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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0. 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 5×1019 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.
5. A manufacturing method as in
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 5×1019 atoms/cm3,
wherein the reduction of the oxygen concentration is effected by passing said process gas through a molecular sieve or zeolite which adsorbs oxygen.
7. A method of claim 6 5, wherein said process gas is filtered in advance of introduction into said reaction chamber.
0. 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 4×1019 atoms/cm3.
10. A manufacturing method as in
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 4×1018 atoms/cm3;
wherein the reduction of the carbon concentration is effected by passing said process gas through a molecular sieve or zeolite which adsorbs carbon.
0. 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 5×1015 atoms/cm3.
0. 12. A method as in
0. 13. A manufacturing method as in
14. A method as in claims 1, 8, or 11 where 5 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 where 5 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 where 5 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.
18. A method as in claims 1, 8, or 11 where 5 or 10, wherein said impurity is boron and the boron concentration at said interface between the p-type and intrinsic layers is 2×1015 to 2×1017 atoms/cm3.
19. A method as in claims 1, 8, or 11 where 5 or 10, wherein said first layer comprises p-type, non-single crystalline SixC1-x (0<x<1) and said impurity comprises boron.
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abovesaid above 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 5×1019 atoms/cm3 as low as 5×1018 atoms/cm3, and/or carbon at a concentration level less than 4×1019 4×1018 atoms/cm3 as low as 4×1015 atoms/cm3, and/or phosphorus at a concentration at least as low as 5×1015 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 1×1019 to 6×1020 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
With the photoelectric conversion device shown in
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
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
In the case of the photoelectric conversion device of a present invention shown in
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
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
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
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
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.
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