CA1232051A - Semiconductor device and method of manufacturing the same - Google Patents
Semiconductor device and method of manufacturing the sameInfo
- Publication number
- CA1232051A CA1232051A CA000443019A CA443019A CA1232051A CA 1232051 A CA1232051 A CA 1232051A CA 000443019 A CA000443019 A CA 000443019A CA 443019 A CA443019 A CA 443019A CA 1232051 A CA1232051 A CA 1232051A
- Authority
- CA
- Canada
- Prior art keywords
- layer
- metallic film
- semiconductor device
- transparent conductive
- conductive layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 27
- 239000010410 layer Substances 0.000 claims description 120
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims 8
- 229910052804 chromium Inorganic materials 0.000 claims 5
- 229910052735 hafnium Inorganic materials 0.000 claims 5
- 229910052750 molybdenum Inorganic materials 0.000 claims 5
- 229910052759 nickel Inorganic materials 0.000 claims 5
- 229910052758 niobium Inorganic materials 0.000 claims 5
- 229910052763 palladium Inorganic materials 0.000 claims 5
- 229910052697 platinum Inorganic materials 0.000 claims 5
- 229910052703 rhodium Inorganic materials 0.000 claims 5
- 229910052715 tantalum Inorganic materials 0.000 claims 5
- 229910052719 titanium Inorganic materials 0.000 claims 5
- 229910052721 tungsten Inorganic materials 0.000 claims 5
- 229910052720 vanadium Inorganic materials 0.000 claims 5
- 229910052726 zirconium Inorganic materials 0.000 claims 5
- 239000007795 chemical reaction product Substances 0.000 claims 3
- 238000010406 interfacial reaction Methods 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000002344 surface layer Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000003384 imaging method Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 52
- 238000003556 assay Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 9
- 238000000151 deposition Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 238000001259 photo etching Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 238000005530 etching Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 235000009434 Actinidia chinensis Nutrition 0.000 description 1
- 244000298697 Actinidia deliciosa Species 0.000 description 1
- 235000009436 Actinidia deliciosa Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052685 Curium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001017 electron-beam sputter deposition Methods 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000001883 metal evaporation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/18—High density interconnect [HDI] connectors; Manufacturing methods related thereto
- H01L24/23—Structure, shape, material or disposition of the high density interconnect connectors after the connecting process
- H01L24/24—Structure, shape, material or disposition of the high density interconnect connectors after the connecting process of an individual high density interconnect connector
-
- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02162—Coatings for devices characterised by at least one potential jump barrier or surface barrier for filtering or shielding light, e.g. multicolour filters for photodetectors
- H01L31/02164—Coatings for devices characterised by at least one potential jump barrier or surface barrier for filtering or shielding light, e.g. multicolour filters for photodetectors for shielding light, e.g. light blocking layers, cold shields for infrared detectors
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022491—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of a thin transparent metal layer, e.g. gold
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic System
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1203—Rectifying Diode
- H01L2924/12032—Schottky diode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12043—Photo diode
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S148/00—Metal treatment
- Y10S148/147—Silicides
Abstract
ABSTRACT OF THE DISCLOSURE
A semiconductor device such as a solar cell, photodiode and solid state imaging device comprises a semiconductor layer made of amorphous silicon formed on a given substrate, and a transparent conductive layer formed by an interracial reaction between the amorphous silicon and a metallic film directly formed on the amorphous silicon. This transparent conductive layer is used as a transparent electrode of the device and if necessary the remainder after having partially removed the metallic film for the transparent conductive layer is used as a conductive layer and right shielding film.
A semiconductor device such as a solar cell, photodiode and solid state imaging device comprises a semiconductor layer made of amorphous silicon formed on a given substrate, and a transparent conductive layer formed by an interracial reaction between the amorphous silicon and a metallic film directly formed on the amorphous silicon. This transparent conductive layer is used as a transparent electrode of the device and if necessary the remainder after having partially removed the metallic film for the transparent conductive layer is used as a conductive layer and right shielding film.
Description
~23~20r~L
This invention relates to a semiconductor device having a transparent electrode and a method of manufacturing it which are applicable to a solar cell, photo diode, imaging device or the like.
To enable the prior art to be described with the aid of diagrams the figures of the drawings will first be listed.
Fig. 1 is a sectional view of a conventional solar cell;
Fig. 2 is a sectional view of a conventional photo diode;
Fig. 3 is a sectional view of one embodiment of solar cell according to this invention;
Figs. PA and 4B are a plan view and sectional view of one embodiment of photo diode according to this invention respectively;
Fig. S is a diagram for explaining a sensor of matrix drive contact type;
Fig. PA and 6B are a plan view and a sectional view of one embodiment according to this invention;
Fig. PA - OF, Fig. 8 and Fig. 9 are sectional views of other embodiments according to this invention, respectively; and Fig. 10 is a plan view of the embodiment of Fig. 9 according to this invention.
As well known, such a structure as shown in Fig. 1 has been conventionally adopted in the solar cell, for instance. In Fig. 1, numeral 1 designates a substrate, 2 ~;23~ So an under electrode, 3 a semiconductor, a transparent electrode and 5 an upper electrode of a striped metal.
In the structure of Fig. 1, light is irradiated to the trays- parent electrode 4 to extract holes and electrons so generated through the under electrode 2 and the upper electrode 5. And the photo diode, for example, has been conventionally implemented in a sectional structure such as shown in Fig. 2. In Fig. 2, numeral 6 designates a substrate, 7 an under electrode, 8 a semiconductor, 9 a transparent electrode and lo an upper electrode for current extraction, being commonly made of metal. Light is caused to impinge on the transparent electrode 9 with the result that current according to the incident light flows between the under electrode 7 and the upper electrode 10.
As mentioned above, the conventional photo-sensitive element having a transparent electrode is of a double layer electrode structure in which an upper electrode made of metal is provided on the transparent electrode. This requires, as a manufacturing process, steps of forming the transparent electrode and working it; and forming the upper electrode of metal and working it. Further, as well known, an IT (Indium Tin oxide) is employed as a trays-parent electrode, which material is ordinarily formed by OF sputtering deposition. Thus, this material gives rise to any defects in a semi-conductor surface in forming the IT, and has a difficulty of obtaining an IT film of good quality. Moreover, when the metal to be an upper electrode is worked on the IT film by photo-etching, IT itself may lZ;3;~05~L
be also dissolved since it is a material of considerably weak chemical proof. As above, there have been a number of problems to be solved to use IT as a transparent electrode.
There are the following articles related with IT
mentioned above:
i) JO Vossen, RCA Rev., 32,289 (1971) ii) US. Patent No. 3749658 ~1973), to JO Vossen.
In view of the foregoing, it is an object of this invention to provide a semiconductor device having a trays-parent electrode which can reduce a great deal of electrode making step where hydrogenerated amorphous silicon (hereinafter referred to as "assay") is used as a semi-conductor layer and also solve the above mentioned problems; and a method of manufacturing it.
The gist of the device according to this invention is as follows; a semiconductor material having an assay layer is used and a transparent conductive layer, which is formed on an interface between the assay layer and a metallic film containing at least one selected from the group including Or, Mow W, Tip V, Or, Nub, Tax Hi, Nix Pod, Co, Pi and Rho through an interracial reaction there between, is used as a transparent electrode.
Thus, the gist of the method of manufacturing the device is as follows:
An assay layer is formed on a given substrate a given metallic film containing Or, Mow Wit, etc. mentioned above is formed on the assay layer and the interracial reaction 12~ So there between is caused to form the transparent conductive layer on the interface there between. And the step of removing the metallic film used to form this conductive layer is also included in this method.
Incidentally, as the metallic film, not only an eye-mental substance of the metals mentioned above but also the film including the above mentioned metal such as the mixture, alloy, Creole, Crown, Cranial, etc. can be employed.
The thickness of this metallic film is not critical since it is removed after having formed the transparent conductive layer, and the thickness thereof is normally within the range of 50 to AYE, and more preferably within the range of 500 to AYE. An undue thin film is inferior in uniformity of the film while an undue thick film doesn't give rise to any specific advantage but increases the posy sublet of adversely affecting the semi-conductor layer which is attributable to the stress by the metallic film.
The reacting temperature is within the range of 100 to 250C. In particular, the temperature beyond 250C is not preferable since an assay will degenerate at the tempera-lure. The reacting time is within the range of 20 minutes to one hour. Undue long heating will not provide any specific advantage Heat treatment may be performed either during the step of forming the metallic film (i.e. evaporation in state of heating substrate) or after having formed the metallic film.
.
X3;~)5~
Further, in case where the surface of the assay layer, which appears to be a so-called surface oxide layer, is removed immediately before the metallic film is formed on the assay layer, a transparent conductive layer can be formed without any specific heat treatment. That is, the heat treatment at 60 to 70C is performed for a sample by a metal evaporation source, thus forming the transparent conductive layer The assay of any one of p, i and n conduction type constitutes the transparent conductive layer. It is of course that the assay may contain an impurity such as P, B, N, C, O or Go.
The amorphous silicon which terminates a dangling bond thereof by F, in place of H normally introduced for this purpose, also constitutes the transparent layer.
The thus formed transparent conductive layer is sufficiently practicable from the viewpoint light trays-parentness and also practicable in the resistance since it is less than about 10 kiwi.
This invention uses, as a transparent electrode, a transparent conductive layer formed by an interracial reaction between the amorphous silicon and metal on the basis of the above discovery. In accordance with the present invention, a solar cell such as shown in Fig. 1 for example, is completed by only the steps of forming an assay on a semiconductor 3, depositing Or thereon by evaporation by heat and removing Or while causing a necessary Or portion to remain. The number of fabricating I
steps is reduced by half as compared with the conventional method. Such a problem as may occur in the case of using IT
does not occur. It has been confirmed in the method according to this invention that any method of vacuum-deoosition, electron beam deposition and sputtering deposition naturally constitutes entirely the same transparent electrode in property. Hydrogenated amorphous silicon or n-type amorphous silicon doped with P is preferably employed in this invention.
But, these amorphous silicons are susceptible to natural oxidation so that when it is left in air during one month or so, an oxidation film being several tens A thick will be formed. Thus, forming Or on the oxidation film will not constitute a transparent conductive layer since this oxidation film acts as a reaction stopper. Therefore, this invention must be adapted after this oxidation film has been removed by the enchant of HO system. The hydrogenated amorphous silicon doped with B is more stable than the above materials in chemical property so that even when it is left in air during ten months or so any oxidation film will not be constituted, which always allows a desired conductive layer to be obtained.
The foregoing and other objects, features and advantages of the invention will be apparent from the following, more particular description of the preferred embodiments of the invention.
~'320S~
Embodiment 1:
The example in which this invention is applied to a solar cell will be explained referring to Fig. 3.
First, a Or electrode 12 is formed on a glass substrate 11 by sputtering deposition in an atmosphere such as An gas, with its film thickness being 0.3 em. Plasm id CUD (Chemical Vapor Deposition) is performed at the substrate temperature of 230C to form hydrogenated amorphous silicon (assay) 13 containing P (n-layer) on the Or electrode 12 using a mixed gas composed of PHI gas and Sue gas (mixture ratio:
PH3/SiH4 , 0.5V%); to form an assay 14 (i-layer) on the n-layer using only Sue gas: and to form an assay 15 con-twining B (p-layer) on the i-layer using a mixed gas composed of B2H6 gas and Sue gas (mixture ratio: B2H6/SiH4 _ 0.5V%), sequentially. The film thickness of each layer may be about AYE for the n-layer, about AYE for the i-layer and about AYE for the p-layer, for example. Next, at the substrate temperature within the range of 100 to 250C since the reacting speed slows down at the 1 23~0~
1 temperature below 100C while a higher proportion of hydrogen atoms may be decomposed at the temperature above 250C, deposition is performed to form a Or layer being 0.1 em thick on the entire surface of the P-layer, succeeded by forming an Al layer king l em thick thereon.
The time required for heat treatment in this case is about 60 to 30 minutes. Although it is of course that only the Or layer may be formed with the thickness of 0.4 my it is more advantac3eous to use the Al layer since lo it reduces an electric resistance. Namely, the range of 0.1 to 0.4 em about the thickness of the Or layer is preferably used since it facilitates succeeding treatments and places the electric resistance within an optimum range. In the final step, photo etching is performed to remove the Creole portion other than the Creole portion to be a stripe electrode 17. Incidentally, a phosphoric acid etching liquid is used for Al while ammonium curium (IV) nitrate solution is used for Cr. Thus, a trays-parent electrode 16 and the stripe electrode 17 are formed, thereby completing a solar cell. In the embody-mint mentioned above, the assess are stacked on the glass substrate 11 in the order of n, i and p layer, but they may be stacked in the entirely opposite order (i.e.
p, i and n).
Embodiment 2:
The example in which this invention is applied to a photo diode will be explained referring to Figs. PA
~2320S~
1 and 4B which are a plan view and sectional view, no-spectively.
First, a Or layer being 0.3 em thick is formed on a glass substrate 18 and photo etching is performed for the Or layer to form a Or electrode 19. As in the embodiment l, an n-layer 20, i-layer 21 and palaver, which are Swiss, respectively, are sequentially formed on the Or electrode 19 by means of plasma CUD and there-after photoetcning is performed to remove the assay while a part of the assay is left. It is carried out by plasma asker using CF4 gas. Thereafter, an Sue layer 23 being 2 em thick it formed on the resultant entire surface by sputtering deposition and the Sue on the a-Sigh and the peripheral portion of the substrate is removed by photo etching. The Sue is removed by a hydrofluoric acid etching liquid. And at the substrate temperature of the range of 100 to 250C, another Or layer being 0.1 em thick and an Al layer being 1 em thick are formed on the resultant surface by vacuum deposition. At the final step, the Creole layer other than a part 24 of the Creole layer is removed by photo-etching. It is of course that the Creole layer on a contact hole in the Sue layer 23 on the assay layers is removed. A transparent electrode 25 remains on the contact hole, which is formed by the interdependence (interracial reaction) between the Creole layer and the assay, and is to be a light window for the photo diode.
As described above, when the Creole layer corresponding ~232~
to the portion to which light is intended to be incident is removed, the transparent electrode remains on the portion while the remaining Creole layer also acts as a metal for light shading, thereby specifying a light window area correctly and easily. Thus, the photo diode is completed.
For simplicity of explanation, the example of making one photo diode has been described in the above.
However, one-dimentional or two-dimentional photo diode array can be easily made in entirely the same manner by replacing a photo mask. Incidentally, in the above embodiment, the Al layer is formed on the Or layer, but in place of Or a metal such as Crown having Or as a main component, My or W can be used and instead of Al, such a metal as A, No and Pi can be used. And the p-layer 22 of assay can be done without in practical use.
Embodiment 3:
There has been proposed a matrix contact type sensor as a linear sensor array such as disclosed in Japanese Utility Model Application Laid-Open No. 57-53760 laid open on 1982. As shown in Fig. 5, this kind of sensor is a configuration in which a plurality of pair of diodes (designated with DUB and Do in the figure) con-netted in series the polarities of which are opposite to each other are arranged in one dimension. Fig. 5, numeral 25 designates a drive circuit and 27 is a detect circuit.
~32C~5~
l This invention is most suitable to fabricate a linear sensor array of diode arrangement. The fabric acting process will be explained referring to Figs. PA
and 6B which illustrate a plan structure and a sectional structure, respectively. A Or film being 0.2 thick is formed on a glass substrate 28 at the substrate temperature of 200C by vacuum deposition ox sputtering deposition. Next, a Or electrode 29 is formed by photo-etching. As in the embodiments 1 and I an assay film 37 is stacked and worked as shown in the figure. This film is formed at the substrate temperature of 200 to 250C by plasma CUD (Chemical Vapor Deposition). This film includes an n-layer, an i-layer and a p layer. And the n-layer is formed using a mixed gas composed of PHI
gas and Sue gas (mixture ratio: PH3/SiH4 0.5 vow%) as a raw material gas. The i-layer is formed using Sue.
Tao ply or is former using a mixed gas coy owed of EYE
gas and Sue gas (mixture ratio: B2H6/SiH4 _ 0.5 vow%).
The film thickness of each layer may be about AYE (n-layer), about AYE (i-layer) and about AYE (p-layer).
This assay film is etched while causing the portion to be diodes to remain. Next, an insulating film 30 such as Sue glass is formed with the thickness of upwards of l em by sputtering deposition and contacts holes 31, 32, 33 and 34 are photo-etched. Hydrofluoric acid is employed as an etching liquid. A Or film being 0.1 em thick and an Al film being 1.5 em thick are formed on the resultant entire surface at the substrate tempera-lure of 100 to 250C. Thereafter, a Creole electrode ~L1232~
1 35 is formed by photo etching, and at a same time the Creole film is removed in the contact hole 32 on the photo diode. Thus, a transparent electrode 36 of trays-parent conductive layer remains on the photo diode, which is to be a window for incident light. As such, the application of this invention to this embodiment ensures that a linear sensor array sensor of matrix drive type is made through a simple and easy fabricating process.
Although the Or electrode 29 was employed in this embody-mint such a metal as Tax Nick, Ma, W, Al, Pi, Pod, No etc.can also be used as an electrode. The multiple layer including these metals may be used.
Furthermore, in this embodiment the double layer composed of Or and Al was adopted as a metal film for developing a transparent electrode and the upper metallic wiring 35 obtained by working the metal film.
A single layer or multiple layer, however, may be used provided that its structure is such that one selected from the group including Or, Mow Tip V, Or, Nub, Tax W, Hi, Nix Pod, Co, Pi and Rho or the metal having the selected one element as a main component is in contact with the amorphous silicon film. And in this embody-mint, stacking was carried during heating but heating may be performed at 100 to 250C after the stacking.
Moreover, although a blocking diode was placed at a common electrode side in this embodiment, the block-in diode and the photo diode may be replaced by each other.
~2~20~
1 There are liner sensor array arrangements such as shown in Figs. PA to OF in addition to the above described arrangement. One photosensitive element is constituted by the blocking diode DUB and the photo diode Do in Figs. PA and 7B, by the blocking diode DUB and a photo conductive film 52 in Figs. 7C and ED, and my the photo diode Do and a capacitor consisting of an upper metal electrode 42, an insulator 53 and an under metal-fig electrode 29 in Figs. YE and OF, respectively. Figs.
PA, 7C and YE illustrate such a structure that two cells are arranged horizontally while Figs. 7B, ED and OF
illustrate such a structure that they are arranged vertically. It is evident that this invention is apply-cable to all the structures shown in these figures in such a manner that the previously mentioned transparent electrode is formed on only the contact hole over the photo diode and the photo conductive film as a window for incident light in these figures. In this embodiment, a p-i-n diode was adopted for each diode but a Skeptic diode may also be employed.
Incidentally, in Figs. PA to OF, reference numeral 28 designates a glass substrate; 29 an under metallic electrode; 30 an insulating film; 37, 37' a semiconductor material for constituting a diode; 40, 49, 50 a p-type semiconductor layer, i-type semiconductor layer and n-type semiconductor layer, respectively; 42 an upper metallic electrode; and 51 a transparent electrode according to this invention.
~3205~
1 Embodiment 4:
The sectional structure of this embodiment is illustrated in Fig. 8, which is the same as the embody-mint 3 except that in the embodiment 3 the transparent electrode 36 is caused to remain on only the photo diode while no this embodiment 4, Creole, which corresponds to the part indicated by letter "A" in the neighborhood of the photo diode, is removed to form a hole. Such an arrangement enables the light L to enter from the lower side of the glass substrate 28 as indicated by an arrow.
That is, this arrangement can be adapted to such a device that the list L is caused to enter from the lower side of the glass substrate 28, and the light reflected at a manuscript I placed in proximity to the sensor is caused to enter the photo diode thereby to read the manuscript M through photoelectric conversion.
Embodiment 5:
Explanation will be made on the embodiment that this invention is adapted to a solid state imaging device using a photo conductive film.
As disclosed in Japanese Patent Application Laid-Open No. 51-10715 laid open on 1981, this device is such that a photo conductive film made of a photo conductor such as an assay for photo-electric conversion is formed on a semiconductor substrate TIC substrate for scanning) having at least switches two-dimentionally arranged and a scanner for transmitting photoelectrons derived through ~232~
1 the switches and corresponding to an optical image. Fig.
9 shows a basic structure of this device. The IT part for scanning is made by an ordinary process for manufas-luring a semiconductor device. First, a thin Sue film being about AYE is formed on a p-type So substrate 60, and an Sweeney is formed on a predetermined area of the Sue Calm, with its thickness being about AYE. The Sue film is made by a common CUD technique and the Sweeney film is made by the CUD technique in No atmosphere.
Next, the So substrate is subjected to local oxidation in such an atmosphere as I 2 = 1:8 to form an Sue layer I This method is directed to local oxidation of So for an isolation between elements commonly called LOOS. The above Sweeney film and Sue film are once removed partially and a gate insulating film 71 for an MOW transistor is formed by an Sue film.
exit, a gate portion 69 of polysilicon and, diffusion areas 70, 61 are formed and an Sue film 72 is formed on the resultant surface. A window for deriving an electrode for the diffusion area 61 is bored in this film 72 by etching. Al is deposited to form an electrode with its thickness being AYE. An Sue film 63 being AYE thick is formed, an window for deriving an electrode is bored on the diffusion area pa by etching, and Al or My is deposited with its thickness of l em as an electrode 64. Incidentally, the electrode 64 is formed so wide as to cover the diffusion areas 70 and 61 and the gate portion. This is because an incident light to a signal processing area between elements may zoos 1 cause an undesired blooming.
A phGtoconductive film 65 is formed by sputter-in in an atmosphere of the mixed gas composed of An and H
at 0.2 Torn. The hydrogen convent is 6 molt. That is, the reactive sputtering is performed at a frequency of 13.56 MHz and input of 300 W using a silicon target to stack the photo conductive film 65 of 1 em on the IT
substrate for scanning. Thereafter, Or is stacked by AYE at the substrate temperature of 100 to 250C by sputtering or vacuum deposition. Next, patterning is carried out so as to section the photosensitive element as shown in a plan view of a photosensitive part of Fig. 10. Thus, a transparent conductive film 66 is formed on the photosensitive element, which also acts as a shading 67 enhance a resolution so as to restrict an angle of the incident light for one photosensitive element.
Although MOW transistor was used as a scanning IT in this embodiment a COD or BUD may also be adapted in place of the MOW transistor.
where the shading 67 is not required, the remainder of Or at only the peripheral portion of a photo conductive layer will not cause any serious problem.
B and P were used as a Dupont for the assay in this embodiment, but it is evident that N, C, O, G, etc. may be used. And F may be used as a terminator of a dangling bond instead of H.
This invention relates to a semiconductor device having a transparent electrode and a method of manufacturing it which are applicable to a solar cell, photo diode, imaging device or the like.
To enable the prior art to be described with the aid of diagrams the figures of the drawings will first be listed.
Fig. 1 is a sectional view of a conventional solar cell;
Fig. 2 is a sectional view of a conventional photo diode;
Fig. 3 is a sectional view of one embodiment of solar cell according to this invention;
Figs. PA and 4B are a plan view and sectional view of one embodiment of photo diode according to this invention respectively;
Fig. S is a diagram for explaining a sensor of matrix drive contact type;
Fig. PA and 6B are a plan view and a sectional view of one embodiment according to this invention;
Fig. PA - OF, Fig. 8 and Fig. 9 are sectional views of other embodiments according to this invention, respectively; and Fig. 10 is a plan view of the embodiment of Fig. 9 according to this invention.
As well known, such a structure as shown in Fig. 1 has been conventionally adopted in the solar cell, for instance. In Fig. 1, numeral 1 designates a substrate, 2 ~;23~ So an under electrode, 3 a semiconductor, a transparent electrode and 5 an upper electrode of a striped metal.
In the structure of Fig. 1, light is irradiated to the trays- parent electrode 4 to extract holes and electrons so generated through the under electrode 2 and the upper electrode 5. And the photo diode, for example, has been conventionally implemented in a sectional structure such as shown in Fig. 2. In Fig. 2, numeral 6 designates a substrate, 7 an under electrode, 8 a semiconductor, 9 a transparent electrode and lo an upper electrode for current extraction, being commonly made of metal. Light is caused to impinge on the transparent electrode 9 with the result that current according to the incident light flows between the under electrode 7 and the upper electrode 10.
As mentioned above, the conventional photo-sensitive element having a transparent electrode is of a double layer electrode structure in which an upper electrode made of metal is provided on the transparent electrode. This requires, as a manufacturing process, steps of forming the transparent electrode and working it; and forming the upper electrode of metal and working it. Further, as well known, an IT (Indium Tin oxide) is employed as a trays-parent electrode, which material is ordinarily formed by OF sputtering deposition. Thus, this material gives rise to any defects in a semi-conductor surface in forming the IT, and has a difficulty of obtaining an IT film of good quality. Moreover, when the metal to be an upper electrode is worked on the IT film by photo-etching, IT itself may lZ;3;~05~L
be also dissolved since it is a material of considerably weak chemical proof. As above, there have been a number of problems to be solved to use IT as a transparent electrode.
There are the following articles related with IT
mentioned above:
i) JO Vossen, RCA Rev., 32,289 (1971) ii) US. Patent No. 3749658 ~1973), to JO Vossen.
In view of the foregoing, it is an object of this invention to provide a semiconductor device having a trays-parent electrode which can reduce a great deal of electrode making step where hydrogenerated amorphous silicon (hereinafter referred to as "assay") is used as a semi-conductor layer and also solve the above mentioned problems; and a method of manufacturing it.
The gist of the device according to this invention is as follows; a semiconductor material having an assay layer is used and a transparent conductive layer, which is formed on an interface between the assay layer and a metallic film containing at least one selected from the group including Or, Mow W, Tip V, Or, Nub, Tax Hi, Nix Pod, Co, Pi and Rho through an interracial reaction there between, is used as a transparent electrode.
Thus, the gist of the method of manufacturing the device is as follows:
An assay layer is formed on a given substrate a given metallic film containing Or, Mow Wit, etc. mentioned above is formed on the assay layer and the interracial reaction 12~ So there between is caused to form the transparent conductive layer on the interface there between. And the step of removing the metallic film used to form this conductive layer is also included in this method.
Incidentally, as the metallic film, not only an eye-mental substance of the metals mentioned above but also the film including the above mentioned metal such as the mixture, alloy, Creole, Crown, Cranial, etc. can be employed.
The thickness of this metallic film is not critical since it is removed after having formed the transparent conductive layer, and the thickness thereof is normally within the range of 50 to AYE, and more preferably within the range of 500 to AYE. An undue thin film is inferior in uniformity of the film while an undue thick film doesn't give rise to any specific advantage but increases the posy sublet of adversely affecting the semi-conductor layer which is attributable to the stress by the metallic film.
The reacting temperature is within the range of 100 to 250C. In particular, the temperature beyond 250C is not preferable since an assay will degenerate at the tempera-lure. The reacting time is within the range of 20 minutes to one hour. Undue long heating will not provide any specific advantage Heat treatment may be performed either during the step of forming the metallic film (i.e. evaporation in state of heating substrate) or after having formed the metallic film.
.
X3;~)5~
Further, in case where the surface of the assay layer, which appears to be a so-called surface oxide layer, is removed immediately before the metallic film is formed on the assay layer, a transparent conductive layer can be formed without any specific heat treatment. That is, the heat treatment at 60 to 70C is performed for a sample by a metal evaporation source, thus forming the transparent conductive layer The assay of any one of p, i and n conduction type constitutes the transparent conductive layer. It is of course that the assay may contain an impurity such as P, B, N, C, O or Go.
The amorphous silicon which terminates a dangling bond thereof by F, in place of H normally introduced for this purpose, also constitutes the transparent layer.
The thus formed transparent conductive layer is sufficiently practicable from the viewpoint light trays-parentness and also practicable in the resistance since it is less than about 10 kiwi.
This invention uses, as a transparent electrode, a transparent conductive layer formed by an interracial reaction between the amorphous silicon and metal on the basis of the above discovery. In accordance with the present invention, a solar cell such as shown in Fig. 1 for example, is completed by only the steps of forming an assay on a semiconductor 3, depositing Or thereon by evaporation by heat and removing Or while causing a necessary Or portion to remain. The number of fabricating I
steps is reduced by half as compared with the conventional method. Such a problem as may occur in the case of using IT
does not occur. It has been confirmed in the method according to this invention that any method of vacuum-deoosition, electron beam deposition and sputtering deposition naturally constitutes entirely the same transparent electrode in property. Hydrogenated amorphous silicon or n-type amorphous silicon doped with P is preferably employed in this invention.
But, these amorphous silicons are susceptible to natural oxidation so that when it is left in air during one month or so, an oxidation film being several tens A thick will be formed. Thus, forming Or on the oxidation film will not constitute a transparent conductive layer since this oxidation film acts as a reaction stopper. Therefore, this invention must be adapted after this oxidation film has been removed by the enchant of HO system. The hydrogenated amorphous silicon doped with B is more stable than the above materials in chemical property so that even when it is left in air during ten months or so any oxidation film will not be constituted, which always allows a desired conductive layer to be obtained.
The foregoing and other objects, features and advantages of the invention will be apparent from the following, more particular description of the preferred embodiments of the invention.
~'320S~
Embodiment 1:
The example in which this invention is applied to a solar cell will be explained referring to Fig. 3.
First, a Or electrode 12 is formed on a glass substrate 11 by sputtering deposition in an atmosphere such as An gas, with its film thickness being 0.3 em. Plasm id CUD (Chemical Vapor Deposition) is performed at the substrate temperature of 230C to form hydrogenated amorphous silicon (assay) 13 containing P (n-layer) on the Or electrode 12 using a mixed gas composed of PHI gas and Sue gas (mixture ratio:
PH3/SiH4 , 0.5V%); to form an assay 14 (i-layer) on the n-layer using only Sue gas: and to form an assay 15 con-twining B (p-layer) on the i-layer using a mixed gas composed of B2H6 gas and Sue gas (mixture ratio: B2H6/SiH4 _ 0.5V%), sequentially. The film thickness of each layer may be about AYE for the n-layer, about AYE for the i-layer and about AYE for the p-layer, for example. Next, at the substrate temperature within the range of 100 to 250C since the reacting speed slows down at the 1 23~0~
1 temperature below 100C while a higher proportion of hydrogen atoms may be decomposed at the temperature above 250C, deposition is performed to form a Or layer being 0.1 em thick on the entire surface of the P-layer, succeeded by forming an Al layer king l em thick thereon.
The time required for heat treatment in this case is about 60 to 30 minutes. Although it is of course that only the Or layer may be formed with the thickness of 0.4 my it is more advantac3eous to use the Al layer since lo it reduces an electric resistance. Namely, the range of 0.1 to 0.4 em about the thickness of the Or layer is preferably used since it facilitates succeeding treatments and places the electric resistance within an optimum range. In the final step, photo etching is performed to remove the Creole portion other than the Creole portion to be a stripe electrode 17. Incidentally, a phosphoric acid etching liquid is used for Al while ammonium curium (IV) nitrate solution is used for Cr. Thus, a trays-parent electrode 16 and the stripe electrode 17 are formed, thereby completing a solar cell. In the embody-mint mentioned above, the assess are stacked on the glass substrate 11 in the order of n, i and p layer, but they may be stacked in the entirely opposite order (i.e.
p, i and n).
Embodiment 2:
The example in which this invention is applied to a photo diode will be explained referring to Figs. PA
~2320S~
1 and 4B which are a plan view and sectional view, no-spectively.
First, a Or layer being 0.3 em thick is formed on a glass substrate 18 and photo etching is performed for the Or layer to form a Or electrode 19. As in the embodiment l, an n-layer 20, i-layer 21 and palaver, which are Swiss, respectively, are sequentially formed on the Or electrode 19 by means of plasma CUD and there-after photoetcning is performed to remove the assay while a part of the assay is left. It is carried out by plasma asker using CF4 gas. Thereafter, an Sue layer 23 being 2 em thick it formed on the resultant entire surface by sputtering deposition and the Sue on the a-Sigh and the peripheral portion of the substrate is removed by photo etching. The Sue is removed by a hydrofluoric acid etching liquid. And at the substrate temperature of the range of 100 to 250C, another Or layer being 0.1 em thick and an Al layer being 1 em thick are formed on the resultant surface by vacuum deposition. At the final step, the Creole layer other than a part 24 of the Creole layer is removed by photo-etching. It is of course that the Creole layer on a contact hole in the Sue layer 23 on the assay layers is removed. A transparent electrode 25 remains on the contact hole, which is formed by the interdependence (interracial reaction) between the Creole layer and the assay, and is to be a light window for the photo diode.
As described above, when the Creole layer corresponding ~232~
to the portion to which light is intended to be incident is removed, the transparent electrode remains on the portion while the remaining Creole layer also acts as a metal for light shading, thereby specifying a light window area correctly and easily. Thus, the photo diode is completed.
For simplicity of explanation, the example of making one photo diode has been described in the above.
However, one-dimentional or two-dimentional photo diode array can be easily made in entirely the same manner by replacing a photo mask. Incidentally, in the above embodiment, the Al layer is formed on the Or layer, but in place of Or a metal such as Crown having Or as a main component, My or W can be used and instead of Al, such a metal as A, No and Pi can be used. And the p-layer 22 of assay can be done without in practical use.
Embodiment 3:
There has been proposed a matrix contact type sensor as a linear sensor array such as disclosed in Japanese Utility Model Application Laid-Open No. 57-53760 laid open on 1982. As shown in Fig. 5, this kind of sensor is a configuration in which a plurality of pair of diodes (designated with DUB and Do in the figure) con-netted in series the polarities of which are opposite to each other are arranged in one dimension. Fig. 5, numeral 25 designates a drive circuit and 27 is a detect circuit.
~32C~5~
l This invention is most suitable to fabricate a linear sensor array of diode arrangement. The fabric acting process will be explained referring to Figs. PA
and 6B which illustrate a plan structure and a sectional structure, respectively. A Or film being 0.2 thick is formed on a glass substrate 28 at the substrate temperature of 200C by vacuum deposition ox sputtering deposition. Next, a Or electrode 29 is formed by photo-etching. As in the embodiments 1 and I an assay film 37 is stacked and worked as shown in the figure. This film is formed at the substrate temperature of 200 to 250C by plasma CUD (Chemical Vapor Deposition). This film includes an n-layer, an i-layer and a p layer. And the n-layer is formed using a mixed gas composed of PHI
gas and Sue gas (mixture ratio: PH3/SiH4 0.5 vow%) as a raw material gas. The i-layer is formed using Sue.
Tao ply or is former using a mixed gas coy owed of EYE
gas and Sue gas (mixture ratio: B2H6/SiH4 _ 0.5 vow%).
The film thickness of each layer may be about AYE (n-layer), about AYE (i-layer) and about AYE (p-layer).
This assay film is etched while causing the portion to be diodes to remain. Next, an insulating film 30 such as Sue glass is formed with the thickness of upwards of l em by sputtering deposition and contacts holes 31, 32, 33 and 34 are photo-etched. Hydrofluoric acid is employed as an etching liquid. A Or film being 0.1 em thick and an Al film being 1.5 em thick are formed on the resultant entire surface at the substrate tempera-lure of 100 to 250C. Thereafter, a Creole electrode ~L1232~
1 35 is formed by photo etching, and at a same time the Creole film is removed in the contact hole 32 on the photo diode. Thus, a transparent electrode 36 of trays-parent conductive layer remains on the photo diode, which is to be a window for incident light. As such, the application of this invention to this embodiment ensures that a linear sensor array sensor of matrix drive type is made through a simple and easy fabricating process.
Although the Or electrode 29 was employed in this embody-mint such a metal as Tax Nick, Ma, W, Al, Pi, Pod, No etc.can also be used as an electrode. The multiple layer including these metals may be used.
Furthermore, in this embodiment the double layer composed of Or and Al was adopted as a metal film for developing a transparent electrode and the upper metallic wiring 35 obtained by working the metal film.
A single layer or multiple layer, however, may be used provided that its structure is such that one selected from the group including Or, Mow Tip V, Or, Nub, Tax W, Hi, Nix Pod, Co, Pi and Rho or the metal having the selected one element as a main component is in contact with the amorphous silicon film. And in this embody-mint, stacking was carried during heating but heating may be performed at 100 to 250C after the stacking.
Moreover, although a blocking diode was placed at a common electrode side in this embodiment, the block-in diode and the photo diode may be replaced by each other.
~2~20~
1 There are liner sensor array arrangements such as shown in Figs. PA to OF in addition to the above described arrangement. One photosensitive element is constituted by the blocking diode DUB and the photo diode Do in Figs. PA and 7B, by the blocking diode DUB and a photo conductive film 52 in Figs. 7C and ED, and my the photo diode Do and a capacitor consisting of an upper metal electrode 42, an insulator 53 and an under metal-fig electrode 29 in Figs. YE and OF, respectively. Figs.
PA, 7C and YE illustrate such a structure that two cells are arranged horizontally while Figs. 7B, ED and OF
illustrate such a structure that they are arranged vertically. It is evident that this invention is apply-cable to all the structures shown in these figures in such a manner that the previously mentioned transparent electrode is formed on only the contact hole over the photo diode and the photo conductive film as a window for incident light in these figures. In this embodiment, a p-i-n diode was adopted for each diode but a Skeptic diode may also be employed.
Incidentally, in Figs. PA to OF, reference numeral 28 designates a glass substrate; 29 an under metallic electrode; 30 an insulating film; 37, 37' a semiconductor material for constituting a diode; 40, 49, 50 a p-type semiconductor layer, i-type semiconductor layer and n-type semiconductor layer, respectively; 42 an upper metallic electrode; and 51 a transparent electrode according to this invention.
~3205~
1 Embodiment 4:
The sectional structure of this embodiment is illustrated in Fig. 8, which is the same as the embody-mint 3 except that in the embodiment 3 the transparent electrode 36 is caused to remain on only the photo diode while no this embodiment 4, Creole, which corresponds to the part indicated by letter "A" in the neighborhood of the photo diode, is removed to form a hole. Such an arrangement enables the light L to enter from the lower side of the glass substrate 28 as indicated by an arrow.
That is, this arrangement can be adapted to such a device that the list L is caused to enter from the lower side of the glass substrate 28, and the light reflected at a manuscript I placed in proximity to the sensor is caused to enter the photo diode thereby to read the manuscript M through photoelectric conversion.
Embodiment 5:
Explanation will be made on the embodiment that this invention is adapted to a solid state imaging device using a photo conductive film.
As disclosed in Japanese Patent Application Laid-Open No. 51-10715 laid open on 1981, this device is such that a photo conductive film made of a photo conductor such as an assay for photo-electric conversion is formed on a semiconductor substrate TIC substrate for scanning) having at least switches two-dimentionally arranged and a scanner for transmitting photoelectrons derived through ~232~
1 the switches and corresponding to an optical image. Fig.
9 shows a basic structure of this device. The IT part for scanning is made by an ordinary process for manufas-luring a semiconductor device. First, a thin Sue film being about AYE is formed on a p-type So substrate 60, and an Sweeney is formed on a predetermined area of the Sue Calm, with its thickness being about AYE. The Sue film is made by a common CUD technique and the Sweeney film is made by the CUD technique in No atmosphere.
Next, the So substrate is subjected to local oxidation in such an atmosphere as I 2 = 1:8 to form an Sue layer I This method is directed to local oxidation of So for an isolation between elements commonly called LOOS. The above Sweeney film and Sue film are once removed partially and a gate insulating film 71 for an MOW transistor is formed by an Sue film.
exit, a gate portion 69 of polysilicon and, diffusion areas 70, 61 are formed and an Sue film 72 is formed on the resultant surface. A window for deriving an electrode for the diffusion area 61 is bored in this film 72 by etching. Al is deposited to form an electrode with its thickness being AYE. An Sue film 63 being AYE thick is formed, an window for deriving an electrode is bored on the diffusion area pa by etching, and Al or My is deposited with its thickness of l em as an electrode 64. Incidentally, the electrode 64 is formed so wide as to cover the diffusion areas 70 and 61 and the gate portion. This is because an incident light to a signal processing area between elements may zoos 1 cause an undesired blooming.
A phGtoconductive film 65 is formed by sputter-in in an atmosphere of the mixed gas composed of An and H
at 0.2 Torn. The hydrogen convent is 6 molt. That is, the reactive sputtering is performed at a frequency of 13.56 MHz and input of 300 W using a silicon target to stack the photo conductive film 65 of 1 em on the IT
substrate for scanning. Thereafter, Or is stacked by AYE at the substrate temperature of 100 to 250C by sputtering or vacuum deposition. Next, patterning is carried out so as to section the photosensitive element as shown in a plan view of a photosensitive part of Fig. 10. Thus, a transparent conductive film 66 is formed on the photosensitive element, which also acts as a shading 67 enhance a resolution so as to restrict an angle of the incident light for one photosensitive element.
Although MOW transistor was used as a scanning IT in this embodiment a COD or BUD may also be adapted in place of the MOW transistor.
where the shading 67 is not required, the remainder of Or at only the peripheral portion of a photo conductive layer will not cause any serious problem.
B and P were used as a Dupont for the assay in this embodiment, but it is evident that N, C, O, G, etc. may be used. And F may be used as a terminator of a dangling bond instead of H.
Claims (25)
1. A semiconductor device comprising a substrate; a semiconductor layer made of amorphous silicon formed on said substrate; a transparent conductive layer formed by an interfacial reaction between the amorphous silicon layer and a portion of a metallic film directly formed on the amorphous silicon layer; and the remaining portion of said metallic film extending on said transparent conductive layer; said remaining portion of said metallic film being patterned to selectively expose a predetermined portion of the surface of said transparent conductive layer so that incident light impinges on the exposed surface portion of said transparent conductive layer.
2. A semiconductor device according to claim 1, wherein at least the portion of said metallic film that reacts with the amorphous silicon layer to form said transparent conductive layer contains at least one element selected from the group consisting of Cr, Mo, W, Ti, V, Zr, Nb, Ta, Hf, Ni, Pd, Co, Pt and Rh.
3. A semiconductor device according to claim 1, wherein the remaining patterned portion of said metallic film serves as an electrode.
4. A semiconductor device according to claim 3, wherein said electrode has a stripe form.
5. A semiconductor device according to claim 1, wherein the remaining patterned portion of said metallic film serves as a shading layer.
6. A semiconductor device comprising:
a substrate;
a semiconductor layer made of amorphous silicon formed on said substrate;
a transparent conductive layer formed on said semi-conductor layer, said transparent conductive layer comprising a reaction product of the amorphous silicon of said semiconductor layer and a metal material; and a metallic film disposed on said transparent conductive layer, said metallic film being patterned to selectively expose a predetermined portion of the surface of said transparent conductive layer so that incident light impinges on the exposed surface portion of said transparent conductive layer.
a substrate;
a semiconductor layer made of amorphous silicon formed on said substrate;
a transparent conductive layer formed on said semi-conductor layer, said transparent conductive layer comprising a reaction product of the amorphous silicon of said semiconductor layer and a metal material; and a metallic film disposed on said transparent conductive layer, said metallic film being patterned to selectively expose a predetermined portion of the surface of said transparent conductive layer so that incident light impinges on the exposed surface portion of said transparent conductive layer.
7. A semiconductor device according to claim 6, wherein said metal material is at least one element selected from the group consisting of Cr, Mo, W, Ti, V, Zr, Nb, Ta, Hf, Ni, Pd, Co, Pt and Rh.
8. A semiconductor device according to claim 6, wherein said patterned metallic film serves as an electrode.
9. A semiconductor device according to claim 8, wherein said electrode has a stripe form.
10. A semiconductor device according to claim 6, wherein said patterned metallic film serves as a shading layer.
11. A semiconductor device according to claim 6, further comprising an electrode formed between said substrate and said semiconductor layer.
12. A semiconductor device according to claim 6, wherein said patterned metallic film serves as an upper electrode and an under electrode is interposed between said semiconductor layer and said substrate.
13. A semiconductor device according to claim 7, wherein said metallic film is made of said at least one element selected from said group.
14. A semiconductor device according to claim 7, wherein said metallic film is made of a metal material different from said group.
15. A semiconductor device according to claim 7, wherein said metallic film includes a portion which adjoins said transparent conductive layer and is made of said at least one element of said group; the remaining portion of the metallic film being made of a metal material different from the at least one element selected from said group.
16. A semiconductor device comprising:
(a) a substrate;
(b) an amorphous silicon layer formed on said substrate;
(c) a transparent conductive layer formed on said amorphous silicon layer, said transparent conductive layer comprising a reaction product of the amorphous silicon of said amphorous silicon layer and at least one element selected from the group consisting of Cr, Mo, W, Ti, V, Zr, Nb, Ta, Hf, Ni, Pd, Co, Pt and Rh; and (d) a metallic film formed on said transparent conductive layer, said metallic film being patterned to selectively expose a predetermined portion of the surface of said transparent conductive layer so that incident light impinges on the exposed surface portion of said transparent conductive layer.
(a) a substrate;
(b) an amorphous silicon layer formed on said substrate;
(c) a transparent conductive layer formed on said amorphous silicon layer, said transparent conductive layer comprising a reaction product of the amorphous silicon of said amphorous silicon layer and at least one element selected from the group consisting of Cr, Mo, W, Ti, V, Zr, Nb, Ta, Hf, Ni, Pd, Co, Pt and Rh; and (d) a metallic film formed on said transparent conductive layer, said metallic film being patterned to selectively expose a predetermined portion of the surface of said transparent conductive layer so that incident light impinges on the exposed surface portion of said transparent conductive layer.
17. A semiconductor device according to claim 16, wherein said metallic film it made of said at least one element of said group.
18. A semiconductor device according to claim 16, wherein said metallic film is made of a metal material different from said group.
19. A semiconductor device according to claim 16, wherein said metallic film includes a portion which adjoins said transparent conductive layer and is made of said at least one element of said group and a remaining portion which is made of a metal material different from said group.
20. A semiconductor device comprising:
(a) a substrate;
(b) a semiconductor layer made of amorphous silicon formed on said substrate;
(c) a metallic film formed on said semiconductor layer;
(d) a transparent conductive layer interposed between said semiconductor layer and said metallic film, said transparent conductive layer comprising a reaction product of the amorphous silicon of said semiconductor layer and the metal material forming said metallic film; and e) said metallic film being patterned to selectively expose a predetermined portion of the surface of said transparent conductive layer so that incident light impinges on the exposed surface portion of said transparent conductive layer.
(a) a substrate;
(b) a semiconductor layer made of amorphous silicon formed on said substrate;
(c) a metallic film formed on said semiconductor layer;
(d) a transparent conductive layer interposed between said semiconductor layer and said metallic film, said transparent conductive layer comprising a reaction product of the amorphous silicon of said semiconductor layer and the metal material forming said metallic film; and e) said metallic film being patterned to selectively expose a predetermined portion of the surface of said transparent conductive layer so that incident light impinges on the exposed surface portion of said transparent conductive layer.
21. A semiconductor device according to claim 20, wherein the metal material of said metallic film is at least one element selected from the group consisting of Cr, Mo, W, Ti, V, Zr, Nb, Ta, Hf, Ni, Pd, Co, Pt and Rh.
22. A method of manufacturing a semiconductor device comprising the steps of forming an amorphous silicon layer on a given substrate, forming a metallic film on the amorphous silicon layer during heat treatment or carrying out the heat treatment after forming metal film and removing a desired area for light incidence from said metallic film, said heat treatment being for the formation of an interfacial reaction layer between the amorphous silicon layer and the metallic film.
23. A method of manufacturing a semiconductor device according to claim 22, wherein said metallic film contains at least one selected from the group consisting of Cr, Mo, W, Ti, V, Zr, Nb, Ta, Hf, Ni, Pd, Co, Pt and Rh.
24. A method of manufacturing a semiconductor device according to claim 23, wherein said metallic film is composed of plural layers and the layer in contact with the amorphous silicon layer contains at least one selected from said group.
25. A method of manufacturing a semiconductor device according to claim 22, wherein after said amorphous silicon layer is formed, a surface layer thereof is removed and then said metallic layer is formed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57220641A JPS59110179A (en) | 1982-12-16 | 1982-12-16 | Semiconductor device and manufacture thereof |
| JP220641/1982 | 1982-12-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1232051A true CA1232051A (en) | 1988-01-26 |
Family
ID=16754146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000443019A Expired CA1232051A (en) | 1982-12-16 | 1983-12-12 | Semiconductor device and method of manufacturing the same |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US4788582A (en) |
| EP (1) | EP0111899B1 (en) |
| JP (1) | JPS59110179A (en) |
| CA (1) | CA1232051A (en) |
| DE (1) | DE3381711D1 (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59110179A (en) * | 1982-12-16 | 1984-06-26 | Hitachi Ltd | Semiconductor device and manufacture thereof |
| US4529619A (en) * | 1984-07-16 | 1985-07-16 | Xerox Corporation | Ohmic contacts for hydrogenated amorphous silicon |
| US4774207A (en) * | 1987-04-20 | 1988-09-27 | General Electric Company | Method for producing high yield electrical contacts to N+ amorphous silicon |
| DE68927845T2 (en) * | 1988-09-30 | 1997-08-07 | Kanegafuchi Chemical Ind | Solar cell with a transparent electrode |
| JPH07105483B2 (en) * | 1988-12-16 | 1995-11-13 | 鐘淵化学工業株式会社 | Semiconductor image sensor |
| JPH02186636A (en) * | 1989-01-12 | 1990-07-20 | Seiko Epson Corp | Wiring of integrated circuit device |
| IL96561A0 (en) * | 1989-12-28 | 1991-09-16 | Minnesota Mining & Mfg | Amorphous silicon sensor |
| US5254480A (en) | 1992-02-20 | 1993-10-19 | Minnesota Mining And Manufacturing Company | Process for producing a large area solid state radiation detector |
| US5449924A (en) * | 1993-01-28 | 1995-09-12 | Goldstar Electron Co., Ltd. | Photodiode having a Schottky barrier formed on the lower metallic electrode |
| JP2701726B2 (en) * | 1993-12-28 | 1998-01-21 | 日本電気株式会社 | Solid-state imaging device |
| US6117771A (en) * | 1998-02-27 | 2000-09-12 | International Business Machines Corporation | Method for depositing cobalt |
| US6323417B1 (en) | 1998-09-29 | 2001-11-27 | Lockheed Martin Corporation | Method of making I-III-VI semiconductor materials for use in photovoltaic cells |
| US6376868B1 (en) | 1999-06-15 | 2002-04-23 | Micron Technology, Inc. | Multi-layered gate for a CMOS imager |
| US6445014B1 (en) | 1999-06-16 | 2002-09-03 | Micron Technology Inc. | Retrograde well structure for a CMOS imager |
| US6310366B1 (en) | 1999-06-16 | 2001-10-30 | Micron Technology, Inc. | Retrograde well structure for a CMOS imager |
| US6654057B1 (en) | 1999-06-17 | 2003-11-25 | Micron Technology, Inc. | Active pixel sensor with a diagonal active area |
| US6414342B1 (en) | 1999-06-18 | 2002-07-02 | Micron Technology Inc. | Photogate with improved short wavelength response for a CMOS imager |
| US6326652B1 (en) * | 1999-06-18 | 2001-12-04 | Micron Technology, Inc., | CMOS imager with a self-aligned buried contact |
| US6204524B1 (en) | 1999-07-14 | 2001-03-20 | Micron Technology, Inc. | CMOS imager with storage capacitor |
| JP3414343B2 (en) | 1999-11-26 | 2003-06-09 | 日本電気株式会社 | Image sensor and method of manufacturing the same |
| US6407440B1 (en) | 2000-02-25 | 2002-06-18 | Micron Technology Inc. | Pixel cell with high storage capacitance for a CMOS imager |
| US6455836B1 (en) * | 2000-04-25 | 2002-09-24 | Agilent Technologies, Inc. | Metallic optical barrier for photo-detector array is also interconnecting electrode |
| US6611037B1 (en) * | 2000-08-28 | 2003-08-26 | Micron Technology, Inc. | Multi-trench region for accumulation of photo-generated charge in a CMOS imager |
| US6689950B2 (en) * | 2001-04-27 | 2004-02-10 | The Boeing Company | Paint solar cell and its fabrication |
| AU2002321022A1 (en) * | 2001-05-16 | 2002-11-25 | Stmicroelectronics N.V. | Optoelectronic component having a conductive contact structure |
| DE102004031950A1 (en) * | 2003-06-26 | 2005-02-10 | Kyocera Corp. | Semiconductor / electrode contact structure and such a semiconductor device using |
| EP1854141A1 (en) * | 2005-02-28 | 2007-11-14 | OC Oerlikon Balzers AG | Method of fabricating an image sensor device with reduced pixel cross-talk |
| US8501522B2 (en) * | 2008-05-30 | 2013-08-06 | Gtat Corporation | Intermetal stack for use in a photovoltaic cell |
| US7915522B2 (en) | 2008-05-30 | 2011-03-29 | Twin Creeks Technologies, Inc. | Asymmetric surface texturing for use in a photovoltaic cell and method of making |
| US20100116942A1 (en) * | 2008-06-09 | 2010-05-13 | Fitzgerald Eugene A | High-efficiency solar cell structures |
| DE102008051670A1 (en) * | 2008-10-15 | 2009-11-05 | H2 Solar Gmbh | Metallic or non-metallic silicides for photo-electrochemical decomposition of water and photovoltaic electricity generation, is illuminated, optionally in contact with water |
| US20110124146A1 (en) * | 2009-05-29 | 2011-05-26 | Pitera Arthur J | Methods of forming high-efficiency multi-junction solar cell structures |
| US8604330B1 (en) | 2010-12-06 | 2013-12-10 | 4Power, Llc | High-efficiency solar-cell arrays with integrated devices and methods for forming them |
| US9312426B2 (en) | 2011-12-07 | 2016-04-12 | International Business Machines Corporation | Structure with a metal silicide transparent conductive electrode and a method of forming the structure |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2112812C2 (en) * | 1971-03-17 | 1984-02-09 | Licentia Patent-Verwaltungs-Gmbh, 6000 Frankfurt | Semiconductor component with lattice-shaped metal electrode and method for its production |
| US3753774A (en) * | 1971-04-05 | 1973-08-21 | Rca Corp | Method for making an intermetallic contact to a semiconductor device |
| US4142195A (en) * | 1976-03-22 | 1979-02-27 | Rca Corporation | Schottky barrier semiconductor device and method of making same |
| FR2463508A1 (en) * | 1979-08-16 | 1981-02-20 | Anvar | Ohmic contact mfr. on hydrogenated amorphous silicon - using intermediate layer starved of hydrogen |
| JPS56103477A (en) * | 1980-01-21 | 1981-08-18 | Hitachi Ltd | Photoelectric conversion element |
| US4278704A (en) * | 1980-01-30 | 1981-07-14 | Rca Corporation | Method for forming an electrical contact to a solar cell |
| US4297393A (en) * | 1980-02-28 | 1981-10-27 | Rca Corporation | Method of applying thin metal deposits to a substrate |
| JPS56157075A (en) * | 1980-05-09 | 1981-12-04 | Hitachi Ltd | Photoelectric transducing device |
| US4322453A (en) * | 1980-12-08 | 1982-03-30 | International Business Machines Corporation | Conductivity WSi2 (tungsten silicide) films by Pt preanneal layering |
| JPS57152174A (en) * | 1981-03-13 | 1982-09-20 | Hitachi Ltd | Manufacture of light receiving device |
| JPS584924A (en) * | 1981-07-01 | 1983-01-12 | Hitachi Ltd | Forming method for semiconductor device electrode |
| US4534099A (en) * | 1982-10-15 | 1985-08-13 | Standard Oil Company (Indiana) | Method of making multilayer photoelectrodes and photovoltaic cells |
| JPS59110179A (en) * | 1982-12-16 | 1984-06-26 | Hitachi Ltd | Semiconductor device and manufacture thereof |
-
1982
- 1982-12-16 JP JP57220641A patent/JPS59110179A/en active Granted
-
1983
- 1983-12-12 CA CA000443019A patent/CA1232051A/en not_active Expired
- 1983-12-15 EP EP19830112624 patent/EP0111899B1/en not_active Expired - Lifetime
- 1983-12-15 DE DE8383112624T patent/DE3381711D1/en not_active Expired - Lifetime
-
1986
- 1986-11-10 US US06/929,056 patent/US4788582A/en not_active Expired - Fee Related
-
1988
- 1988-10-03 US US07/252,144 patent/US5151385A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0481353B2 (en) | 1992-12-22 |
| EP0111899A2 (en) | 1984-06-27 |
| DE3381711D1 (en) | 1990-08-09 |
| US4788582A (en) | 1988-11-29 |
| US5151385A (en) | 1992-09-29 |
| EP0111899A3 (en) | 1987-01-28 |
| EP0111899B1 (en) | 1990-07-04 |
| JPS59110179A (en) | 1984-06-26 |
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