US3620832A - Electrode system particularly semiconductor electrode system and method of producing the same - Google Patents

Electrode system particularly semiconductor electrode system and method of producing the same Download PDF

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US3620832A
US3620832A US630000A US3620832DA US3620832A US 3620832 A US3620832 A US 3620832A US 630000 A US630000 A US 630000A US 3620832D A US3620832D A US 3620832DA US 3620832 A US3620832 A US 3620832A
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grains
layer
electrode
electrode layer
granular
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Ties Siebolt Te Velde
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US Philips Corp
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US Philips Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0384—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including other non-monocrystalline materials, e.g. semiconductor particles embedded in an insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes

Definitions

  • the so-coated layer is thereafter subjected to an abra sive on a carrier comprising grains whose average diameter is smaller than the average diameter of the electrically active grains and whose diameter exceeds the average spacing between the active grains to remove only the electrode layer covering the exposed grain peaks without abrading the grains themselves.
  • the grain size of the abrasive is critical to avoid grains of the abrasive being lodged in the depressions between the grains of the semiconductive material and to avoid removing portions of the semiconductive grains.
  • FIGA A first figure.
  • the invention relates to a method of manufacturing an electrode system comprising a granular layer, for example, a semiconductor granular layer substantially of the thickness of one grain, the grains being embedded in an insulating filling substance, said granular layer being coated by at least one electrode layer, which is in contact with the grains and which consists of a pattern of coherent, electrically good-conducting domains between the grains on the filling substance and of electrically usually more poorly conductive domains on the grains in which method, in order to obtain said electrode layer, a coherent, uninterrupted electrically good-conducting electrode layer is applied to the granular layer, after which portions of the electrode layer on the grains are selectively removed.
  • the invention furthermore relates to an electrode system manufactured by the method according to the invention.
  • Electrode systems of the kind set forth may comprise radiation-sensitive grains and may be used as radiation detectors, in which case radiation energy is incident to the photosensitive granular layer, in which it produces electric voltage or impedance differences, which can be measured by means of electrodes provided on the granular layer, at least one of which electrodes has to be transparent to the incident radiation.
  • Examples of these uses are inter alia photoresistors and photocells for exposure meters; such electrode systems may furthermore be employed for converting radiation energy into electric energy, inter alia in so-called solar batteries.
  • electrode systems comprising a granular layer are interesting.
  • the electrode systems of the kind set forth involve often the problem of having to provide on the granular layer at least one electrode layer for current input or current output, which electrode layer has to satisfy conflicting requirements.
  • the electrode layer should have a low sheet resistance, whereas on the other hand at the contact area with the grains the electrode should have properties which may contradict said low sheet resistance.
  • the electrode system comprising a granular layer is, for example, an electro-optical device
  • at lease one of the electrodes applied to the granular layer has to be transparent, at least on the grains, to the radiation incident to the grains or emanating from the grains.
  • an electrode layer of unhomogeneous structure is desired, in which l coherent, good-conducting domains between the grains and less good-conducting domains of the desired radiation-transparent properties on top of the grains are provided.
  • the invention has for its object to provide a particularly rapid method for applying such an unhomogeneous electrode layer.
  • the invention is based on the discovery that in the case of a granular layer, on the electrode side of which the filling substance exhibits subsidences between the grains, parts of the electrode layer located on the grains can be selectively removed by abrading this side of the electrode-covered granular layer, while the parts of the electrode layer located in the subsidences of the filling substance between the grains are substantially not affected by the abrasive.
  • a method of manufacturing an electrode system of the kind referred to above is characterized in that the manufacture starts from a granular layer, the filling substance between the grains having a thickness considerably smaller than the average grain thickness, so that at lease on one side the-granular layer exhibits subsidences or hollows or depressions between the grains and in that on said side the granular layer is coated by an electrically good-conducting electrode layer, after which by abrading the granular layer on said side only portions of the electrode layer on the grains are removed owing to the subsidences between the grains.
  • Abrasion may be carried out by various grinding or abrading agents. It is advantageous to use an abrasive whose grains have such a size that they cannot reach the bottom of the subsidence. Therefore a preferred embodiment of the method according to the invention is characterized in that the granular layer is abraded by means of an abrasive whose grains have a diameter exceeding the average distance between the grains on the granular layer, so that they cannot reach down to the bottom of the depressions. It is preferred to use an abrasive, the grain diameter of which is more than twice and less than five times the average distance between the grains of the granular layer.
  • an abrasive whose grains have a considerably smaller diameter than the average grain diameter of the granular layer is abraded with the aid of an abrasive whose grains have a diameter which is considerably smaller than the average grain diameter of the granular layer, said abrasive being applied to a carrier.
  • the carrier is desired for preventing the abrading grains from attacking the electrode layer in the subsidences between the grains of the granular layer.
  • the carrier should preferably have such a flexibility that it can follow the shape of the granular layer, so that in practice each grain of the granular layer comes into contact with the abrasive.
  • lt is advantageous to use an abrasive in this case, the grain diameter of which is less than one-fifth, preferably less than one-tenth of the average grain diameter of the granular layer.
  • a granular layer is used, the grains of which consist of cadmium sulfide and the filling substance of which consists of polyurethane.
  • the abrasion produces openings in the electrode layers on the heads of the grains, while the contact between the electrode layer and the grains is maintained.
  • This method has the advantage that in a single operation an electrode is formed, which is good conducting between the grains, while on the heads of the grains the incident and the emerging radiations are not hindered, while the resultant contact, though only present on part of the grain surface, is in many cases sufficient.
  • the contact it is advantageous to subject the granular layer, subsequent to abrasion, to an ion or electron bombardment.
  • a further preferred embodiment of the method according to the invention is characterized in that subsequent to the removal of only the parts of the electrode layer from the heads of the grains a second electrode layer, conductively connected to the first electrode layer, is applied to at least the free grain portions.
  • a second electrode layer is used, in an important, preferred embodiment, which layer has a greater transparency than the first electrode layer for electromagnetic radiation to be emitted by the grains or for a radiation to which the grains are sensitive.
  • the method described above may be used with different combinations of grains and electrode materials.
  • the invention is, however, particularly important for the manufacture of electrode systems having a granular layer whose grains consist mainly of photoconductive sulfides and/or selenides of cadmium and zinc, while the grains are covered by an electrode layer containing indium or an indium alloy. Between the electrode layer and the grains an ohmic contact is then established.
  • the electrode layer may be applied without preliminary treatment of the granular layer. In order to obtain a satisfactory ohmic contact it is, however, often desired to subject the granular layer to an ion or electron bombardment prior to the application of the electrode layer.
  • the invention furthermore relates to an electrode system manufactured by the method according to the invention.
  • FIGS. 1 to 3 illustrate diagrammatically in cross-sectional views consecutive steps of the manufacture of part of a photoresistor according to a method according to the invention
  • FIG. 4 is a diagrammatic plan view of the photoresistor the manufacture of which is illustrated in a cross-sectional view taken on the line [-1 in FIGS. I to 3 and FIGS. to 8 illustrate diagrammatically in cross-sectional views consecutive stages of the manufacture of part of a solar cell obtained by a method according to the invention.
  • FIGS. 1 to 4 A first embodiment of a method of manufacturing an electrode system will now be described with reference to FIGS. 1 to 4; said system comprises a granular layer 1, 2, having grains I (FIG. 3) of a semiconductor material having substantially the thickness of one grain, the grains being embedded in an insulating filling substance 2; this granular layer 1, 2 is covered by at least one electrode layer 3, 4 which is in contact with the grains 1 and which consists of a pattern of coherent, electrically good-conducting domains 3 between the grains on the filling substance 2 and electrically less good-conducting domains 4 on the heads of the grains; in order to obtain said electrode layer on the granular layer 1, 2 a coherent, uninterrupted, electrically good-conducting electrode layer 3 (see FIG.
  • the starting material is again a granular layer 1, 2 stuck by an adhesive layer 7 (FIG. 1) to support 8 and cohering by means of a filling substance 2, operating as a binder, and having granular portion 9 free of the filling substance; this granular layer is covered by an electrode layer 3.
  • the grains 1 consist of photoconductive cadmium sulfide, activated by about 10 to 10" percent by weight of copper and gallium.
  • Such a granular layer may be obtained by various means. In connection with the necessity of forming subsidences between the grains, the following, very appropriate method is carried out.
  • a carrier for example, a glass plate 1 is coated, by immersion in a solution of gelatine in water, with a gelatine layer 7 of a few microns thick.
  • Photoconductive cadmium sulfide grains of a diameter of about 35 u are sunk into the still-swollen gelatine layer, after which the gelatine is hardened by drying and the grains not adhering to the support are removed. Then polyurethane is applied as a binder between the grains on the gelatine.
  • This may be carried out by dipping the carrier with the granular layer in a solution of materials known commercially under the trademarks of Desmophen” and Desmodur” in ethylacetate; when pulling the plate up, a thin layer is left on the granular layer, which layer is converted by a hardening process of, for example, 8 hours, at 75, into polyurethane.
  • the initially less viscous mixture withdraws from the heads of the grains, so that subsequent to hardening a granular layer is obtained, the grains of which project from the filling substance on the side remote from the carrier, while the filling substance between the grains has a thickness which is considerably smaller than the average grain thickness, so that on the side remote from the carrier the granular layer exhibits subsidences between the grains, which has also been described in my copending application, Ser. No. 629,999, filed Apr. 1 l, 1967.
  • the resultant granular layer may be directly coated by vapor deposition by an electrode layer 3.
  • the granular layer is preferably subjected to an ion or electron bombardment prior to the application of the electrode layer 3. In the present embodiment this is achieved by exposing the granular layer to a gas discharge for about 4 minutes at a voltage of l kv. (discharge current about 50 ma. with an electrode surface of I00 cmF).
  • a gas discharge for about 4 minutes at a voltage of l kv. (discharge current about 50 ma. with an electrode surface of I00 cmF).
  • the side of the granular layer remote from the carrier is then covered by the electrode layer 3, which establishes a substantially ohmic contact with the cadmium sulfide grains; for example, an indium layer of a thickness of 5,000 A. is applied from the vapor phase.
  • the granular layer is abraded by means of grains I0 of alumina having a diameter lying between about I50 p. and 250 t. This diameter is greater than twice and smaller than five times the average distance between the grains of the layer, in this case 70 to I00 ;1..
  • the abrasive grains 10 are used in the dry state and rubbed by means of a piece of cloth or another soft object 16 (see FIG. 1) with a light pressure across the granular layer. Owing to their size the abrasive grains cannot reach the coherent portions 3 of the electrode layer located in the subsidences between the grains on the filling substance, so that only the parts of the electrode layer on the heads of the grains 5 are removed.
  • holes 4 are made on the grains (see FIGS. 2 and 4) in the electrode layer; while portions 6 of the electrode layer remain in contact with the grains at the edges of the holes.
  • abrading is ceased and, if desired, any residues of polyurethane on the abraded grain parts may be removed by a dissolving or etching process.
  • the abraded side of the granular layer is then again exposed to a gas discharge.
  • an approximately 50 LL thick, hardening radiation-pervious, flexible layer ll of a synthetic resin is then applied to the granular layer, for example, of polyurethane, and after hardening of said layer the granular layer is removed from the carrier 8 by dissolving the gelatine layer 7 in water, so that on the side of the carrier the grain portions 12 are free.
  • the free side of the granular layer is exposed to a gas discharge and a second electrode layer 13 (see FIG. 3) is applied thereto by vapor deposition of indium to a thickness of about 5,000 A.
  • FIG. 3 a photoresistor formed by a flexible sheet is formed as is shown in FIG. 3 in a cross-sectional view and in FIG. 4 in a plan view.
  • FIGS. 5 to 8 A second example of the method according to the invention will be described with reference to FIGS. 5 to 8 for the manufacture of a solar cell.
  • the same reference numerals of the two embodiments designate corresponding parts.
  • the starting material is again (see FIG. 5) a granular layer 1, 2 stuck by means of a gelatine layer 7 to a carrier 8 and consisting of grains 1 of photoconductive cadmium sulfide of an average diameter of about 35 u, embedded in a binder 2 of polyurethane and manufactured in the manner described above; on the side remote from the carrier the granular layer exhibits subsidences between the grains and is coated completely, for example by vapor deposition, with an electrode layer 3, 5.
  • the electrode layer 3, 5 consists in this example of about 0.1 1. thick copper layer.
  • the granular layer is then abraded on the side remote from the carrier (see FIG. 1) by means of abrasive grains 21 of alumina of a diameter of about 5 p, applied to a flexible support 22 of a sheet of silicon rubber of about 0.2 mm. thickness.
  • the diameter of the abrasive grains is smaller than one-fifth of the mean grain diameter of the granular layer. Under given conditions it may be advantageous to use still smaller abrasive grains of a diameter smaller than one-tenth of the average diameter of the grains of the granular layer.
  • the abrasive grains 21 may be applied to the support 22, for example, by pouring out the silicon rubber in the liquid state on a glass plate and strewing alumina grains after which the silicon rubber is caused to harden to fonn a flexible sheet, in which the abrasive grains are partially embedded. Abrasion is performed by arranging a cushion 23 of foam plastics or another very elastic material on the carrier 22 with the abrasive grains (FIG. 5) and thereon a nonelastic flat object 24 and by rubbing the carrier of the abrasive grains by hand of by a machine with slight pressure across the granular layer.
  • the carrier 22 follows the contours of the granular layer and only the portions of the electrode layer 3, 5 on the heads of the grains are removed so that (see (FIG. 6) a structure similar to that of FIG. 2 of the first embodiment is obtained. Portions 6 of the electrode layer remain in contact with the grains 1, although this is not required in this example with a view to the electrode layer 25 to be applied afterwards.
  • the resultant layer is coated with a second, radiationpervious, less good-conductive electrode layer 25 of copper by vapor deposition to a thickness of about 100 A., which layer establishes a contact with the portions 3 of the initial copper layer 3, 5 and a rectifying contact with the grains 1.
  • a gas discharge prior to the application of the electrode layer 25 is, of course, omitted.
  • the layer 25 is coated with a radiation-pervious, hardening, preferably flexible plastics layer 11, for example, of polyurethane of a thickness of about 50 ;1.
  • the granular layer is removed from the carrier by dissolving the gelatine layer 7 in water, so that on the side of the carrier grain portions are exposed. These exposed sides of the grains are subjected to a gas discharge and (see FIG. 8) an electrode layer 13 is applied by vapor deposition of an about 5,000 A. thick indium layer. This electrode layer 13 establishes an ohmic contact with the grains.
  • a solar cell which also has the shape of a flexible sheet; radiation 26 can strike through the pervious plastics layer 11 and the pervious copper layer 25, the rectifying copper cadmium sulfide contact.
  • the electrode layer 13 and a portion 14 of the electrode layer 3, 25 clear of the layer 11 may be provided with contacts, from which the photovoltage produced by the incident radiation can be derived.
  • grains of other material than cadmium sulfide may be employed and in dependence upon the use of the resultant electrode system they need not be photoconductive, for example, for the manufacture of diodes, capacitors, bolometers, nonlinear resistors and the like.
  • filling substances of quite different materials may be used, for example epoxyresins or photohardening lacquers in accordance with the use and the technique used for the formation of the starting granular layer, while also the covering layer 11 (see FIGS. 3, 7 and 8) may consist not only of polyurethane but also of, for example, methylmethacrylate or another hardening synthetic resin pervious or not pervious to radiation.
  • an electrode layer may be replaced by a gas discharge for local discharge of the photoconductve layer.
  • an electrode layer may be provided previously between the carrier and the granular layer.
  • an electrical device comprising a granular layer of electrically active grains having electrode means therefor with at least one of the electrodes having highly electrically conductive portions between the grains
  • the improvement comprising the steps of embedding a layer of said grains substantially the thickness of one grain in an electrically insulating filling substance such that at least at one side of the layer the filling substance level between the grains lies below the grain peaks, applying on the said one side a coating of an electrically conductive material to form a continuous electrode layer of high electrical conductivity having higher portions on the grain peaks and lower portions on the intervening filler substance, and thereafter subjecting the electrode coated side of the layer to an abrasive comprising on a carrier grains whose diameter is smaller than the average diameter of the electrically active grains in the granular layer and whose diameter exceeds the average spacing between the electrically active grains in the granular layer to remove only the higher electrode layer portions coating the grain peaks thereby exposing the grain surfaces without abrading the grains and leaving in position lower electrode layer portions on the fill
  • the grains comprise cadmium sulfide, zinc sulfide, cadmium selenide, or zinc selenide.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photovoltaic Devices (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
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US630000A 1966-04-14 1967-04-11 Electrode system particularly semiconductor electrode system and method of producing the same Expired - Lifetime US3620832A (en)

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NL6604959A NL6604959A (no) 1966-04-14 1966-04-14

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US (1) US3620832A (no)
JP (1) JPS4527028B1 (no)
AT (1) AT269238B (no)
BE (1) BE697072A (no)
CH (1) CH499184A (no)
DE (1) DE1614235A1 (no)
ES (1) ES339178A1 (no)
FR (1) FR1519071A (no)
GB (1) GB1186074A (no)
IL (1) IL27769A (no)
NL (1) NL6604959A (no)
NO (1) NO121223B (no)
OA (1) OA02586A (no)
SE (1) SE333025B (no)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3947707A (en) * 1973-06-18 1976-03-30 U.S. Philips Corporation JFET optical sensor with capacitively charged buried floating gate
US4107724A (en) * 1974-12-17 1978-08-15 U.S. Philips Corporation Surface controlled field effect solid state device
US4728581A (en) * 1986-10-14 1988-03-01 Rca Corporation Electroluminescent device and a method of making same
US6066872A (en) * 1992-04-30 2000-05-23 Kabushiki Kaisha Toshiba Semiconductor device and its fabricating method
US6642656B2 (en) * 2000-03-28 2003-11-04 Ngk Insulators, Ltd. Corrosion-resistant alumina member and arc tube for high-intensity discharge lamp

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE8814637U1 (no) * 1987-12-16 1989-03-02 Reiling, Reinhold

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2201196A (en) * 1939-06-27 1940-05-21 Carborundum Co Manufacture of granular coated materials
US2904613A (en) * 1957-08-26 1959-09-15 Hoffman Electronics Corp Large area solar energy converter and method for making the same
US2915785A (en) * 1951-10-04 1959-12-08 Valentini Luciano Manufacturing mats from rubber derivatives
US3031344A (en) * 1957-08-08 1962-04-24 Radio Ind Inc Production of electrical printed circuits
US3108021A (en) * 1961-06-12 1963-10-22 Int Rectifier Corp Cadmium sulfide photo-cell

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2201196A (en) * 1939-06-27 1940-05-21 Carborundum Co Manufacture of granular coated materials
US2915785A (en) * 1951-10-04 1959-12-08 Valentini Luciano Manufacturing mats from rubber derivatives
US3031344A (en) * 1957-08-08 1962-04-24 Radio Ind Inc Production of electrical printed circuits
US2904613A (en) * 1957-08-26 1959-09-15 Hoffman Electronics Corp Large area solar energy converter and method for making the same
US3108021A (en) * 1961-06-12 1963-10-22 Int Rectifier Corp Cadmium sulfide photo-cell

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3947707A (en) * 1973-06-18 1976-03-30 U.S. Philips Corporation JFET optical sensor with capacitively charged buried floating gate
US4107724A (en) * 1974-12-17 1978-08-15 U.S. Philips Corporation Surface controlled field effect solid state device
US4728581A (en) * 1986-10-14 1988-03-01 Rca Corporation Electroluminescent device and a method of making same
US6066872A (en) * 1992-04-30 2000-05-23 Kabushiki Kaisha Toshiba Semiconductor device and its fabricating method
US6642656B2 (en) * 2000-03-28 2003-11-04 Ngk Insulators, Ltd. Corrosion-resistant alumina member and arc tube for high-intensity discharge lamp

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NO121223B (no) 1971-02-01
OA02586A (fr) 1970-05-05
IL27769A (en) 1971-01-28
CH499184A (de) 1970-11-15
NL6604959A (no) 1967-10-16
ES339178A1 (es) 1968-04-16
BE697072A (no) 1967-10-16
GB1186074A (en) 1970-04-02
FR1519071A (fr) 1968-03-29
AT269238B (de) 1969-03-10
JPS4527028B1 (no) 1970-09-04
DE1614235A1 (de) 1970-08-27
SE333025B (no) 1971-03-01

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