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Publication numberUSRE38727 E1
Publication typeGrant
Application numberUS 08/999,682
Publication dateApr 19, 2005
Filing dateOct 8, 1997
Priority dateAug 24, 1982
Publication number08999682, 999682, US RE38727 E1, US RE38727E1, US-E1-RE38727, USRE38727 E1, USRE38727E1
InventorsShunpei Yamazaki
Original AssigneeSemiconductor Energy Laboratory Co., Ltd.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Photoelectric conversion device and method of making the same
US RE38727 E1
Abstract
A photoelectric conversion device has a non-single-crystal semiconductor laminate member formed on a substrate having a conductive surface, and a conductive layer formed on the non-single-crystal semiconductor laminate member. The non-single-crystal semiconductor laminate member has such a structure that a first non-single-crystal semiconductor layer having a P or N first conductivity type, an I-type second non-single-crystal semiconductor layer and a third non-single-crystal semiconductor layer having a second conductivity type opposite the first conductivity type are laminated in this order. The first (or third) non-single-crystal semiconductor layer is disposed on the side on which light is incident, and is P-type. The I-type non-single-crystal semiconductor layer has introduced thereinto a P-type impurity, such as boron which is distributed so that its concentration decreases towards the third (or first) non-single-crystal semiconductor layer in the thickwise direction of the I-type layer.
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Claims(19)
1. A method for manufacturing a photoelectric conversion device comprising the steps of:
forming a first impurity, non-single crystalline semiconductor layer of a first conductivity type on a substrate in a reaction chamber;
depositing a substantially intrinsic semiconductor layer on said first impurity layer by introducing process gas into said reaction chamber together with a dopant gas comprising boron, the introducing ratio of said dopant gas to said process gas being monotonically decreased throughout the deposition of the intrinsic semiconductor layer in order that the impurity concentration in said intrinsic semiconductor layer is monotonically decreased from the interface between said first impurity and intrinsic semiconductor layers;
forming a second impurity, non-single crystalline semiconductor layer of a second conductivity type opposite to said first conductivity type, the impurity semiconductor layer adjacent to the heavier doping side of said intrinsic layer having the same conductivity type as that corresponding to the dopant gas for said intrinsic semiconductor layer;
forming an electrode arrangement for said conversion device; and
reducing the oxygen concentration in said substantially intrinsic layer to a level less than 51019 atoms/cm3.
2. A manufacturing method according to claim 1 5, wherein the process gas is a hydride or halide of silicon and the dopant gas is a hydride or halide of boron.
3. A manufacturing method according to claim 2 5, wherein the concentration of the dopant gas relative to the concentration of the process gas is continuously decreased with time within a range of less than 5 ppm.
4. A method as in claim 3 where5, wherein said level is as low as 51018 atoms/cm3.
5. A manufacturing method as in claim 1 wherefor manufacturing a photoelectric conversion device comprising the steps of:
forming a first impurity, non-single crystalline semiconductor layer of a first conductivity type on a substrate in a reaction chamber;
depositing a substantially intrinsic semiconductor layer on said first impurity layer by introducing process gas into said reaction chamber together with a dopant gas comprising boron, the introducing ratio of said dopant gas to said process gas being monotonically decreased throughout the deposition of the intrinsic semiconductor layer in order that the impurity concentration in said intrinsic semiconductor layer is monotonically decreased from the interface between said first impurity and intrinsic semiconductor layers;
forming a second impurity, non-single crystalline semiconductor layer of a second conductivity type opposite to said first conductivity type, the impurity semiconductor layer adjacent to the heavier doping side of said intrinsic layer having the same conductivity type as that corresponding to the dopant gas for said intrinsic semiconductor layer;
forming an electrode arrangement for said conversion device; and
reducing the oxygen concentration in said substantially intrinsic layer to a level less than 510 19 atoms/cm 3,
wherein the reduction of the oxygen concentration is effected by passing said process gas through a molecular sieve or zeolite which adsorbs oxygen.
6. A method of claim 1 5, wherein said semiconductor layer is made of amorphous semiconductor.
7. A method of claim 6 5, wherein said process gas is filtered in advance of introduction into said reaction chamber.
8. A method for manufacturing a photoelectric conversion device comprising the steps of:
forming a first impurity, non-single crystalline semiconductor layer of a first conductivity type on a substrate in a reaction chamber;
depositing a substantially intrinsic semiconductor layer on said first impurity layer by introducing process gas into said reaction chamber together with a dopant gas comprising boron, the introducing ratio of said dopant gas to said process gas being monotonically decreased throughout the deposition of the intrinsic semiconductor layer in order that the impurity concentration in said intrinsic semiconductor layer is monotonically decreased from the interface between said first impurity and intrinsic semiconductor layers;
forming a second impurity, non-single crystalline semiconductor layer of a second conductivity type opposite to said first conductivity type, the impurity semiconductor layer adjacent to the heavier doping side of said intrinsic layer having the same conductivity type as that corresponding to the dopant gas for said intrinsic semiconductor layer;
forming an electrode arrangement for said conversion device; and
reducing the carbon concentration in said substantially intrinsic layer to a level less than 41019 atoms/cm3.
9. A method as in claim 8 where10, wherein said level is as low as 41015 atoms/cm3.
10. A manufacturing method as in claim 8method for manufacturing a photoelectric conversion device comprising the steps of:
forming a first impurity, non-single crystalline semiconductor layer of a first conductivity type on a substrate in a reaction chamber;
depositing a substantially intrinsic semiconductor layer on said first impurity layer by introducing process gas into said reaction chamber together with a dopant gas comprising boron, the introducing ratio of said dopant gas to said process gas being monotonically decreased throughout the deposition of the intrinsic semiconductor layer in order that the impurity concentration in said intrinsic semiconductor layer is monotonically decreased from the interface between said first impurity and intrinsic semiconductor layers;
forming a second impurity, non-single crystalline semiconductor layer of a second conductivity type opposite to said first conductivity type, the impurity semiconductor layer adjacent to the heavier doping side of said intrinsic layer having the same conductivity type as that corresponding to the dopant gas for said intrinsic semiconductor layer;
forming an electrode arrangement for said conversion device; and
reducing the carbon concentration in said substantially intrinsic layer to a level less than 410 18 atoms/cm 3 ;
wherein the reduction of the carbon concentration is effected by passing said process gas through a molecular sieve or zeolite which adsorbs carbon.
11. A method for manufacturing a photoelectric conversion device comprising the steps of:
forming a first impurity, non-single crystalline semiconductor layer of a first conductivity type on a substrate in a reaction chamber;
depositing a substantially intrinsic semiconductor layer on said first impurity layer by introducing process gas into said reaction chamber together with a dopant gas comprising boron, the introducing ratio of said dopant gas to said process gas being monotonically decreased throughout the deposition of the intrinsic semiconductor layer in order that the impurity concentration in said intrinsic semiconductor layer is monotonically decreased from the interface between said first impurity and intrinsic semiconductor layers;
forming a second impurity, non-single crystalline semiconductor layer of a second conductivity type opposite to said first conductivity type, the impurity semiconductor layer adjacent to the heavier doping side of said intrinsic layer having the same conductivity type as that corresponding to the dopant gas for said intrinsic semiconductor layer;
forming an electrode arrangement for said conversion device; and
reducing the phosphorus concentration in said substantially intrinsic layer to a level less than 51015 atoms/cm3.
12. A method as in claim 11 where said level is as low as 51015 atoms/cm3.
13. A manufacturing method as in claim 11 where the reduction of the phosphorus concentration is effected by passing said process gas through a molecular sieve or zeolite which adsorbs phosphorus.
14. A method as in claims 1, 8, or 11 where5 or 10, wherein said first conductivity type is n-type and said second conductivity type is p-type.
15. A method as in claims 1, 8, or 11 where5 or 10, wherein said first conductivity type is p-type and said second conductivity type is n-type.
16. A method as in claims 1, 8, or 11 where5 or 10, wherein the ratio of said impurity concentration at the interface between said second impurity and intrinsic semiconductor layers to that at said interface between said first impurity and the intrinsic semiconductor layers is 1/10 to 1/100.
17. A method as in claim 16wherewherein said ratio is 1/20 to 1/40.
18. A method as in claims 1, 8, or 11 where5 or 10, wherein said impurity is boron and the boron concentration at said interface between the p-type and intrinsic layers is 21015 to 21017 atoms/cm3.
19. A method as in claims 1, 8, or 11 where5 or 10, wherein said first layer comprises p-type, non-single crystalline SixC1-x (0<x<1) and said impurity comprises boron.
Description

This application is a continuation of Ser. No. 06/785,586, filed Oct. 8, 1985, which itself was a division of application Ser. No. 06/564,213 filed Dec. 22, 1983, both now abandoned.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of Ser. No. 08/408,781, filed Mar. 22, 1995, now abandoned; which is a reissue application for U.S. Pat. No. 5,077,223, which issued from Ser. No. 07/443,015, filed Nov. 29, 1989; which is a continuation of Ser. No. 06/785,586, filed Oct. 8, 1985, now abandoned; which is a divisional of Ser. No. 06/564,213 filed Dec. 22, 1983, now U.S. Pat. No. 4,581,476; which is a continuation-in-part of Ser. No. 06/525,459, filed Aug. 22, 1983, now U.S. Pat. No. 4,591,892.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a photoelectric conversion device which has a non-single-crystal semiconductor laminate member having formed therein at least one PIN junction, and a method for the manufacture of such a photoelectric conversion device.

2. Description of the Prior Art

A photoelectric conversion device of the type including a non-single-crystal semiconductor laminate member having formed therein at least one PIN junction usually has the non-single-crystal semiconductor laminate member formed on a substrate having a conductive surface and a conductive layer formed on the non-single-crystal semiconductor laminate member. The non-single-crystal semiconductor laminate member has at least a first non-single-crystal semiconductor layer of a P or N first conductivity type, an I type second non-single-crystal semiconductor layer formed on the first non-single-crystal semiconductor layer and a third non-single-crystal semiconductor layer formed on the second non-single-crystal semiconductor layer and having a second conductivity type opposite from the first conductivity type. The first, second and third non-single-crystal semiconductor layers form one PIN junction.

In this case, for example, the substrate has such a structure that a light-transparent conductive layer is formed as a first conductive layer on a light-transparent insulating substrate body. The first and third non-single-crystal semiconductor layers of the non-single-crystal semiconductor laminate member are P- and N-type, respectively. Further, the conductive layer on the non-single-crystal semiconductor laminate member is formed as a second conductive layer on the N-type third non-single-crystal semiconductor layer.

With the photoelectric conversion device of such a structure as described above, when light is incident on the side of the light-transparent substrate towards the non-single-crystal semiconductor laminate member, electron-hole pairs are created by the light in the I-type second non-single-crystal semiconductor layer. Holes of the electron-hole pairs thus created pass through the P-type first non-single-crystal semiconductor layer to reach the first conductive layer, and electrons flow through the N-type third non-single-crystal semiconductor layer into the second conductive layer. Therefore, photocurrent is supplied to a load which is connected between the first and second conductive layers, thus providing a photoelectric conversion function.

In conventional photoelectric conversion devices of the type described above, however, since the I-type second non-single-crystal semiconductor layer is formed to contain oxygen with a concentration above 1020 atoms/cm3, and/or carbon with a concentration above 1020 atoms/cm3, and/or phosphorus with a concentration as high as above 51017 atoms/cm3, the I-type non-single-crystal semiconductor layer inevitably contains impurities imparting N conductivity type, with far lower concentrations than in the P-type first non-single-crystal semiconductor layer and the N-type third non-single-crystal semiconductor layer.

In addition, the impurity concentration has such a distribution that it undergoes substantially no variations in the thickness direction of the layer.

On account of this, in the case where the second non-single-crystal semiconductor layer is formed thick with a view to creating therein a large quantity of electron-hole pairs in response to the incidence of light, a depletion layer, which spreads into the second non-single-crystal semiconductor layer from the PI junction defined between the P-type first and the I-type second non-single-crystal semiconductor layers, and a depletion layer, which spreads into the second non-single-crystal semiconductor layer from the NI junction defined between the N-type third and the I-type second non-single-crystal semiconductor layers, are not linked together. In consequence, the second non-single-crystal semiconductor layer has, over a relatively wide range thickwise thereof at the central region in that direction, a region in which the bottom of the conduction band and the top of the valence band of its energy band are not inclined in the directions, necessary for the holes and electrons to drift towards the first and third non-single-crystal semiconductor layers, respectively. Therefore, the holes and electrons of the electron-hole pairs created by the incident light in the second non-single-crystal semiconductor layer, in particular, the electrons and holes generated in, the central region of the second layer in its thickness direction, are not effectively directed to the first and third non-single-crystal semiconductor layers, respectively.

Accordingly, the prior art photoelectric conversion devices of the above-described structure have the defect that even if the second non-single-crystal semiconductor layer is formed thick for creating a large quantity of electron-hole pairs in response to incident light, a high photoelectric conversion efficiency cannot be obtained.

Further, even if the I-type second non-single-crystal semiconductor layer is thick enough to permit the depletion layer extending into the second non-single-crystal semiconductor layer from the PI junction between the P-type first non-single-crystal semiconductor layer on the side on which light is incident and the I-type second non-single-crystal semiconductor layer formed on the first semiconductor layer and the depletion layer extending into the second non-single-crystal semiconductor layer from the NI junction between the N-type third non-single-crystal semiconductor layer on the side opposite from the side of the incidence of light and the I-type second non-single-crystal semiconductor layer to be linked together, the expansion of the former depletion layer diminishes with the lapse of time for light irradiation by virtue of a known light irradiation effect commonly referred to as the Staebler-Wronsky effect, because the I-type non-single-crystal semiconductor layer forming the PI junction contains impurities which impart N conductivity type as mentioned previously. Finally, the abovesaid depletion layers are disconnected from each other. In consequence, there is formed in the central region of the second non-single-crystal semiconductor layer in the thickness direction thereof a region in which the bottom of the conduction band and the top of the valence band of the energy band are not inclined in the directions in which the holes and electrons of the electron-hole pairs created by the incidence of light are drifted towards the first and third non-single-crystal semiconductor layers, respectively.

Accordingly, the conventional photoelectric conversion devices of the abovesaid construction have the defect that the photoelectric conversion efficiency is impaired by the long-term use of the devices.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a novel photoelectric conversion device which is able to achieve a far higher photoelectric conversion efficiency than that obtainable with the conventional devices described above.

Another object of the present invention is to provide a novel photoelectric conversion device the photoelectric conversion efficiency of which is hardly or only slightly lowered by the Staebler-Wronski effect even if it is used for a long period of time.

Yet another object of the present invention is to provide a novel method which permits easy manufature of the photoelectric conversion device having the abovesaid excellent features.

In accordance with an aspect of the present invention, the first (or third) non-single-crystal semiconductor layer of the non-single-crystal laminate member is a layer on the side on which light is incident and is of P conductivity type, and the I-type second non-single-crystal semiconductor layer has introduced therein an impurity for imparting thereto P type conductivity, which is distributed so that the impurity concentration continuously decreases towards the third (or first) non-single-crystal semiconductor layer in the thickness direction of the I-type layer.

In this case, for example, the substrate is light-transparent and, accordingly, the first non-single-crystal semiconductor layer is disposed on the side where light is incident. The first and third non-single-crystal semiconductor layers are P- and N-type, respectively, and the I-type second non-single-crystal semiconductor layer has introduced therein an impurity for imparting thereto P-type conductivity, such as boron, so that its concentration in the region adjacent the first non-single-crystal semiconductor layuer is higher than the concentration in the region adjacent the third non-single-crystal semiconductor layer.

On account of this, even if the I-type second non-single-crystal semiconductor layer is formed relatively thick for creating therein a large quantity of electron-hole pairs in response to the incidence of light, the depletion layer extending into the second non-single-crystal semiconductor layer from the PI junction between the first and second non-single-crystal semiconductor layers and the depletion layer extending into the second non-single-crystal layer from the NI junction between the third and second non-single-crystal semiconductor layers are joined together. Accordingly, the holes and electrons which are produced in the central region of the second non-single crystal semicondutor layer in its thickwise direction are also effectively drifted towards the first and third non-sinlge-crystal semiconductor layers, respectively.

Moreover, even if the I-type second non-single-crystal semiconductor layer contains impurities which impart thereto N-type conductivity, because it is formed to contain oxygen and/or carbon and phosphorus in large quantities as described previously, boron, which imparts P-type conductivity and is introduced into the second non-single-crystal semiconductor layer, combines with oxygen, and/or carbon, and/or phosphorus. Besides, the P-type impurity introduced into the second non-single-crystal semiconductor layer has a high concentration in the region thereof adjacent the P-type first non-single-crystal semiconductor layer, that is, on the side of the PI junction. Therefore, the expansion of the depletion layer spreading into the second non-single-crystal semiconductor layer from the PI junction between the first and second non-single-crystal semiconductor layers is scarcely or only slightly diminished by the light irradiation effect (the Staeabler-Wronski effect).

Accordingly, the photoelectric conversion device of the present invention retains a high photoelectric conversion efficiency, even if used for a long period of time.

In accordance with another aspect of the present invention, the second non-single-crystal semiconductor layer, which has introduced thereinto an impurity which imparts P-type conductivity, with such a distribution that its concentration continuously decreases towards the N-type third (or first) non-single-crystal semiconductor layer in the thickness direction of the second layer, can easily be formed, through a CVD (Chemical Vapor Deposition) method using a semiconductor material gas and an impurity material gas for imparting P-type conductivity, merely by continuously decreasing (or increasing) the concentration of the depart material gas relative to the semiconductor material gas with the lapse of time.

Accordingly, the manufacturing method of the present invention allows ease in the fabrication of the photoelectric conversion device of the present invention which possesses the aforementioned advantages.

Other objects, features and advantages of the present invention will become more fully apparent from the detailed description take in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to D are sectional views schematically illustrating a sequence of steps involved in the manufacture of a photoelectric conversion device in accordance with an embodiment of the present invention;

FIG. 2A is a sectional view schematically illustrating a first embodiment of the photoelectric conversion device by the manufacturing method shown in FIG. 1;

FIG. 2B is a graph showing the concentration distributions of impurities introduced into first, second, and third non-single-crystal semiconductor layers of the photoelectric conversion device depicted in FIG. 2A;

FIG. 2C is a graph showing the energy band of the photoelectric conversion device shown in FIG. 2A;

FIG. 3 is a graph showing the voltage V (volt)current density I (mA/cm2) characteristic of the photoelectric conversion device of FIG. 2, in comparison with the characteristric of a conventional photoelectric conversion device;

FIG. 4 is a graph showing variations (%) in the photoelectric conversion efficiency of the photoelectric conversion device of the present invention, shown in FIG. 2, in comparison with a conventional photoelectric conversion device;

FIG. 5A is a sectional view schematically illustrating a second embodiment of the photoelectic conversion device of the present invention;

FIG. 5B is a graph showing concentration distributions of impurities introduced into first second, and third non-single-crystal semiconductor layers of the second embodiment of the present invention;

FIG. 6A is a sectional view sechematically illustrating a third embodiment of the photoelectric conversion device of the present invention; and

FIG. 6B is a graph showing the concentration distributions of impurities introduced into first, second, and third non-single-crystal semiconductor layers of the photoelectric conversion device shown in FIG. 6A.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

A description will be given of, with reference to FIGS. 1 and 2, of a first embodiment of the photoelectric conversion device of the present invention, along with the manufacturing method of the present invention.

The manufacture of the photoelectric conversion device starts with the preparation of an insulating, light transparent substrate 1 as of glass (FIG. 1).

A light-transparent conductive layer 2 is formed on the substrate 1 (FIG. 1B).

The conductive layer 2 is formed of, for example, a tin oxide, or a light-transparent conductive material consisting principally of a tin oxide. The conductive layer 2 is formed by, for example, a known vacuum evaporation method to a thickness of, for instance, 0.1 to 0.2 μm.

Next, a non-single-crystal semiconductor laminate member 3 is formed on the conductive layer 2 (FIG. 1C).

The non-single-crystal semiconductor laminate member 3 has such a stucture that a P-type non-single-crystal semiconductor layer 4, an I-type non-single-crystal semiconductor layer 5 and an N-type non-single-crystal semiconductor layer 6 are sequentially formed in this order. These non-single-crystal semiconductor layers 4, 5 and 6 form a PIN junction.

The non-single-crystal semiconductor layer 4 of the non-single-crystal semiconductor laminate member 3 is formed of, for example, Si, SixC1-x (where 0<<1, for instance, =0.8) or Ge in an amorphous, semiamorphous, or microcrystalline form. The non-single-crystal semiconductor layer 4 is, for example, 100 angstroms thick. Moreover, the energy band gap of layer 4 is preferably larger than that of layer 5.

The non-single-crystal semiconductor layer 4 is formed by a CVD method which employs a semiconductor material gas composed of a hydride or halide of a semiconductor, such as Si, Si,Ge1-x (where oxl), or Ge, and an impurity material gas composed of a hydride or halide of a P-type impurity, for instance, diborane (B2H6), The CVD method may or may not employ a glow discharge (plasma), or light. In this case non-single-crystal semiconductor layer 4 has a p-type impurity introduced therein (boron) in a concentration above about 11018 and as high as 11019 to 61020 atoms/cm3, as shown in FIG. 2B.

The non-single-crystal semiconductor Iayer 5 is formed of, for instance, amorphous or semi-amorphous silicon, and has a thickness of, for example, 3 to 0.8 μm, in particular, 0.5 μm.

The non-single-crystal semiconductor layer 5 is formed by a CVD method which uses a semiconductor raw material gas composed of a hydride or halide of silicon, for example, SinH2n+2 (where n is greater than or equal to 1), or SiFm (where m is greater than or equal to 2), and a deposit material gas composed of a hydride or halide of a P-type impurity, for instance, diborane (B2H6), the CVD method may or may not employ a glow discharge (plasma), or light. In this case, by decreasing the concentration of the deposit material gas relative to the concentation of the semiconductor material gas within a range of less than 5 ppm with the lapse of time, the non-single-crystal semiconductor layer 5 is formed having introduced thereinto a P-type impurity (boron) the concentration of which linearly and continuously decreases in the thickness direction of the layer towards the non-single-crystal semiconductor layer 6 as shown in FIG. 2B. The concentration of the P-type impurity in the non-single-crystal semiconductor layer 5 is high on the side of the non-single-crystal semiconductor layer 4 as compared with the impurity concentration on the side of the non-single-crystal semiconductor layer 6. The ratio of the impurity concentration in the layer 5 at one end thereof adjacent the layer 6 to the concentration at the other end adjacent the layer 4 is 1/10 to 1/100, preferably, 1/20 to 1/40. In practice, the P-type impurity (boron) has a concentration of 21015 to 21017 atoms/cm3 at the end of the layer 5 adjacent the layer 4 and a concentration below 11015 atoms/cm3 at the end of the layer 5 adjacent the layer 6.

The non-single-crystal semiconductor layer 5 is formed by the abovesaidabove said CVD method. In this case, the semiconductor raw material gas is one that is obtained by passing a semiconductor raw material gas through a molecular sieve or zeolite which adsorbs oxygen, and/or carbon and/or phosphorus. Accordingly, the non-single-crystal semiconductor layer 5 is formed to contain oxygen at a concentration less than 51019 atoms/cm3 as low as 51018 atoms/cm3, and/or carbon at a concentration level less than 41019 410 18 atoms/cm3 as low as 41015 atoms/cm3, and/or phosphorus at a concentration at least as low as 51015 atoms/cm3.

The non-single-crystal semiconductor layer 6 is formed of, for instance, microcrystalline silicon, and has a thickness of, for example, 100 to 300 angstroms. Moreover, the energy band gap of layer 6 is preferably larger than that of layer 5.

The non-single-crystal semiconductor layer 6 is formed by a CVD method which employs a semiconductor raw material gas composed of a hydride or halide of silicon, for example, SinH2n+2 (where n is greater than or equal to 1) or SiFm (where m is greater than or equal to 2), and an impurity material gas composed of a hydride or halide of an N-type impurity, for instance, phosphine (PH3), the CVD method may or may not employ a glow discharge (plasma) or light. In this case, the non-single-crystal semiconductor layer 6 has an N-type impurity (phosphorus) introduced thereinto with a concentration of 11019 to 61020 atoms/cm3, as shown in FIG. 2.

Next, a conductive layer 7 is formed on the non-single-crystal semiconductor laminate member 3 made up of the non-single-crystal semiconductor layers 4, 5. Moreover, the energy band gap of layer 6 is, preferably larger than that of layer 5. and 6, that is, on the non-single-crystal semiconductor layer 6 (FIG. 1D).

The conductive layer 7 has such a structure that a light-transparent conductive layer 8 formed of, for example, a tin oxide or a light-transparent conductive material consisting principally of tin oxide, and a reflective conductive layer 9 formed of a metal, such as aluminum, silver or the like, are formed in this order. In this case, the conductive layer 8 is formed to a thickness of 900 to 1300 angstroms by means of, for example, vacuum evaporation, and the conductive layer 9 is also formed by vacuum evaporation.

In the manner described above, the first embodiment of the photoelectric conversion device of the present invention shown in FIG. 2A is manufactured.

With the photoelectric conversion device shown in FIG. 2A, when light 10 is incident on the side of the substate 1 towards the non-single-crystal semiconductor laminate member 3, electron-hole pairs are created in the I-type non-single-crystal semiconductor layer 5 in response to the light 10. The holes of the electron-hole pairs thus produced flow through the P-type non-single-crystal semiconductor layer 4 into the light-transparent conductive layer 2, and the electrons flow through the N-type non-single-crystal semiconductor layer 6 into the conductive layer 7. Therefore, photocurrent is supplied to a load which is connected between the conductive layers 2 and 7, thus providing the photoelectric conversion function.

In this case, the I-type non-single-crystal semiconductor layer 5 has a P-type impurity (boron) introduced thereinto which is distributed so that the impurity concentration continuously decreases towards the non-single-crystal semiconductor layer 6 in the thickness direction of the layer 5, as shown in FIG. 2B. On account of this, even if the I-type non-single-crystal semiconductor layer 5 is formed thick for generating therein a large quantity of electraonhole pairs in response to the incident of light, a depletion layer (not shown) which extends into the non-single-crystal semiconductor layer 5 from the PI junction 11 between the P-type non-single-crystal semiconductor layer 4 and the I-type non-single-crystal semiconductor layer 5 and a depletion (not shown) layer which extends into the non-single-crystal semiconductor layer 5 from the NI junction 12 between the N-type non-single-crystal semiconductor layer 6 and the non-single-crystal semiconductor layer 5 are joined together. Therefore, the I-type non-single-crystal semiconductor layer 5, as viewed from the bottom of the conduction band and the top of the valence bands of its enegy band, has a gradient that effectively causes holes and electrons drift towards the non-single-crystal semiconductor layers 4 and 6, respectively.

Accordingly, the photoelectric conversion device of the present invention, shown in FIG. 2A, achieves a higher photoelectric conversion efficiency than do the conventional photoelectric conversion devices.

A photoelectric conversion device corresponding to the conventional one and which is identical in construction with the photoelectric conversion device of the present invention shown in FIG. 2A, except that the concentration of the N-type impurity in the I-type non-single-crystal semiconductor layer 5 is about 1016 atoms/cm3 which is far lower than the impurity concentrations in the P-type and I-type non-single-crystal semiconductor layers 4 and 6 because the I-type non-single-crystal semiconductor layer 5 is formed to contain oxygen, and/or carbon, and/or phosphorus in large quantities, as referred to previously, provided a voltage V (volt)-current density I (mA/cm2) characteristic as indicated by curve 30 in FIG. 3. Accordingly, the open-circuit voltage was 0.89 V, the short-circuit current density I 16.0 mA/cm2, the fill factor was 61%, and the photoelectric conversion efficiency about 8.7%. In contrast thereto, the photoelectric conversion device of the present invention shown in FIG. 2A, provided the voltage V -current density I characteristic as indicated by curve 31 in FIG. 3, obtained. Accordingly, the open-circuit voltage V was 0.92 V, which is higher than was with the abovesaid device corresponding to the prior art device; the current density I was 19.5 mA/cm2; the fill factor was 68%; and the photoelectric conversion efficiency was about 12.2%. Incidentally, these results were obtained under the conditions wherein the photoelectric conversion devices, each having the non-single-crystal semiconductor laminate member 3 of a 1.05 cm2 area, were exposed to irradiation by light with an intensity of AM1 (100 mW/cm2).

In the case of the photoelectric conversion device of a present invention shown in FIG. 2A, since the I-type non-single-crystal semiconductor layer 5 has boron introduced thereinto as a P-type impurity the boron, combines with the oxygen and/or carbon and/or phosphorus contained in the non-single-crystal semiconductor layer 5. In addition, the concentration of the P-type impurity (boron) is high on the side of the PI junction 11, that is, on the side of the P-type non-single-crystal semiconductor layer 4. Accordingly, the expansion of the depletion layer extending into the I-type non-single-crystal semiconductor layer 5 from the PI junction 11 between the P-type non-single-crystal semiconductor layer 4 and the I-type non-single-crystal semiconductor layer 5 is hardly or only slightly diminished by the light irradiation effect (the Staebler-Wronski effect).

For this reason, according to the photoelectric conversion device of the present invention, the aforesaid high photoelectric conversion efficiency is hardly impaired by long-term use.

In addition the aforesaid photoelectric conversion device corresponding to the prior art one which provided the voltage V-current density I characteristeristic indicated by the curve 30 in FIG. 3, exhibited variations (%) in the photoelectric conversion efficiency relative to the light irradiation time T (hr) as indicated by curve 40 in FIG. 4. In contrast thereto, in the case of the photoelectric conversion device of the present invention, the photoelectric conversion efficiency varied with the light irradiation time T as indicated by curve 41 in FIG. 4. That is, the photoelectric conversion efficiency slightly increased in an early stage and, thereafter, it decreased only very slightly with time. These result were also obtained under the same conditions mentioned previously in connection with FIG. 3.

As described above, the first embodiment of the photoelectric conversion device of the present invention possesses the advantage that it provides a higher photoelectric conversion efficiency than do the conventional photoelectric conversion devices, even when used for a long period of time.

Further, the manufacturing method of the present invention shown in FIG. 1 employs a series of simple steps such as forming the conductive layer 2 on the substrate 1, forming the non-single-crystal semiconductor layers 4, 5 and 6 on the conductive layer 2 through the CVD method to provide the non-single-crystal semiconductor laminate member 3 and forming the conductor layer 7 on the non-single-crystal semiconductor laminate member 3, The I-type non-single-crystal semiconductor layer 5 is formed by a CVD method using a semiconductor raw material gas and a P-type deposit (boron) gas and, in this case, simply by continuously changing the concentration of the deposit material gas relative to the concentration of the semiconductor raw material gas as a function of time, the P-type impurity is introduced into the layer 5 with such a concentration distribution that its concentration continuously decreases towards the non-single-crystal semiconductor layer 6 in the thickness direction of the layer 5.

Accordingly, the manufacturing method of the present invention allows ease in the fabrication of the photoelectric conversion device of the present invention which has the aforementioned advantages.

Incidentally, the first embodiment illustrated in FIG. 2 shows the case in which the impurity contained in the I-type non-single-crystal semiconductor layer 5 has such a concentration distribution as shown in FIG. 2B in which the concentration linearly and continuously drops towards the non-single-crystal semiconductor layer 6.

As will be appreciated from the above, however, even if the impurity introduced in the I-type non-single-crystal semiconductor layer 5 has a concentration profile such that the impurity concentration drops stepwise and continuously towards the non-single-crystal semiconductor layer 6 as shown in FIG. 5 which illustrates a second embodiment of the present invention, and even if the impurity in the layer 5 has such a concentration distribution that the impurity concentration decreases non-linearily and continuously towards the layer 6 in a manner to obtain a concentration distribution such that the impurity concentration abruptly drops in the end portion of the layer 5 adjacent the layer 6 as shown in FIG. 6 which illustates a third embodiment of the present invention, the photoelectric conversion device of the present invention produces the same excellent operation and effects as are obtainable with the photoelectric conversion device shown in FIG. 2.

Further, the foregoing description has been given of the case where light is incident on the photoelectric conversion device from the side of the substrate 1 and, accordingly, the non-single-crytal semiconductor layer 4 of the non-single-crystal semiconductor laminate member 3 on the side on which the light is incident is P-type.

But, also in case where the photoelectric conversion device is arranged to be exposed to light on the side opposite from the substrate 1, the non-single-crystal semiconductor layer 6 of the non-single-crystal semiconductor laminate member 3 on the side of the incidence of light is P-type, the non-single-crystal semiconductor layer 4 on the side of the substrate 1 is N-type and the non-single-crystal semiconductor layer 5 has introduced thereinto a P-type impurity (boron) which is distributed so that the impurity concentration continuously decreases towards the non-single-crystal semiconductor layer 4 in the thickness direction of the layer 5, the same excellent operation and effects as described previously can be obtained, as will be understood from the foregoing description. In this case, however, the conductive layer 7 must be substituted with a light-transparent one. The substrate 1 and the conductive layer 2 need not be light-transparent.

While in the foregoing the non-single-crystal semiconductor laminate member 3 has one PIN junction, it is also possible to make the laminate member 3 have two or more PIN junctions and to form each of the two or more I-type non-single-crystal semiconductor layers so that the P-type impurity introduced therein may have the aforesaid concentration distribution.

It will be apparent that many modifications and variations may be effected without departing from the scope of the novel concepts of the present invention.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2882243Dec 24, 1953Apr 14, 1959Union Carbide CorpMolecular sieve adsorbents
US2971607Jul 14, 1958Feb 14, 1961Union Carbide CorpMethod for purifying silance
US3155621Jul 13, 1962Nov 3, 1964Plessey Co LtdProduction of silicon with a predetermined impurity content
US3462422Sep 26, 1966Aug 19, 1969Searle & Co17 - oxygenated androsta/estra-4,6,8(14)-trien - 3 - ones,dihydro congeners,and intermediates
US3492175Dec 17, 1965Jan 27, 1970Texas Instruments IncMethod of doping semiconductor material
US3785122Jan 27, 1972Jan 15, 1974Y YatsurugiProcess for preparing 4,5a zeolite and method for separating mixtures using same
US3892606Jun 28, 1973Jul 1, 1975IbmMethod for forming silicon conductive layers utilizing differential etching rates
US3982912May 6, 1974Sep 28, 1976Yoshifumi YatsurugiMethod for preparation of an improved K-A type zeolite and for separation by adsorption polar and non-polar molecules
US4064521Jul 30, 1976Dec 20, 1977Rca CorporationSemiconductor device having a body of amorphous silicon
US4109271May 27, 1977Aug 22, 1978Rca CorporationAmorphous silicon-amorphous silicon carbide photovoltaic device
US4117506 *Jul 28, 1977Sep 26, 1978Rca CorporationSolar cells
US4226898Mar 16, 1978Oct 7, 1980Energy Conversion Devices, Inc.Amorphous semiconductors equivalent to crystalline semiconductors produced by a glow discharge process
US4239554Jul 16, 1979Dec 16, 1980Shunpei YamazakiSemiconductor photoelectric conversion device
US4409311 *Mar 8, 1982Oct 11, 1983Minolta Camera Kabushiki KaishaElectrography, silicon
US4409805Jan 28, 1982Oct 18, 1983Wang Tzu ChengKey operated lock
US4418132Jun 23, 1981Nov 29, 1983Shunpei YamazakiMember for electrostatic photocopying with Si3 N4-x (0<x<4)
US4425143Aug 24, 1981Jan 10, 1984Shin Tohoku Chemical Industries Inc.Thermoconductive and heat resistant
US4459163Mar 5, 1982Jul 10, 1984Chronar CorporationAmorphous semiconductor method
US4460670Nov 19, 1982Jul 17, 1984Canon Kabushiki KaishaPhotoconductive member with α-Si and C, N or O and dopant
US4461820 *Feb 1, 1982Jul 24, 1984Canon Kabushiki KaishaAmorphous silicon electrophotographic image-forming member having an aluminum oxide coated substrate
US4464521Feb 8, 1983Aug 7, 1984Ashland Oil, Inc.Curable composition and use thereof
US4469527Dec 1, 1981Sep 4, 1984Tokyo UniversityMethod of making semiconductor MOSFET device by bombarding with radiation followed by beam-annealing
US4471042May 4, 1979Sep 11, 1984Canon Kabushiki KaishaModified by oxygen; high dark resistance; semiconductors
US4485146Jul 29, 1982Nov 27, 1984Asahi Glass Company LtdGlass body provided with an alkali diffusion-preventing silicon oxide layer
US4489782Dec 12, 1983Dec 25, 1984Atlantic Richfield CompanyViscous oil production using electrical current heating and lateral drain holes
US4490208Jul 1, 1982Dec 25, 1984Agency Of Industrial Science And TechnologyMethod of producing thin films of silicon
US4520380Oct 7, 1983May 28, 1985Sovonics Solar SystemsAmorphous semiconductors equivalent to crystalline semiconductors
US4549889May 31, 1983Oct 29, 1985Semiconductor Energy Laboratory Co., Ltd.Refining process of reactive gas for forming semiconductor layer
US4581476Dec 22, 1983Apr 8, 1986Semiconductor Energy Laboratory Co., Ltd.Non-single-crystal semiconductor laminate containing pin junction
US4582395Jul 30, 1981Apr 15, 1986Kabushiki Kaisha Suwa SeikoshaActive matrix assembly for a liquid crystal display device including an insulated-gate-transistor
US4591892Aug 22, 1983May 27, 1986Semiconductor Energy Laboratory Co., Ltd.Semiconductor photoelectric conversion device
US4681984Mar 10, 1986Jul 21, 1987Siemens AktiengesellschaftAging resistance
US4710786Jun 9, 1986Dec 1, 1987Ovshinsky Stanford RSilicon matrices with density reducing elements
US4742012Dec 30, 1986May 3, 1988Toa Nenryo Kogyo K.K.Method of making graded junction containing amorphous semiconductor device
US4758527May 5, 1987Jul 19, 1988Semiconductor Energy Laboratory Co., Ltd.Method of making semiconductor photo-electrically-sensitive device
US4766477Jul 11, 1986Aug 23, 1988Canon Kabushiki KaishaCarbon, sulfur, nitrogen, oxygen
US4843451Jul 29, 1988Jun 27, 1989Sanyo Electric Co., Ltd.Photovoltaic device with O and N doping
US4888305Mar 9, 1989Dec 19, 1989Semiconductor Energy Laboratory Co., Ltd.Method for photo annealing non-single crystalline semiconductor films
US4889783Nov 2, 1987Dec 26, 1989Semiconductor Energy Laboratory Co., Ltd.Printing member for electrostatic photocopying
US5043772May 7, 1986Aug 27, 1991Semiconductor Energy Laboratory Co., Ltd.Semiconductor photo-electrically-sensitive device
US5077223Nov 29, 1989Dec 31, 1991Semiconductor Energy Laboratory Co., Ltd.Forming doped non-single crystalline semiconductor
US5294555Jan 30, 1992Mar 15, 1994Seiko Epson CorporationSemiconductors
US5315132Dec 8, 1992May 24, 1994Semiconductor Energy Laboratory Co., Ltd.Semiconductors
US5349204Dec 7, 1993Sep 20, 1994Semiconductor Energy Laboratory, Co., Ltd.Semiconductor device
US5391893May 1, 1991Feb 21, 1995Semicoductor Energy Laboratory Co., Ltd.Nonsingle crystal semiconductor and a semiconductor device using such semiconductor
US5521400Nov 29, 1994May 28, 1996Semiconductor Energy Laboratory Co., Ltd.Semiconductor photoelectrically sensitive device with low sodium concentration
US5543636Jun 7, 1995Aug 6, 1996Semiconductor Energy Laboratory Co., Ltd.Insulated gate field effect transistor
EP0180781A2Oct 4, 1985May 14, 1986Fuji Electric Corporate Research And Development Ltd.Process for producing amorphous silicon solar cells and product produced thereby
GB2130008A Title not available
JP53152887A Title not available
JPH0696391A Title not available
JPS511389A Title not available
JPS5511329A Title not available
JPS5513939A Title not available
JPS5529154A Title not available
JPS5578524A Title not available
JPS5740940A Title not available
JPS5828873A Title not available
JPS5892218A Title not available
JPS5935423A Title not available
JPS5935488A Title not available
JPS54136274A Title not available
JPS54158190A Title not available
JPS56135968A Title not available
JPS57110356A Title not available
JPS57146561A Title not available
JPS57146562A Title not available
JPS57182546A Title not available
JPS57187972A Title not available
JPS57211078A Title not available
JPS58155774A Title not available
JPS59115574A Title not available
Non-Patent Citations
Reference
1A. Delahoy and R. Griffith, "Impurities Effects In a-Si:H Solar Cells Due to Air, Oxygen, Nitrogen, Phosphine, or Monochlorosilane in the Plasma", Journal of Applied Physics, vol. 52, No. 10, pp. 6337-6346 (1981).
2A. Delahoy and R. Griffith, Proceeding of the 15th IEEE Photovoltaics Specialists Conference, IEEE Press, pp. 704-712, 1981, "Impurity Effects In a-Si:H Solar Cells".
3A. Delahoy and R. Griffity, "Impurities Effects In a-Si:H Solar Cells Due to Air, Oxygen, Nitrogen, Phosphine, or Monochlorosilane in the Plasma", Journal of Applied Physics, vol. 52, No. 10, pp. 6337-6346 (1981).
4A. Delahoy, et al., "Impurity Effects in a-Si:H Solar Cells", IEEE Proceedings of the 15th Photovoltaic Specialists Conference, Kissimmee, Florida, pp. 704-712 (1981).
5A. Homyak et al., Delivering Hydrogen to Meet < 1 ppb Impurity Levels Without the use of Purifiers, Solid State Technology, Gas Handling and Delivery, Oct. 1995, 4 pages.
6A. Pecora et al., "Off-Current in Polycrystalline Silicon Thin Film Transistors: An Analysis of the Thermally Generated Component", Solid-State Electronics, vol. 38, No. 4, pp. 845-850, (1995).
7A. Yusa et al., Ultrahigh Purification of Silane for Semiconductor Silicon, Journal of the Electrochemical Society, vol. 122, No. 12, Dec. 1975, pp. 1700-1705.
8A.S. Grove, P. Lamond, et al.; Electro-Technology, p. 40-43, Published 1965; "Stable MOS Transistors".
9Amorphous Semiconductor, Technologies and Devices, 1982, Editor Y. Hamakawa, et al., pp. 194-198 North Holland Publishing Corporation [QC 611.8 A5J3].
10B. Ali Khan and R. Pandya, "Activation Energy of Source-Drain Current in Hydrogenated and Unhydrogenated Polysilicon Thin-Film Transistors" IEEE Transactions on Electron Devices, vol. 37, No. 7, Jul. 1990.
11B. Yurash and B.E. Deal; J. Electrochem. Soc., 15, 1191, Published 1968; "A Method for Determining Sodium Content of Semiconductor Processing Materials".
12B.E. Deal, Jap. J. Appl. Phys., 16(Suppl. 16-1), pp. 29-35, 1977; " Invited: New Developments in Materials and Processing Aspects of Silicon Device Technology".
13C. Magee and D. Carlson, "Investigation of the Hydrogen and Impurity Contents of Amorphous Silicon by Secondary Ion Mass Spectrometry", Solar Cells, vol. 2, pp. 365-376 (1980).
14C. Magee et al., Investigation of the Hydrogen and Impurity Contents of Amorphous Silicon by Secondary Ion Mass Spectrometry, Solar Cells, vol. 2, 1980, pp. 365-376.
15C.C. Tsai, "Impurities in Bulk a-Si:H, Silicon Nitride, and at the a-Si:H/Silicon Nitride Interface", Material Research Society Symposia Proceedings, vol. 33, pp. 297-300 (1984).
16D. Carlson, "Amorphous Thin Films for Terrestrial Solar Cells", D.E. Carlson, Journal of Vacuum Science Technology, vol. 20, No. 3, pp. 290-295 (Mar. 1982).
17D. Carlson, "The Effects of Impurities and Temperature on Amorphous Silicon Solar Cells", IEEE Technical Digest for the 1977 IEDM in Washington, D.C., pp. 214-217 (IEEE New York, 1977).
18D. Neamen, Semiconductor Physics and Devices, Irwin Press, 1992.
19D. Passoja et al., Some Aspects of the Structure-Properties Relationships Associated With Haze in SOS, Journal of Crystal Growth, vol. 58, 1982, pp. 44-52.
20D. Staebler, R. Crandall, and R. Williams, "Stability Test on p-i-n Amorphous Silicon Solar Cells", Conference Record of the 15th IEEE Photovoltaic Specialists Conference, 249-250, 1981.
21Declaration Of Robert Cote In Support of SEL's Motion For Summary Judgment Dismissing Samsung's Inequitable Conduct Defense To The '636 Patent.
22E.H. Nicollian and J.R. Brews, MOS (Metal-Oxide-Semiconductor) Physics and Technology, Chap. 5, "Control of Oxide Charges", pp. 754-775, 1982.
23E.H. Snow, A.S. Grove, B.E. Deal; J. Appl. Phys., vol. 36, No. 5, pp. 1664-1673, Published 1965, "Ion Transport Phenomena in Insulating Films".
24 *Fifth E.C., Photovoltaic Solar Energy Conference, Oct. 1983, Kavouri (Athens), Greece.*
25Friedel and Ladenburg, Annalen 143,124, 1967.
26G. Hetherington and L.W. Bell, Phys. Chem. Glasses, vol. 8, No. 5, pp. 206-208, Oct. 1967; "Letter to the Editor".
27G. Robertson, et al., Boron -Free Silicon Detectors, Final Report of Sep. 1984 to Jun. 1988, Wright Research and Development Center, Materials Laboratory, WRDC-TR-90-4079, Sep. 1990, pp. 121-131.
28G. Scilla and G. Ceaser, Xerox Corporation Reported, "Determination on Metallic Impurities in a-Si:H by SIMS" Surface and Interface Analysis, vol. 4, No. 6, 1982.
29H. Boyd, Non-Contaminating Gas Containment, Control, and Delivery Systems for VLSI-Class Wafer Fabrication, Microelectronic Manufacturing and Testing, Mar. 1984, pp. 1-6.
30H. Branz, "Hydrogen Collision Model of Light-Induced Metastability in Hydrogenated Amorphous Silicon", Solid State Communications, in Press, 9/97.
31H. Dersch, J. Stuke and J. Beichler; Phys. Stat. Sol. (b)105,265, 1981 " Electron Spin Resonance of Doped Glow-Discharge Amorphous Silicon".
32H. Tuan, "Amorphous Silicon Thin Film Transistor and its Applications to Large-Area Electronics", Materials Research Society Symposia Proceedings, vol. 33, pp. 247-257 (1984).
33Hirose, "Amorphous Silicon Material", Denshi Zairyou, Jan. 1981, pp. 56-58.
34J. Knights, et al., "Phys. Rev. Lett., 39, 712, 1977" pp 279-284 (1980) "Electronic and Structural Properties of Plasma-Deposited a-Si:O:H- The Story of O<SUB>2</SUB>".
35J. Knights, R. Street, and G. Lucovski, Journal of Non-Crystalline Solids, 35&36, 279-284, 1980.
36J. Leroueille, Physics Stat. Sol. (A)67, 177, 1981, "Influence of Carbon on Oxygen Behavior in Silicon".
37J. Maurits et al., Abstracts of the Electrochemical Society, 90-2, 1990.
38J. Maurits et al., The Effect of Polysilicon Impurities on Minority Carrier Lifetime in CZ Silicon Crystals, 22nd IEEE Photovoltaic Specialists Conference, Oct. 1991, pp. 309-314.
39J. Maurits, Advanced Silicon Materials Inc. 1997.
40J. Pankove, Hydrogenated Amorphous Silicon, vol. 21 A,B,C,D Semiconductors and Semimetals Series, Academic Press, 1984.
41J.E.A. Maurits, Problems and Solutions in the Preparation of SOS Wafers, Solid State Technoloty, Apr. 1977, 6 pages.
42J.E.A. Maurits, SOS Wafers-Some Comparisons to Silicon Wafers, IEEE Transactions on Electron Devices, vol. ED-25, No. 8, Aug. 1978, pp. 359-363.
43J.L. Briesacher et al., Gas Purification and Measurement at the PPT Level, J. Electrochem. Soc., vol. 138, No. 12, Dec. 1991, pp. 3717-3718 and 3723.
44J.R. Davis, Instabilities in MOS Devices, Chap. 4, "Mobile Ions", pp. 65-81, 1981.
45Japanese Patent Document 57-13777 with English translation published Jan. 23, 1982, Japan.
46Japanese Patent No. 54-136274 issued Oct. 23, 1979 to Hayafuji et al.
47Japanese Patent No. 55-29155 issued Mar. 1, 1980 to Yamazaki.
48Japanese Patent No. 56-4287 issued Jan. 17, 1981 to Carlson.
49Japanese Patent No. 56-45083 issued Apr. 24, 1981 to Carlson.
50Japanese Patent No. 56-64476 issued Jun. 1, 1981 to Allen et al.
51Japanese Patent No. 57-1272 issued Jan. 6, 1982 to Uchida et al.
52Japanese Patent No. 57-187972 isued Nov. 18, 1982 to Uchida et al.
53Japanese Patent No. 57-40940 issued Mar. 6, 1982 to Shibamata et al.
54Japanese Patent No. 58-92218 issued Jun. 1, 1983 to Yamazaki.
55K. Harii et al., "Self-Alignment Type a-Si:H TFT", 27p-L-16, Extended Abstract of the Japanese Applied Physics Society (Sep. 27, 1983).
56Kamei et al., "Deposition and Extensive Light Soaking of Highly Pure Hydrogenated Amorphous Silicon", pp. 2380-2382, Apr. 22, 1996.
57M. Hirose, In Hydrogenated Amorphous Silicon, Semiconductors and Semimetals Series, vol. 21, 1984.
58M. Stutzmann, et al., Phy. Rev. 32, pp 23, 1985, "Light-induced Metastable Defects In Hydrogenated Amorphous Silicon-A Systematic Study".
59Metheson Gases and Equipment Catalogue, 1992.
60Moller et al., low level baron doping and tight induced effects in amorphous silicon. IEEE photovoltaic specialist conference, San Diego, CA Sep. 27-30, 1982, Published Jan. 1983.
61P. Schmidt, Contamination-Free High Temperature Treatment of Silicon or Other Materials, J. Electrochem. Soc.: Solid-State Science and Technology, Jan. 1983, pp. 186-189.
62P. Vanier, et al., "New Features of the Temperature Dependence of Photoconductivity in Plasma-Deposited Hydrogenated Amorphous Silicon Alloys", Journal of Applied Physics, vol. 52, No. 8, pp. 5235-5242 (1981).
63P. Vanier, et al., "Study of Gap States in a-Si:H Alloys By Measurements of Photoconductivity and Spectral Response of MIS Solar Cells", American Institute of Physics, Proceedings of the International Conference on Tetrahedrally Bonded Amorphous Semicondutors, Carefree, Arizona, pp. 237-232 (1981).
64P.A. Taylor, Purification Techniques and Analytical Methods for Gaseous and Metallic Impurities in High-Purity Silane, Journal Crystal Growth, vol. 89, 1988, pp. 28-38.
65P.F. Schmidt and C.W. Pearce, J. Electrochem. Soc., 128, pp. 630-636, 1981; "A Neutron Activation Analysis Study of the Sources of Transition Group Metal Contamination in the Silicon Device Manufacturing Process".
66P.F. Schmidt, Solid-State Tech., 26(6), 147, 1983; "Furnace Contamination and its Remedies".
67Paesler et al., Phys. Rev. Lett., 41, 1492, 1978, "New Development in the Study of Amorphous Silicon Hydrogen Alloys: The Story of O".
68R. B. Swaroop, "Advances in Silicon Technology for the Semiconductor Industry", Solid State Technology, 1983, pp. 111-114.
69R. Coderman et al., Mass Spectrometric Studies of Impurities in Silane and Their Effects on the Electronic Properties of Hydrogenated Amorphous Silicon, J. Appl. Phys., vol. 54, No. 7, Jul. 1983, pp. 3987-3992.
70R. Colclaser, Wiley, "Microelectronics: Processing and Device Design", 1980.
71R. Corderman, et al., "Mass Spectrometric Studies of Impurities in Silane and Their Effects on the Electronic Properties of Hydrogenated Amorphous Silicon", Journal of Applied Phyusics, vol. 54, No. 7, pp. 3987-3992 (1983), submitted Sep., 1982.
72R. Crandall, D. Carlson, and H. Weakleam, Applied Physics Letters., vol. 44, pp. 200-201, 1984 " Role of Carbon in Hydrogenated Amorphous Silicon Solar Cell Degradation".
73R. Kriegler, et al., "The Effect of HCl and Cl<SUB>2 </SUB>on the Thermal Oxidation of Silicon", Journal of Electrochemical Society: Solid-State Science and Technology, p. 388-392 (1972).
74R.J. Kriegler et al., J. Electrochem. Soc., 119, 388, 1972; "The Effect of HCL and CL<SUB>2 </SUB>on the Thermal Oxidation of Silicon".
75R.J. Kriegler, Proc. Semiconductor Silicon 1973, The Electrochemical Society, Princeton, N.J., p. 363, 1973.
76R.P. Roberge et al., Gaseous Impurity Effects in Silicon Epitaxy, Semiconductor International, Jan. 1987, pp. 77-81.
77R.W. Lee, J. Chem. Phys., vol. 38, No. 2, pp. 448-455, 1963; "Diffusin of Hydrogen in Natural and Synthetic Fused Quartz".
78S. Guha, Conference Record of the 25th Photovoltaics Specialists Conference, pp. 1017-1022, IEEE Press, 1996, "Amorphous Silicon Alloy Solar Cells and Modules-Opportunities and Challenges".
79S. Mayo and W.H. Evans, J. Electrochem. Soc., 124, pp. 780-785, 1977; "Development of Sodium Contamination in Semiconductor Oxidation Atmospheres at 1000 C.".
80S. Mayo, J. Appl. Phys., 47, 4012, 1976.
81S. Sze, "Physics of Semiconductor Devices", Div. of John Wiley & Sons, 1981.
82S. Sze, "Physics of Semiconductor Devices", John Wiley & Sons, pp. 567-571 (1969).
83S.K. Iya, Production of Ultra-High-Purity Polycrystalline Silicon, Journal of Crystal Growth, vol. 75, 1986, pp. 88-90.
84Scilla et al., Determination of Metallic Impurities in a-Si:H by SIMS, Surface and Interface Analysis, vol. 4, No. 6, 1982, pp. 253-254.
85Silane-Ultraplus (TM) II SiH<SUB>4</SUB>, Linde Union Carbide Specialty Gases Product Information, May 10, 1990, 2 pages.
86Silicon on Sapphire, Update II, Union Carbide, Bulletin 1980, F-EMG-5801-4M, 4 pages.
87Silicon Source Gases for Chemical Vapor Deposition, Solid State Technology, May 1989, pp. 143-147.
88Szydlo et al., "High Current Post-Hydrogenated Chemical Vapor Deposited Amorphous Silicon PIN Diodes", pp. 988-990, Jun. 1, 1992.
89T. Deacon, Silicon Epitaxy: An Overview, Microelectronic Manufacturing and Testing, Sep. 1984, pp. 89-92.
90T. Takahashi et al., Instrumentation, 47, 3, 1976.
91T. Takaishi, et al., "Changes in the Sieving Action and Thermal Stability of Zeolite a Produced by Ion-Exchange", Journal of the Chemical Society: Faraday Transactions I, part. 1, pp. 97-105 (1975).
92T.J. Donahue et al., PECVD of Silicon Epitaxial Layers, Semiconductor International, Aug. 1985, pp. 142-146.
93The prior work of C.C. Tsai as evidenced by the document: C.C. Tsai, et al., "Amorphous Si Prepared in a UHV Plasma Deposition System", Journal on Non-Crystalline Solids, Proceedings of the Tenth International Conference on Amorphous and Liquid Semiconductors in Tokyo, vols. 59&60, pp. 731-734 (1983).
94Tsai et al., "Amorphous Si Prepared in a UHV Plasma Deposition System", Journal of Non-Crystalline Solids, Proceedings of the Tenth International Conference on Amorphous and Liquid Semiconductors in Tokyo, vols. 59 & 60, p. 731-734 (1983).
95Uchida et al., "Large Area Amorphous Silicon Solar Cell", Denshi Zairyou, Jan. 1980, pp. 75-81.
96W. Beyer and R. Fisher, Appl. Phys. Lett., 31, 850, 1977.
97W. Spear, et al., "Doping of Amorphous Silicon By Alkali Ion Implantations", Philosophical Magazine B, vol. 39, No. 2, pp. 159-165 (1979).
98Y. Matsushita et al., Jap. J. Appl. Phys. 19. L101, 1980, "A Study on Thermally Induced Microdefects in Czochralski-Grown Silicon Crystals: Dependence on Annealing Temperature and Starting Materials".
99Yusa, et al., "Ultrahigh Purification of Silane for Semiconductor Silicon", Journal of the Electrochemical Society: Solid-State Science and Technology, vol. 122, No. 12, pp. 1700-1705 (1975).
100Z. Hirose, "Amorphous Silicon", Nikkei Electronics-Special Issue, pp. 163-179 (Dec. 20, 1982).
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Classifications
U.S. Classification438/87, 136/258, 438/96, 257/E31.014, 257/E31.042, 257/E31.012, 136/255, 438/931
International ClassificationH01L31/075, H01L31/0288, H01L31/028, H01L31/0392, H01L31/0376
Cooperative ClassificationY02E10/547, H01L31/077, H01L31/03762, H01L31/03921, H01L31/0288, H01L31/028, Y02E10/548, H01L31/075
European ClassificationH01L31/077, H01L31/028, H01L31/0288, H01L31/0376B, H01L31/0392B, H01L31/075