US3856557A - Process for forming a manganese bismuthide film - Google Patents

Process for forming a manganese bismuthide film Download PDF

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Publication number
US3856557A
US3856557A US00294069A US29406972A US3856557A US 3856557 A US3856557 A US 3856557A US 00294069 A US00294069 A US 00294069A US 29406972 A US29406972 A US 29406972A US 3856557 A US3856557 A US 3856557A
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United States
Prior art keywords
manganese
bismuth
substrate
bismuthide
film
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Expired - Lifetime
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US00294069A
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English (en)
Inventor
W Cuttell
N Truman
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Fujitsu Services Ltd
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Fujitsu Services Ltd
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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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • 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
    • C23C14/58—After-treatment
    • 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
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • 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
    • C23C14/58—After-treatment
    • C23C14/5893—Mixing of deposited material

Definitions

  • a process for the formation of a manganese bismuthide film including depositing bismuth and manganese in vacuo to form a layer upon a common substrate, depositing in vacuo material over the layer to form an air impervious coating and then subjecting, whilst in the presence air, the coated substrate to a temperature regime which converts the manganese and bismuth to a layer of manganese bismuthide.
  • FIG. 1 schematically illustrates the principal stages of the process of the invention.
  • FIG. 2 is a diagrammatic representation of vacuum depositioning apparatus for performing the initial stages of the process
  • FIG. 3 illustrates a coated substrate
  • a first highvacuum unit 1 includes a base plate 2 carrying a column 3 supporting near the upper end thereof a rotatable support plate 4 for mounting substrates 5 which are to be'coated with a manganese bismuthide film.
  • An electron beam unit 6 which includes an electron source (not shown) and suitable electrodes 7 is arranged to direct a beam 8 of electrons towards a target plate 9, carried from an arm 10 mounted on a vertical shaft 11 for rotation about a vertical axis.
  • a motor 12 is provided for rotating the shaft. The motor 12 is used to swing the target plate 9 into and away from the line of the electron beam 8.
  • means not shown are provided for rotating the plate 4 to bring the substrates successively into the depositioning position.
  • suitable masking arrangements will be provided to prevent undesired coating of substrates.
  • a second plate with an aperture could be located below the plate 4 and substrate 5 such that rotating of the plate 4 brings successive substrates into the coating position at the aperture.
  • the rotation can be by means of an electric motor drive or hand drive system.
  • the target plate 9 carries a crucible I3 for receiving material to be melted.
  • a second target plate 14 likewise supported by an arm 15 is swingably mounted upon the shaft 11 for rotation by the motor 12.
  • the relative arrangement can be such that on moving a target into the line of the beam the other target is moved out from the line of the beam or alternatively the targets can be individually adjustable.
  • a transparent closure member 16 is hermetically scalable to the base plate 2.
  • the interior of the member 16 is connectable to a vacuum pump 17 by a suitable conduit 18.
  • the substrate 5 can comprise a glass such as Corning 7059 glass, or other transparent material such as a freshly cleaned optical ruby mica sheet of for example 2.54 X 1.28 mm in dimensions.
  • a glass such as Corning 7059 glass, or other transparent material such as a freshly cleaned optical ruby mica sheet of for example 2.54 X 1.28 mm in dimensions.
  • An advantage of mica is that mica are readily cleaved and has a. basal plane symmetry which is the same as an Mn Bi thereby encouraging expitaxial growth.
  • a further suitable substrate was found to be a pyrex type glass disc some IO centimeters diameter.
  • the coating process according to the invention is carried out as follows:
  • a measured quantity of bismuth is placed in the crucible I3, and a measured quantity of manganese is placed in the crucible 14.
  • the chamber 1 is pumped down to a pressure of the order of 10' torr.
  • the crucible containing the bismuth is brought into line with the electron beam and is vapourised to form a layer 19.-
  • the quantities of bismuth and manganese vapourised are such that the films are deposited in the range 2.8-3: 1 with a preferred range of 3: l.
  • the thickness of the combined film lies within a range of 600 to 1000 Angstrom units.
  • the apparatus used is very high grade vacuum apparatus and preferably should be capable of being pumped down to 10' torr.
  • the coated substrate could be heat treated in the deposition apparatus however this because of the time involved substantially reduces the productivity of the very high grade vacuum apparatus.
  • the coated substrate is, therefore, placed in a second vacuum deposition apparatus and the layers of bismuth and manganese are encapsulated, that is coated with a material which forms an air impervious layer 21 over the bismuth and manganese which does not chemically react with these materials.
  • a convenient material is silicon monoxide.
  • a layer 21 of this material is formed by vapour deposition over the layers of bismuth and manganese.
  • the second vacuum apparatus can be of the oil diffusion pumped system type capable of operating to produce pressures of the order of 10 or torr, since the chamber pressures suitable for the production of the silicon monoxide films are less stringent than for the bismuth and manganese layers.
  • the thickness of the silicon monoxide film is of the order of 6,000 Angstrom units thick.
  • the substrate together with its composite manganese and bismuth film and coated with silicon monoxide is then placed in an oven and is heated in air to a temperature of approximately 200c for at least two hours.
  • the layer of silicon monoxide prevents the oxydation ofthe composite layer during its conversion to the intermediate manganese bismuthide.
  • a preferred heating time period was five hours.
  • the substrate is cooled or is allowed to cool.
  • the substrate is then examined in polarised light to ascertain whether or not the above mentioned conversion is completed. If the conversion is incomplete the substrate is returned to the oven for further heat treatment to complete the conversion stage.
  • the formation of the silicon monoxide layer has two important advantages. Firstly, it avoids the necessity for the heating stage to be carried out in the deposition apparatus, with the result that this apparatus may now be used only for the initial formation of the composite layer, thereby greatly increasing its productivity.
  • the process of conversion may also be improved and speeded up. since it is no longer imperative that the heat treated substrate be cooled in the absence of air before it can be examined. Furthermore, any further heat treatment that may be necessary may readily be applied simply by replacing the substrate in the oven without the need to clear and pump down a vacuum chamber.
  • the bismuth and manganese can be co-deposited. This can be effected by simultaneously vapourising measured quantities of bismuth and manganese thereby producing a film which comprises an intimate mixture of manganese and bismuth which is subsequently converted to the intermetallic compound Mn Bi during the above described heat treatment stage.
  • a process for the formation ofa film of intermetallic manganese bismuthide on a substrate comprising the steps of; depositing under vacuum at a first pressure level manganese and bismuth on to the same region of the substrate; depositing under a vacuum at a second pressure higher than the first level an air impervious layer which is chemically inert to the manganese and bismuth to encapsulate the manganese and the bismuth; tranferring the substrate to a heating zone, and converting the manganese and bismuth into an intermetallic manganese bismuthide by heating the manganese and bismuth under ambient pressure conditions for at least 2 hours at a temperature of approximately 200c.
  • a process for the formation ofa manganese bismuthide film on a substrate comprising the steps of depositing under vacuum at a pressure of at least l0 torr manganese and bismuth on to the substrate; depositing an air impervious layer of silicon monoxide over the manganese and bismuth under vacuum at pressure of 10" torr to 10' torr; transferring the substrate into a.
  • heating zone and converting the manganese and bismuth to an intermetallic manganese bismuthide by heating the manganese and bismuth under ambient pressure conditions for at least two hours at approximately 200c.

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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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Physical Vapour Deposition (AREA)
US00294069A 1971-10-01 1972-10-02 Process for forming a manganese bismuthide film Expired - Lifetime US3856557A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB4577371A GB1371522A (en) 1971-10-01 1971-10-01 Process for forming a manganese bismuthide film

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US3856557A true US3856557A (en) 1974-12-24

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US (1) US3856557A (enExample)
FR (1) FR2156672B3 (enExample)
GB (1) GB1371522A (enExample)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4328763A (en) * 1979-05-03 1982-05-11 Leybold-Heraeus Vaporizer for vacuum deposition installations
US4409079A (en) * 1981-06-24 1983-10-11 Hitachi, Ltd. Method of metallizing sintered ceramics

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2228948A (en) * 1989-02-28 1990-09-12 British Aerospace Fabrication of thin films from a composite target

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3008844A (en) * 1959-09-01 1961-11-14 Grunin Louis Iridescent pigments, effects and products
US3050409A (en) * 1959-11-30 1962-08-21 Owens Illinois Glass Co Manufacture of refractory oxide coatings
US3466224A (en) * 1966-03-02 1969-09-09 Ogretta H Vaughn Pressure vessel of metal and silicon monoxide layers
US3489593A (en) * 1965-03-24 1970-01-13 Nat Res Corp Method of sealing vacuum-deposited metal coatings
US3498818A (en) * 1968-01-23 1970-03-03 Gen Electric Method of making highly reflective aluminum films
US3702240A (en) * 1971-03-04 1972-11-07 Owens Corning Fiberglass Corp Method of making impact resistant inorganic composites

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3008844A (en) * 1959-09-01 1961-11-14 Grunin Louis Iridescent pigments, effects and products
US3050409A (en) * 1959-11-30 1962-08-21 Owens Illinois Glass Co Manufacture of refractory oxide coatings
US3489593A (en) * 1965-03-24 1970-01-13 Nat Res Corp Method of sealing vacuum-deposited metal coatings
US3466224A (en) * 1966-03-02 1969-09-09 Ogretta H Vaughn Pressure vessel of metal and silicon monoxide layers
US3498818A (en) * 1968-01-23 1970-03-03 Gen Electric Method of making highly reflective aluminum films
US3702240A (en) * 1971-03-04 1972-11-07 Owens Corning Fiberglass Corp Method of making impact resistant inorganic composites

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4328763A (en) * 1979-05-03 1982-05-11 Leybold-Heraeus Vaporizer for vacuum deposition installations
US4409079A (en) * 1981-06-24 1983-10-11 Hitachi, Ltd. Method of metallizing sintered ceramics

Also Published As

Publication number Publication date
FR2156672A1 (enExample) 1973-06-01
AU4715872A (en) 1974-04-04
GB1371522A (en) 1974-10-23
FR2156672B3 (enExample) 1975-10-17

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