 1999-09-17 2001-07-10 Gerald Allen Foster Method and apparatus for boronizing a metal workpiece
US20080128094A1 (en) * 2004-10-21 2008-06-05 Tatsuo Fukuda Evaporation Source Device
EP2495041A1 (fr) 2006-06-28 2012-09-05 Saudi Arabian Oil Company Additif de catalyseur pour la réduction de soufre dans une essence à craquage catalytique

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1354702A (en) * 1970-02-12 1974-06-05 Baxter Ltd Alexander Methods of and means for vacuum deposition
US6697571B2 (en) * 2002-03-11 2004-02-24 The Dial Corporation Method and apparatus for selective positioning a wick material in a vapor-dispensing device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2665227A (en) * 1950-06-30 1954-01-05 Nat Res Corp Apparatus and method of coating by vapor deposition
US2665225A (en) * 1950-04-27 1954-01-05 Nat Res Corp Apparatus and process for coating by vapor deposition
US3350219A (en) * 1966-07-07 1967-10-31 Stackpole Carbon Co Evaporating metal employing porous member

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2608436A (en) * 1948-12-16 1952-08-26 Baughman John Leonard Air-conditioning and vaporizing fan
US2597195A (en) * 1950-03-18 1952-05-20 Garland D Runnels Vaporizer
US3068337A (en) * 1958-12-05 1962-12-11 Gen Electric Vaporizer and method for making the same
NL253747A (fr) * 1959-07-13
US3152246A (en) * 1960-03-24 1964-10-06 Philips Corp Device for depositing metal layers from vapour in vacuo
US3362915A (en) * 1965-02-24 1968-01-09 Richard Micek Method of and apparatus for generating silver iodide nuclei
US3413239A (en) * 1966-03-03 1968-11-26 Dow Chemical Co Vermicular graphite structures and method of making
US3627191A (en) * 1968-03-18 1971-12-14 Jesse Carl Hood Jr Solder wick

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2665225A (en) * 1950-04-27 1954-01-05 Nat Res Corp Apparatus and process for coating by vapor deposition
US2665227A (en) * 1950-06-30 1954-01-05 Nat Res Corp Apparatus and method of coating by vapor deposition
US3350219A (en) * 1966-07-07 1967-10-31 Stackpole Carbon Co Evaporating metal employing porous member

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928659A (en) * 1970-02-12 1975-12-23 Alexander Samuel Baxter Methods of and means for vacuum deposition
US3796182A (en) * 1971-12-16 1974-03-12 Applied Materials Tech Susceptor structure for chemical vapor deposition reactor
US3860443A (en) * 1973-03-22 1975-01-14 Fiber Materials Graphite composite
US3931493A (en) * 1973-06-21 1976-01-06 United Technologies Corporation Apparatus and method for the production of metal vapor
US4029829A (en) * 1974-02-08 1977-06-14 Dunlop Limited Friction member
US4027622A (en) * 1974-04-08 1977-06-07 Beckman Instruments G.M.B.H. Apparatus for doping semiconductors in centrifuge
US4336277A (en) * 1980-09-29 1982-06-22 The Regents Of The University Of California Transparent electrical conducting films by activated reactive evaporation
US4803094A (en) * 1988-05-09 1989-02-07 Myers Richard A Metallized coating
US4947789A (en) * 1988-09-30 1990-08-14 Leybold Aktiengesellschaft Apparatus for vaporizing monomers that flow at room temperature
US4986212A (en) * 1989-10-11 1991-01-22 Kazuhiro Shibamoto Metallizing apparatus
US6258172B1 (en) * 1999-09-17 2001-07-10 Gerald Allen Foster Method and apparatus for boronizing a metal workpiece
US20080128094A1 (en) * 2004-10-21 2008-06-05 Tatsuo Fukuda Evaporation Source Device
EP2495041A1 (fr) 2006-06-28 2012-09-05 Saudi Arabian Oil Company Additif de catalyseur pour la réduction de soufre dans une essence à craquage catalytique
EP2497571A1 (fr) 2006-06-28 2012-09-12 Saudi Arabian Oil Company Additif de catalyseur pour la réduction de soufre dans une essence à craquage catalytique

Also Published As

Publication number Publication date
CH531053A (de) 1972-11-30
US3723706A (en) 1973-03-27
BE722019A (fr) 1969-04-08
NL6713713A (fr) 1969-04-14
GB1229879A (fr) 1971-04-28
FR1589261A (fr) 1970-03-23
AT284582B (de) 1970-09-25
SE326874B (fr) 1970-08-03
DE1796216B2 (de) 1976-05-20
DE1796216A1 (de) 1972-04-13

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