US3401054A - Formation of coatings on germanium bodies - Google Patents

Formation of coatings on germanium bodies Download PDF

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Publication number
US3401054A
US3401054A US485078A US48507865A US3401054A US 3401054 A US3401054 A US 3401054A US 485078 A US485078 A US 485078A US 48507865 A US48507865 A US 48507865A US 3401054 A US3401054 A US 3401054A
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germanium
coating
atmosphere
vessel
coatings
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US485078A
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Wilkes John George
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General Electric Co PLC
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General Electric Co PLC
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
    • H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
    • H01L21/02233—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
    • H01L21/02236—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/3165—Inorganic layers composed of oxides or glassy oxides or oxide based glass formed by oxidation
    • H01L21/31654—Inorganic layers composed of oxides or glassy oxides or oxide based glass formed by oxidation of semiconductor materials, e.g. the body itself

Definitions

  • results obtained, in respect of the thickness and quality of the resultant coating, when using such a method depend on a number of factors. Firstly, it may be observed that the best results in respect of coherence of the coating are obtained when using relatively high temperatures (say above 600 C.); with such temperatures, the
  • results are not very dependent on the total pressure of the oxidising atmosphere provided this exceeds the minimum indicated above.
  • the results are, however, very dependent on the amount of water vapour present in the atmosphere; other things being equal, an increase in the amount of water vapour results in an increase in the thickness of the coating and also causes the coating to have a more granular nature.
  • the thickness of the coating is also dependent on the time and temperature of the heat ing, increasing with an increase of either of these factors, while an increase in the time of heating also results in an improvement in the coherence of the coating.
  • an atmosphere consisting essentially of oxygen and water vapour only, although in some cases these active constituents of the atmosphere may be diluted with an inert gas such as nitrogen.
  • a germanium body which has been chemically cleaned in conventional manner, is placed in a steel high pressure vessel which has an internal volume of about 100 cc. and which is lined with platinum to prevent contamination of the contents.
  • a controlled amount of water having a volume in the range 0.1-0.5 cc., is introduced into the vessel, and the vessel is then filled with oxygen at a pressure in the range l00-150 kgs./cm.
  • the sealed vessel is heated in a suitable furnace to a temperature of about 700 C., being maintained at this temperature for about 20 hours and then allowed to cool to room temperature.
  • the oxygen pressure within the vessel increases to about three times its initial value; the amount of water introduced into the vessel is such that the partial pressure of water vapour within the vessel is small compared with that of the oxygen.
  • the germanium body has formed on it a coherent adherent coating of germanium dioxide having a tetragonal crystal structure; the thickness of the oxide coating may be varied over a range of approximately one to twenty microns by choice of the precise value, within the range indicated above, of the volume of water intro quizd into the vessel.
  • the oxide has crystal lattice unit cell dimensions, determined by X-ray analysis, as follows:
  • a method of manufacturing a germanium body having formed on its surface a coherent adherent coating of germanium dioxide having a tetragonal crystal structure which includes the steps of exposing a germanium body, initially free from any surface coating, to an oxidizing atmosphere containing water vapor, the total pressure of said atmosphere being at least 30 kilograms per square centimeter, and heating the said body at a temperature above 400 C., while the body is exposed to said atmosphere.
  • a method of manufacturing a germanium body having formed on its'surface a coherent adherent coating of germanium dioxide having a tetragonal crystal structure which includes the steps of placing a germanium body in a steel pressure vessel lined with platinum, then introducing into the said vessel a volume of water in the range of 0.1% to 0.5% of the internal volume of the vessel, then filling the vessel with oxygen at a pressure in the range of to kilograms per square centimeter and sealing the vessel, then heating the sealed vessel to a tem perature of 700 C. and maintaining it at this temperature for about 20 hours, and then allowing the vessel to cool to room temperature before withdrawing the coated germanium body therefrom.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Physical Vapour Deposition (AREA)

Description

United States Patent 3,401,054 FORMATION OF COATINGS 0N GERMANIUM BODIES John George Wilkes, Hatch End, Middlesex, England, as-
signor to The General Electric Company Limited, London, England No Drawing. Filed Sept. 3, 1965, Ser. No. 485,078
5 Claims. (Cl. 117-201) a germanium body a coating of germanium dioxide having a tetragonal crystal structure, the body is heated above 400 C. while exposed to an oxidising atmosphere containing water vapour, the total pressure of said atmosphere being at least kgs./cm.
The results obtained, in respect of the thickness and quality of the resultant coating, when using such a method depend on a number of factors. Firstly, it may be observed that the best results in respect of coherence of the coating are obtained when using relatively high temperatures (say above 600 C.); with such temperatures, the
results are not very dependent on the total pressure of the oxidising atmosphere provided this exceeds the minimum indicated above. The results are, however, very dependent on the amount of water vapour present in the atmosphere; other things being equal, an increase in the amount of water vapour results in an increase in the thickness of the coating and also causes the coating to have a more granular nature. The thickness of the coating is also dependent on the time and temperature of the heat ing, increasing with an increase of either of these factors, while an increase in the time of heating also results in an improvement in the coherence of the coating.
It will be appreciated that when using a method according to the invention in the manufacture of semiconductor devices, it will normally be required to provide a good coherent coating of well controlled thickness. To this end, it will normally be desirable to carry out the method at a temperature above 600 C., and to choose the water vapour content of the oxidising atmosphere so as to obtain a coating of the desired thickness in a time which is sufiiciently short to be convenient from the point of view of a manufacturing process but at the same time sufficiently long to ensure that the coating has the required degree of coherence; it may be noted that a time of about 20 hours will normally be suitable having regard to these considerations.
It will normally be convenient to use an atmosphere consisting essentially of oxygen and water vapour only, although in some cases these active constituents of the atmosphere may be diluted with an inert gas such as nitrogen.
One method of performing the invention will now be described by way of example.
In this method a germanium body, which has been chemically cleaned in conventional manner, is placed in a steel high pressure vessel which has an internal volume of about 100 cc. and which is lined with platinum to prevent contamination of the contents. A controlled amount of water, having a volume in the range 0.1-0.5 cc., is introduced into the vessel, and the vessel is then filled with oxygen at a pressure in the range l00-150 kgs./cm.
and sealed. The sealed vessel is heated in a suitable furnace to a temperature of about 700 C., being maintained at this temperature for about 20 hours and then allowed to cool to room temperature. During the heating the oxygen pressure within the vessel increases to about three times its initial value; the amount of water introduced into the vessel is such that the partial pressure of water vapour within the vessel is small compared with that of the oxygen.
As a result, the germanium body has formed on it a coherent adherent coating of germanium dioxide having a tetragonal crystal structure; the thickness of the oxide coating may be varied over a range of approximately one to twenty microns by choice of the precise value, within the range indicated above, of the volume of water intro duced into the vessel. The oxide has crystal lattice unit cell dimensions, determined by X-ray analysis, as follows:
that is it is of the form denoted T(I) in British patent specification No. 976,559.
I claim:
1. A method of manufacturing a germanium body having formed on its surface a coherent adherent coating of germanium dioxide having a tetragonal crystal structure, which includes the steps of exposing a germanium body, initially free from any surface coating, to an oxidizing atmosphere containing water vapor, the total pressure of said atmosphere being at least 30 kilograms per square centimeter, and heating the said body at a temperature above 400 C., while the body is exposed to said atmosphere.
2. A method according to claim 1 wherein the said atmosphere consists essentially of oxygen and water vapor, the partial pressure of the water vapor being small compared with that of the oxygen.
3. A method according to claim 1 wherein the germanium body is heated, while exposed to the said atmosphere, at a temperature above 600 C.
4. A method according to claim 3 wherein the said heating of the germanium body is continued for about 20 hours.
5. A method of manufacturing a germanium body having formed on its'surface a coherent adherent coating of germanium dioxide having a tetragonal crystal structure, which includes the steps of placing a germanium body in a steel pressure vessel lined with platinum, then introducing into the said vessel a volume of water in the range of 0.1% to 0.5% of the internal volume of the vessel, then filling the vessel with oxygen at a pressure in the range of to kilograms per square centimeter and sealing the vessel, then heating the sealed vessel to a tem perature of 700 C. and maintaining it at this temperature for about 20 hours, and then allowing the vessel to cool to room temperature before withdrawing the coated germanium body therefrom.
References Cited UNITED STATES PATENTS 3,298,875 l/1967 Schink 117--201 X 3,340,163 9/1967 Bradshaw et al. 117-201 X 3,342,619 9/1967 Chu 117-401 FOREIGN PATENTS 219,126 12/ 1958 Australia.
WILLIAM L. JARVIS, Primary Examiner.

Claims (1)

1. A METHOD OF MANUFACTURING A GERMANIUM BODY HAVING FORMED ON ITS SURFACE A COHERENT ADHERENT COATING OF GERMANIUM DIOXIDE HAVING A TETRAGONAL CRYSTALS STRUCTURE, WHICH INCLUDES THE STEPS OF EXPOSING A GERMANIUM BODY, INITIALLY FREE FROM ANY SURFACE COATING, TO AN OXIDIZING ATMOSPHERE CONTAINING WATER VAPOR, THE TOTAL PRESSURE OF SAID ATMOSPHERE BEING AT LEAST 30 KILOGRAMS PER SQUARE CENTIMETER, AND HEATING THE SAID BODY AT A TEMPERATURE ABOVE 400*C., WHILE THE BODY IS EXPOSED TO SAID ATMOSPHERE.
US485078A 1965-09-03 1965-09-03 Formation of coatings on germanium bodies Expired - Lifetime US3401054A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3525650A (en) * 1965-12-10 1970-08-25 Siemens Ag Method of producing a water-insoluble germanium oxide coating at the surface of a germanium crystal
US3955013A (en) * 1972-12-04 1976-05-04 Grumman Aerospace Corporation Novel process for producing a thin film of germanium

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3298875A (en) * 1962-06-20 1967-01-17 Siemens Ag Method for surface treatment of semiconductor elements
US3340163A (en) * 1962-08-09 1967-09-05 Gen Electric Co Ltd Method for forming a tetragonal crystalline oxide coating on germanium
US3342619A (en) * 1964-04-16 1967-09-19 Westinghouse Electric Corp Method for growing germania films

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3298875A (en) * 1962-06-20 1967-01-17 Siemens Ag Method for surface treatment of semiconductor elements
US3340163A (en) * 1962-08-09 1967-09-05 Gen Electric Co Ltd Method for forming a tetragonal crystalline oxide coating on germanium
US3342619A (en) * 1964-04-16 1967-09-19 Westinghouse Electric Corp Method for growing germania films

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3525650A (en) * 1965-12-10 1970-08-25 Siemens Ag Method of producing a water-insoluble germanium oxide coating at the surface of a germanium crystal
US3955013A (en) * 1972-12-04 1976-05-04 Grumman Aerospace Corporation Novel process for producing a thin film of germanium

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