US3793069A - Process for preparing a layer of compounds of groups ii and vi - Google Patents

Process for preparing a layer of compounds of groups ii and vi Download PDF

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Publication number
US3793069A
US3793069A US00172454A US3793069DA US3793069A US 3793069 A US3793069 A US 3793069A US 00172454 A US00172454 A US 00172454A US 3793069D A US3793069D A US 3793069DA US 3793069 A US3793069 A US 3793069A
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United States
Prior art keywords
film
layer
oxygen
heat treatment
selenium
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Expired - Lifetime
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US00172454A
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English (en)
Inventor
K Shimizu
O Yoshida
K Terakawa
S Aihara
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Toshiba Corp
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Tokyo Shibaura Electric Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
    • 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

Definitions

  • This invention relates to a process for preparing a layer of Groups II Vl compounds with narrow grain size distribution.
  • a film of a large area of a compound or a film of a compound separately distributed over a large area is useful as a light-electricity transducer in a wide range of technical fields, such as solar cells, solid state photosensors for image pickup application, photoconductive film for image pickup tubes, etc.
  • Such films should be furnished not only with electrical properties satisfactory enough for desired performance, but also with uniformity in such properties over a wide area. For instance, local unbalance in photo-sensitivity or intensity of luminescence of a film element not only abates the commercial value thereof, but constitutes a fatal factor which restricts the life of the film element.
  • Such a film is formed by vacuum evaporation or gaseous phase reaction on the surface of a substrate plate.
  • heat treatment is necessary after film formation in many cases.
  • Such heat treatment is generally accompanied by growth of grains which constitute the film. Therefore the characteristics of a film element, especially uniformity of the characteristics over a wide area is often influenced by the grain growth during the heat treatment.
  • it is important to select a suitable temperature but the maximum temperature may be limited because of heat resistance of the substrate material, possible decomposition of the compound constituting the film, etc. Therefore, fluxes are widely employed in such. heat treatment.
  • a typical example of such fluxes used in the heat treatment is cadmium chloride, which is employed in the treatment of cadmium sulfide used for photoconductive elements.
  • Cadmium chloride is effective for cadmium selenide or cadmium sulfoselenide film, too.
  • To make the effect of the heat treatment satisfactory consideration is paid to making the flux concentration as uniform as possible.
  • cadmium chloride is used in the heat treatment of cadmium sulfide or cadmium selenide photoconductive films, a large quantity of chlorine penetrates into the photoconductive film and in some cases the concentration thereof reaches as high as 10 atoms/cc. This chlorine builds up a shallow doner level in the cadmium sulfide or selenide. The existence of such high concentration of a shallow doner level impairs photo-sensitivity of the films and in some other cases retards response to light.
  • such uniformly distributed nuclei which lead to a film of a uniform structure with narrow range grain size distribution are provided on the surface ofa film of Groups II VI compounds by carrying out the heat treatment of said film in an atmosphere comprising an-inert gas and 0.1 10 percent by volume of oxygen on the basis of said inert gas and the vapour of at least one element selected from a group consisting of sulfur, selenium and tellurium.
  • selenium vapour exhibiting saturation vapour pressure at 500C co-exists.
  • This selenium vapour can be mixed with the oxygen prior to the heat treatment or can be generated in situ by suitable means.
  • the grain size of the originally deposited film which is about 1,000 A grows to about 1.5g. and a film having grain size which is quite uniform is obtained.
  • This grain growth is the same as the grain growth which results from a process in which 20 mole percent of cadmium chloride is mixed with cadmium selenide when the substrate plate is treated therewith and the deposited film is heat-treated in a nitrogen atmosphere.
  • the invention of this reference relates to a process of heat treatment in which cadmium selenide is heat-treated together with a flux, and the atmosphere comprises oxygen, nitrogen and cadmium halide vapour, whereby grain growth is effectuated with the cadmium halide flux, and oxygen is added for filling selenium vacancies merely as anauxiliary agent.
  • Curve 4 represents the grain size distribution when a film is heat-treated in an atmosphere in which oxygen and selenium vapour co-exist in accordance with this invention.
  • FIGS. 2 and 3 which show electron photomicrographs of the film of this invention and that of the prior art, shows how superior the film of this invention is to that of the prior art in the grain size and the grain size distribution.
  • the photoconductive film of this invention as represented by FIG. 2, is free from unevenness in photoelectric sensitivity.
  • the desired reaction should contain larger proportions of oxygen than prescribed for concomitance with vapours of selenium, for example, if the reaction is performed in the ordinary air, then oxidation will proceed in excess. This will cause an intermediate oxide to form whose growth should originally stop with the formation of a nucleus prominently to settle on the treated layer to constitute an objectionable surface deposit, with the resultant deterioration of the electric properties of said layer.
  • This limit is 10 percent by volume on the basis of the volume of base or carrier gas such as argon or nitrogen. It is needless to say that too small an amount of oxygen does not work. In order to effectuate smooth creation of grain growth nucleus sites, at least 0.1 percent by volume of oxygen is necessary.
  • the invention has been explained above with respect to cadmium selenide layer in particular.
  • this invention is effectively applicable to compounds of Groups II and VI in general such as cadmium sulfide, cadmium telluride, zinc sulfide, zinc selenide, zinc telluride, and a mixture (solid solution or heterogeneous mixture), and films of multi-layer structure of these compounds, too. Layers of these compounds may contain known impurities.
  • the inert gases which constitute the main component of the heat treatment atmosphere are argon, nitrogen or a mixture thereof.
  • the process of this invention is characterized in that nuclei necessary for uniform grain growth are provided on the surface of a film to be treatedby causing formation and decomposition of intermediate oxide, such as salt of an oxyacid, on the surface of the film in thecourse of the heat treatment.
  • intermediate oxide such as salt of an oxyacid
  • a process for preparing a layer of Group II-VI compound selected from the group consisting of CdX and ZnX, wherein X is an element selected from the group consisting of selenium, sulfur and tellurium which comprises forming a layer of said compound on a substrate plate and heat-treating the resulting layer in an atmosphere comprising an inert gas, 0. ll0 percent by volume of oxygen on the basis of said inert gas and vapor of said group element X whereby uniform grain growth with narrow range grain size distribution is effected.
  • a process for preparing a layer of compounds of Groups II VI characterizedin that a CdSe layer is formed on a substrate plate, the thus formed CdSe layer is heat-treated in an atmosphere comprising an inert gas, 0.1 10 percent by volume of oxygen on the basis of said inert gas and the vapour of selenium at a temperature not lower than 450C, whereby uniform grain growth with narrow range grain size distribution is effected.
  • pressure of the selenium vapour is not less than 1 mm Hg at the heat treatment temperature.

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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical & Material Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Light Receiving Elements (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Formation Of Various Coating Films On Cathode Ray Tubes And Lamps (AREA)
  • Chemical Vapour Deposition (AREA)
US00172454A 1970-08-17 1971-08-17 Process for preparing a layer of compounds of groups ii and vi Expired - Lifetime US3793069A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45071391A JPS5118155B1 (nl) 1970-08-17 1970-08-17

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US3793069A true US3793069A (en) 1974-02-19

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US (1) US3793069A (nl)
JP (1) JPS5118155B1 (nl)
CA (1) CA950806A (nl)
GB (1) GB1320998A (nl)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3870558A (en) * 1971-08-17 1975-03-11 Tokyo Shibouro Electric Co Ltd Process for preparing a layer of compounds of groups II and VI
US4035197A (en) * 1976-03-30 1977-07-12 Eastman Kodak Company Barrier type photovoltaic cells with enhanced open-circuit voltage, and process of manufacture
US4046565A (en) * 1975-03-25 1977-09-06 Addressograph Multigraph Corporation Amorphous selenium coating
US4081290A (en) * 1974-11-08 1978-03-28 Bell Telephone Laboratories, Incorporated Solar cells and photovoltaic devices of InP/CdS
USRE30412E (en) * 1979-04-26 1980-10-07 Eastman Kodak Company CdTe Barrier type photovoltaic cells with enhanced open-circuit voltage, and process of manufacture
US5030477A (en) * 1988-11-14 1991-07-09 Xerox Corporation Processes for the preparation and processes for suppressing the fractionation of chalcogenide alloys
US5045409A (en) * 1987-11-27 1991-09-03 Atlantic Richfield Company Process for making thin film solar cell
US5484736A (en) * 1994-09-19 1996-01-16 Midwest Research Institute Process for producing large grain cadmium telluride
CN103962295A (zh) * 2014-04-30 2014-08-06 齐鲁工业大学 一种硫化锌半导体薄膜的简单高效制备方法
WO2021021731A1 (en) * 2019-07-26 2021-02-04 Alliance For Sustainable Energy, Llc Extreme large grain (1 mm) lateral growth of cd(se,te) alloy thin films by reactive anneals

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622381A (en) * 1968-10-25 1971-11-23 Mitsubishi Electric Corp Method for the preparation of a zinc oxide film

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622381A (en) * 1968-10-25 1971-11-23 Mitsubishi Electric Corp Method for the preparation of a zinc oxide film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Kitamura, S. Influences of Heat-Treatment Upon Cadmium Sulfide Single Crystals, in J. of Phys. Soc. of Japan 16(12): p. 2,430 2,439, Dec. 1961. *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3870558A (en) * 1971-08-17 1975-03-11 Tokyo Shibouro Electric Co Ltd Process for preparing a layer of compounds of groups II and VI
US4081290A (en) * 1974-11-08 1978-03-28 Bell Telephone Laboratories, Incorporated Solar cells and photovoltaic devices of InP/CdS
US4046565A (en) * 1975-03-25 1977-09-06 Addressograph Multigraph Corporation Amorphous selenium coating
US4035197A (en) * 1976-03-30 1977-07-12 Eastman Kodak Company Barrier type photovoltaic cells with enhanced open-circuit voltage, and process of manufacture
USRE30412E (en) * 1979-04-26 1980-10-07 Eastman Kodak Company CdTe Barrier type photovoltaic cells with enhanced open-circuit voltage, and process of manufacture
US5045409A (en) * 1987-11-27 1991-09-03 Atlantic Richfield Company Process for making thin film solar cell
US5030477A (en) * 1988-11-14 1991-07-09 Xerox Corporation Processes for the preparation and processes for suppressing the fractionation of chalcogenide alloys
US5484736A (en) * 1994-09-19 1996-01-16 Midwest Research Institute Process for producing large grain cadmium telluride
CN103962295A (zh) * 2014-04-30 2014-08-06 齐鲁工业大学 一种硫化锌半导体薄膜的简单高效制备方法
CN103962295B (zh) * 2014-04-30 2015-08-19 齐鲁工业大学 一种硫化锌半导体薄膜的简单高效制备方法
WO2021021731A1 (en) * 2019-07-26 2021-02-04 Alliance For Sustainable Energy, Llc Extreme large grain (1 mm) lateral growth of cd(se,te) alloy thin films by reactive anneals

Also Published As

Publication number Publication date
DE2141212B2 (de) 1976-11-25
JPS5118155B1 (nl) 1976-06-08
CA950806A (en) 1974-07-09
DE2141212A1 (de) 1972-02-24
GB1320998A (en) 1973-06-20

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