US3801355A - Plasma deposition of thin layers on substrates - Google Patents

Plasma deposition of thin layers on substrates Download PDF

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Publication number
US3801355A
US3801355A US00246019A US24601972A US3801355A US 3801355 A US3801355 A US 3801355A US 00246019 A US00246019 A US 00246019A US 24601972 A US24601972 A US 24601972A US 3801355 A US3801355 A US 3801355A
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United States
Prior art keywords
cavity
plasma
gas
thin layers
substrate
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Expired - Lifetime
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US00246019A
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English (en)
Inventor
Cakenberghe J Van
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.)
Alcatel CIT SA
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Compagnie Industrielle de Telecommunication CIT Alcatel SA
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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
    • 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
    • C23C14/228—Gas flow assisted PVD deposition
    • 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
    • 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
    • C23C14/3471—Introduction of auxiliary energy into the plasma
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3411—Constructional aspects of the reactor
    • H01J37/3414—Targets
    • H01J37/342—Hollow targets

Definitions

  • ABSTRACT A method for producing thin layers of coating substances on substrates by plasma evaporation, comprising shaping a coating substance as a hollow body, passing a non-reactive gas through the body and subjecting the gas while in the body to an electromagnetic field to form a plasma. Coating material is vaporized from the interior of the body by the plasma, entrained in the gas and carried by the gas to a substrate on which it is deposited in a thin layer.
  • the present invention concerns a method enabling thin layers of mineral substances to be deposited, as well as the device for implementing the method.
  • Thin layers are usually produced by evaporation in a vacuum or by a method called reactive projection.
  • the first method can be used only in cases where the substance to be deposited decomposes when it is brought to a high temperature in a vacuum, into elements having very different vapor pressures and the most volatile of which can have a vapor pressure which can be measured at the depositing temperature. Such is the case, more particularly, with the majority of oxides, certain sulphides as well as of gallum arsenide and gallium phosphide.
  • the second method mentioned above consists in causing the evaporation of the material to be deposited in an electrical discharge at low pressure, between two electrodes one of which consists of the material to be deposited or the metallic component of that material, the other component then being contained in gaseous phase.
  • the material to be deposited is deposited in the form of a thin layer on a substrate, arranged at a few centimeters from that electrode, which can be in contact or otherwise with the second electrode.
  • the first electrode can consist either of zinc oxide or of metallic zinc with a pure gaseous oxygen atmosphere or an atmosphere consisting of oxygen mixed with a neutral gas such as argon.
  • This second method can certainly be used for the above-mentioned substances, but it is unsuitable for semi-conductor materials, for the thin layers thus obtained consist of very small micro-crystals so that certain electrical properties such as the mobility and service life of the charge carriers are subjected to detrimental influence. Moreover, this second method is characterized by a relatively considerable dissipation of energy and a relatively low depositing speed which can, moreover, vary within wide limits.
  • the object of the invention is therefore a method for depositing thin layers which does not have the abovemetnioned disadvantages.
  • It also provides a device for producing thin layers, either on insulating supports or on electrically conductive or semi-conductive supports.
  • the method enabling thin layers to be deposited in a vacuum on the surface of a substrate arranged facing the opening of a cavity in which a gas is injected at a pre-determined pressure is characterized in that a plasma is formed inside the cavity previously lined on the inside with the substance to be deposited.
  • the method also enables layers to be deposited ont the surface of a substrate when the cavity consists directly of the substance to be deposited.
  • the device implementing the method according to the invention is characterized in that it comprises, on the one hand, a high-frequency excitation means generating an electromagnetic field, and, on the other hand, inside a vacuum container, at least a substrate support, a substrate, a cavity lined on the inside with the substance to be deposited and having an opening facing the substrate and a means for injecting a gas at a predetermined pressure into said cavity, promoting the forming of a plasma within said cavity where there is the electromagnetic field.
  • the device implementing the method according to the invention is also characterized in that the support for the substrate comprises an electrical heating means enabling the substrate to be brought to a predetermined temperature.
  • the device according to the invention is characterized in that it comprises, moreover, an electrode in the cavity, this electrode being connected to an appropriate electrical potential so as to produce a spark suitable for causing the starting up of the plasma.
  • the cavity has, to great advantage, a cylindrical shape, the cylindrical wall being provided, on its inside, with longitudinal ribs. Moreover, the insulating container may, to great advantage, be cooled.
  • FIG. 1 is a longitudinal sectional view of an embodiment of the device according to the invention.
  • FIG. 2 is a transversal sectional view of an embodiment of the cavity having a great advantage, used in the device according to the invention.
  • FIG. 3 is a longitudinal sectional view of another embodiment of the device according to the invention.
  • One of the transversal faces of the cavity is provided with an opening 3.
  • the high-frequency excitation device consists, here, of an induction winding 4 surrounding the tube 1 at the level of the cavity. This winding is connected to a high frequency voltage supply 5.
  • a substrate support 6 is placed so as to have a substrate 7 facing the opening 3 in the chamber 2.
  • the electrical heating device 8 enables the substrate 7 to be brought to a required temperature.
  • the substrate support 6 is arranged so as to be able to pivot about an axis 9 in order to bring several substrates successively before the opening 3.
  • the cylindrical wall of the cavity comprises, on the inside, longitudinal ribs 10 so as to reduce the transmission of heat through the wall.
  • a gas is injected into the cavity through the duct 11 so as to produce an atmosphere at a pre-determined pressure therein.
  • the electromagnetic field it induces inside the cavity forms a plasma thereon.
  • the discharge which takes place in the plasma causes a great increase in the temperature of the inside wall of the cavity, this producing a distilling of the inner wall and the establishing of a vapor pressure of the substance to be deposited.
  • This distilled substance escapes through the opening 3 and is deposited on the substrate 7.
  • the plasma is confined inside the cavity.
  • the thin layers thus obtained consist of crystals which are appreciably larger and better formed than those obtained by reactive projection. It has also been noted that the crystalline direction of the thin layers is perfect.
  • the walls of the cavity constitute a thermal screen.
  • the latter have been reinforced by arranging a second cavity round the first. This screen effect enables the energy dissipated in the plasma to be increased so as to bring the inside surface of the cavity to a very high temperature in the order of several thousands of degrees without danger for the insulating tube 1.
  • the device comprises, moreover, an electrode 12 in the opening 3 formed in the chamber 2.
  • This electrode 12 is connected to an appropriate electrical potential supply V so as to produce a spark suitable for promoting the starting up of the plasma.
  • the tube 1 is surrounded by a cooling funnel. It is thus possible to obtain high evaporating speeds and relatively high vapor pressures inside the cavity, this promoting molecular combination.
  • a cylindrical cavity consisting of zinc oxide, 50 mm in diameter and 60 mm in height, has been placed in a quartz tube.
  • An induction winding consisting of three turns made of copper tubing 6 mm in diameter, connected to a highfrequency power generator, has been arranged about the tube, on the level of the cavity.
  • the high-frequency generator After having started up the high-frequency generator so that it supplies a power of 4 kw at 3 mc/s, the rated power is reached after barely a few minutes, and the zinc oxide is then deposited on the substrate in the form of a thin layer which has reached a thickness of 0.5 micron in 1 minute.
  • the induction means implemented to generate the plasma inside the cavity is placed in the vacuum about the cavity.
  • This embodiment shown in FIG. 3, comprises a cylindrical chamber forming a cavity placed in a vacuum container shown in the figure only by its base 30.
  • This chamber 20 is lined inside with 6 the material 21 to be sprayed, it comprises, at its upper part, a central opening 22, and at its lower part, a gas inlet 23.
  • the lateral face 24 of that cylindrical chamber 20 is surrounded by the turns 25 of an induction circuit 26, fed by a HF supply, not shown, arranged outside the container.
  • This induction circuit 26 consists of a hollow conductor internally cooled by a water circuit 27, 27.
  • the induction circuit is held in position by an insulating base 28 fixed to the base 30 of the container.
  • the conductor forming the induction circuit is itself lined with a layer of protective insulating material 29, made of teflon, in a series of experiments, and of glass in another series of measurements.
  • a protective screen 31 made of insulating material completes the protection of the substrate with respect to any pollution caused by the metal forming the induction circuit.
  • a seal ring 32 made of refractory material which is a bad heat conductor arranged round the opening 22 of the cavity 20 provides a poor heat contact between the cavity 20 and the insulating screen 30 while providing satisfactory sealing.
  • the applicant has also produced a device in which the cavity is drilled with several openings so that several substrates are covered simultaneously.
  • the cavity has been divided into several compartments without an appreciable reduction in the depositing speed having been noticed.
  • the devices according to the invention may be used to great advantage, for producing thin layers of various substances: piezo-electric, semi-conductive, optical, magnetic, insulating substances, materials having great dielectric constancy, refractory materials or compounds thereof having a high melting point.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Physical Vapour Deposition (AREA)
US00246019A 1971-04-27 1972-04-20 Plasma deposition of thin layers on substrates Expired - Lifetime US3801355A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
BE102716 1971-04-27

Publications (1)

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US3801355A true US3801355A (en) 1974-04-02

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US00246019A Expired - Lifetime US3801355A (en) 1971-04-27 1972-04-20 Plasma deposition of thin layers on substrates

Country Status (8)

Country Link
US (1) US3801355A (xx)
JP (1) JPS5511744B1 (xx)
BE (1) BE766345A (xx)
CH (1) CH561286A5 (xx)
DE (1) DE2220086C3 (xx)
FR (1) FR2134336B1 (xx)
IT (1) IT965683B (xx)
NL (1) NL7205566A (xx)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3922214A (en) * 1973-03-27 1975-11-25 Cit Alcatel Device for manufacturing thin layers of mineral substances
DE3016022A1 (de) * 1979-04-26 1981-03-26 Optical Coating Laboratory Inc., Santa Rosa, Calif. Verfahren und einrichtung zur herstellung eines duennen, filmartigen belags durch bedampfung unter verwendung einer umschlossenen plasmaquelle
US4687560A (en) * 1985-08-16 1987-08-18 The United States Of America As Represented By The United States Department Of Energy Method of synthesizing a plurality of reactants and producing thin films of electro-optically active transition metal oxides
US4915906A (en) * 1988-06-17 1990-04-10 Canadian Patents And Development Limited/Societie Canadienne Des Brevets Et D'exploitation Limitee Novel zinc-based alloys, preparation and use thereof for producing thermal-sprayed coatings having improved corrosion resistance and adherence
US6177142B1 (en) * 1998-05-28 2001-01-23 John T. Felts Method of forming a film on a substrate
US20030049003A1 (en) * 2001-04-12 2003-03-13 Ahmad Rokan U. High index-contrast fiber waveguides and applications
US20040137168A1 (en) * 2002-11-22 2004-07-15 Vladimir Fuflyigin Dielectric waveguide and method of making the same
US20090252945A1 (en) * 2008-04-04 2009-10-08 Arno Refke Method and apparatus for the coating and for the surface treatment of substrates by means of a plasma beam

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2245779B1 (xx) * 1973-09-28 1978-02-10 Cit Alcatel
DE2830134C2 (de) 1978-07-08 1983-12-08 Wolfgang Ing.(grad.) 7981 Grünkraut Kieferle Verfahren zum Ablagern einer Metall- oder Legierungsschicht auf ein elektrisch leitendes Werkstück
DE2857102C2 (de) * 1978-07-08 1983-12-01 Wolfgang Ing.(grad.) 7981 Grünkraut Kieferle Vorrichtung zum Eindiffundieren und Auflagern einer Metall- oder Legierungsschicht auf ein elektrisch leitendes Werkstück
GB2085482B (en) * 1980-10-06 1985-03-06 Optical Coating Laboratory Inc Forming thin film oxide layers using reactive evaporation techniques

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1065108A (en) * 1964-04-09 1967-04-12 Western Electric Co Production of oxide films on solid substrates
NL130959C (xx) * 1965-12-17
DE1905058C3 (de) * 1969-02-01 1973-10-04 Leybold-Heraeus Gmbh & Co, Kg, 5000 Koeln-Bayental Vorrichtung für die Beschichtung von Werkstücken durch Hochfrequenz-Plasmazerstäubung von Werkstoffen im Vakuum

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3922214A (en) * 1973-03-27 1975-11-25 Cit Alcatel Device for manufacturing thin layers of mineral substances
DE3016022A1 (de) * 1979-04-26 1981-03-26 Optical Coating Laboratory Inc., Santa Rosa, Calif. Verfahren und einrichtung zur herstellung eines duennen, filmartigen belags durch bedampfung unter verwendung einer umschlossenen plasmaquelle
US4268711A (en) * 1979-04-26 1981-05-19 Optical Coating Laboratory, Inc. Method and apparatus for forming films from vapors using a contained plasma source
US4687560A (en) * 1985-08-16 1987-08-18 The United States Of America As Represented By The United States Department Of Energy Method of synthesizing a plurality of reactants and producing thin films of electro-optically active transition metal oxides
US4915906A (en) * 1988-06-17 1990-04-10 Canadian Patents And Development Limited/Societie Canadienne Des Brevets Et D'exploitation Limitee Novel zinc-based alloys, preparation and use thereof for producing thermal-sprayed coatings having improved corrosion resistance and adherence
US6177142B1 (en) * 1998-05-28 2001-01-23 John T. Felts Method of forming a film on a substrate
US6180185B1 (en) * 1998-05-28 2001-01-30 John T. Felts Method of forming a film on a substrate
US6898359B2 (en) 2001-04-12 2005-05-24 Omniguide Communications High index-contrast fiber waveguides and applications
US6788864B2 (en) 2001-04-12 2004-09-07 Omniguide Communications High index-contrast fiber waveguides and applications
US6801698B2 (en) 2001-04-12 2004-10-05 Omniguide Communications High index-contrast fiber waveguides and applications
US20030049003A1 (en) * 2001-04-12 2003-03-13 Ahmad Rokan U. High index-contrast fiber waveguides and applications
US20050259944A1 (en) * 2001-04-12 2005-11-24 Emilia Anderson High index-contrast fiber waveguides and applications
US7142756B2 (en) 2001-04-12 2006-11-28 Omniguide, Inc. High index-contrast fiber waveguides and applications
US7190875B2 (en) 2001-04-12 2007-03-13 Omniguide, Inc. Fiber waveguide formed from chalcogenide glass and polymer
US20040137168A1 (en) * 2002-11-22 2004-07-15 Vladimir Fuflyigin Dielectric waveguide and method of making the same
US20040141702A1 (en) * 2002-11-22 2004-07-22 Vladimir Fuflyigin Dielectric waveguide and method of making the same
US20080141724A1 (en) * 2002-11-22 2008-06-19 Omniguide, Inc. Dielectric waveguide and method of making the same
US7854149B2 (en) 2002-11-22 2010-12-21 Omniguide, Inc. Dielectric waveguide and method of making the same
US20090252945A1 (en) * 2008-04-04 2009-10-08 Arno Refke Method and apparatus for the coating and for the surface treatment of substrates by means of a plasma beam

Also Published As

Publication number Publication date
DE2220086B2 (de) 1981-07-23
FR2134336A1 (xx) 1972-12-08
DE2220086A1 (de) 1972-11-16
BE766345A (fr) 1971-09-16
FR2134336B1 (xx) 1974-05-10
DE2220086C3 (de) 1982-05-06
JPS5511744B1 (xx) 1980-03-27
IT965683B (it) 1974-02-11
CH561286A5 (xx) 1975-04-30
NL7205566A (xx) 1972-10-31

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