JPH10163509A - I-iii-vi compound semiconductor and thin-film solar battery using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase the photocurrent output of a thin-film solar battery by heat-treating a precursor formed by successively laminating a first metallic layer, a first group III-VI element compound layer, and a second group III-VI element compound layer upon another on a substrate, containing an alkali metal to a prescribed temperature in a prescribed atmosphere. SOLUTION: A precursor has a first metallic layer 12, formed on a substrate 13 containing an alkali metal, a first group III-VI element compound layer 11 which is formed on the metallic layer 12 and contains a group III-VI element compound, and a second group III-VI element compound layer 20 which is formed on the layer 11 and contains a group III-VI element compound. A I-III-VI compound semiconductor 14 is formed by heat-treating the precursor to a prescribed temperature in a prescribed atmosphere. The heat-treatment is seleniding treatment in which selenium is injected into the precursor, by heating the precursor in the atmosphere of a selenium gaseous phase.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device, and more particularly to a precursor of a group I-III-VI compound semiconductor and a thin-film solar cell manufactured using the same.

[0002]

2. Description of the Related Art FIG. 6 is a view for explaining a first conventional example, in which a precursor using solid-phase selenization technology and an I-III-VI group compound semiconductor manufactured using the same are used. It is sectional drawing for demonstrating.

The first of this kind of I-III-VI compound semiconductors
As a conventional example, for example, Japanese Unexamined Patent Application Publication No. 1-231313 (Title of Invention: Manufacturing method of semiconductor film, filing date:
(November 28, 1988) (see FIG. 6).

In a precursor 6 according to a first conventional example, a molybdenum (Mo) metal electrode layer 2, a copper layer 3, an indium (In) layer 4, and a selenium (Se) layer 5 are laminated on a glass substrate 1 in this order. It was composed.

[0005] The precursor 6 having such a laminated structure
By using a solid-phase selenization method of heat-treating Cu
I-III-VI group compound semiconductors 7, 2 such as InGaSe2 were produced.

FIG. 7 is a view for explaining the second conventional example, and illustrates a precursor using a gas phase selenization method and an I-III-VI group compound semiconductor manufactured using the precursor. FIG.

A second method for producing an I-III-VI group compound semiconductor using a vapor-phase selenization technique in which a precursor of Cu-In is reacted in a selenium vapor phase such as Se or H2Se.
FIG. 7 shows a conventional example.

The precursor in the second prior art example is configured such that a molybdenum (Mo) metal electrode layer 2, a copper (Cu) layer 3, and an indium (In) layer 4 are laminated on a glass substrate 1 in this order. .

The precursor having such a laminated structure is prepared by using the vapor-phase selenization method described above to obtain CuI.
I-III-VI group compound semiconductors 7, 2 such as nGaSe2 were produced.

FIG. 8A shows a CuI using the solid-state selenization technique of the first conventional example or the gas-phase selenization technique of the second conventional example.
I-III-V prepared using various precursors of nSe2 series
FIG. 8B is a chart for explaining the relationship between the crystal grain size and the sodium content in the group I-based compound semiconductor, and FIG.
Are Cu (In, Ga) Se2 based precursors using the solid-phase selenization technology of the first conventional example or the gas-phase selenization technology of the second conventional example, and I-III- fabricated using the precursors. 6 is a table for explaining a relationship between a crystal grain size and a sodium content in a group VI compound semiconductor. .

As shown in FIG. 8 (a), any of the CuInSe2 based precursors using the solid-phase selenization technique of the first conventional example or the vapor-phase selenization technique of the second conventional example is used. Even in I-III-VI group compound semiconductors,
A crystal grain size of 1 μm or less was obtained.

[0012] Similarly, as shown in FIG.
In any of the I-III-VI group compound semiconductors prepared using various precursors of Cu (In, Ga) Se2 based on the conventional solid-phase selenization technology or the second conventional gas-phase selenization technology. Also, a crystal grain size of 0.5 μm or less was obtained.

[0013]

However, in the first or second prior art I-III-VI group compound semiconductors, a CIS semiconductor such as CuInSe2 or Cu (In, Ga) Se2 is used. No matter which precursor of the system is used, only a crystal grain size of about 1 to 0.5 μm can be obtained, so that it is difficult to realize a high photoelectric conversion efficiency exceeding 10%, and the photo carrier has a long life. There was a technical problem that it was difficult to convert.

In other words, it is difficult to extract a large photocurrent from such an I-III-VI group compound semiconductor, and as a result, a thin-film solar cell fabricated using such an I-III-VI group compound semiconductor can be obtained. There was a technical problem that it was difficult to extract a large photocurrent with a battery.

On the other hand, CuInSe, which is a CIS semiconductor,
In order to increase the crystal grain size in either the 2-system or Cu (In, Ga) Se2 system precursor, an alkali metal such as sodium is doped into the precursor, and the precursor after the doping is selenized. Accordingly, it is known that the crystal grain size can be increased.

However, an alkali metal such as sodium, which is excluded as a heavy metal impurity in a semiconductor process, can be locally injected or diffused into a predetermined position by a predetermined amount with high precision, and does not adversely affect other processes as an impurity. There was a need for a precursor structure that could be used.

An object of the present invention is to solve such conventional problems, and in particular, to a substrate or an alkali supply layer containing an alkali metal, a first group III-VI element compound layer (or a single group VI element). Layer) and a second III-VI element compound layer (or a second metal layer) and a precursor (laminated in this order) is subjected to heat treatment (selenization treatment) in which the precursor is heated at a predetermined temperature in a predetermined atmosphere. Formed by
Alkali metals such as sodium, which are excluded as heavy metal impurities in the semiconductor process, are locally and precisely doped by a predetermined amount by a predetermined amount according to the I-III-VI group compound semiconductor, and used in other processes. Implementing a precursor structure that can prevent adverse effects as impurities,
As a result, it is an object of the present invention to increase the crystal grain size in any of the CuInSe 2 -based or Cu (In, Ga) Se 2 -based precursors that are CIS-based semiconductors.

Further, due to the fact that a large crystal grain size is obtained, high photoelectric conversion efficiency exceeding 10% is achieved,
It is another object of the present invention to extend the life of a photocarrier and, as a result, to increase the output of a photocurrent.

Another object of the present invention is to increase the output of photocurrent in a thin-film solar cell by manufacturing a thin-film solar cell using such an I-III-VI group compound semiconductor.

[0020]

According to a first aspect of the present invention, there is provided an I-III-VI group compound semiconductor comprising a first metal layer formed on a substrate containing an alkali metal.
A first III-VI element compound layer 11 having a III-VI element compound formed on the first metal layer 12;
Performing a heat treatment of heating a precursor 24 having a second III-VI element compound layer 20 having a III-VI element compound formed on the I-VI element compound layer 11 at a predetermined temperature in a predetermined atmosphere; The I-III-VI group compound semiconductor 14 is characterized by being formed by

According to the first aspect of the present invention, a Group III-VI element compound which is highly reactive to an alkali metal such as sodium (element symbol: Na) excluded as a heavy metal impurity in a semiconductor process. Since the layer 11 and the second group III-VI element compound layer 20 can be arranged in the order of high reactivity near the substrate 13 containing an alkali metal, the alkali metal can be locally and precisely deposited at a predetermined position by a predetermined amount. Thus, doping can be performed by heat treatment. Furthermore,
As long as no heat treatment is applied, an effect is obtained that the structure of the precursor 24 can be realized in which other processes are not adversely affected as impurities.

As a result, CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to a second aspect of the present invention, there is provided an I-III-VI group compound semiconductor, comprising a first metal layer formed on a substrate containing an alkali metal and a first metal layer formed on the substrate.
II-III-VI compound formed on II-III
A precursor 24 having a group VI element compound layer 11 and a second metal layer 16 having a copper element (element symbol: Cu) formed on the first group III-VI element compound layer 11 is placed in a predetermined atmosphere at a predetermined temperature. An I-III-VI group compound semiconductor 14 formed by performing a heat treatment of heating.

According to the second aspect of the present invention, the first III-VI group element compound layer 11 having a high reactivity with an alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process is made of an alkali metal. Since it can be arranged in the vicinity of the containing substrate 13, it becomes possible to dope the alkali metal from the substrate 13 with high accuracy by a predetermined amount locally at a predetermined position. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, CIS based semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

In addition, since a large crystal grain size is obtained, a high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to a third aspect of the present invention, there is provided an I-III-VI group compound semiconductor 14, wherein the first metal layer 12 and the first metal layer 1 are formed on a substrate 13 containing an alkali metal.
A precursor 2 having a group VI element single layer 15 formed on the second group 2 and a first III-VI element compound layer 11 having a group III-VI element formed on the group VI element single layer 15
4 is a group I-III-VI group compound semiconductor 14 formed by performing a heat treatment of heating No. 4 in a predetermined atmosphere at a predetermined temperature.

According to the third aspect of the present invention, a group VI elemental element layer 1 having high reactivity with an alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process.
5 or the first III-VI group element compound layer 11 can be arranged in the order of high reactivity near the substrate 13 containing an alkali metal. Doping treatment can be performed by the heat treatment. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, CuIn which is a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

In addition, since a large crystal grain size is obtained, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to a fourth aspect of the present invention, there is provided an I-III-VI group compound semiconductor 14, wherein the first metal layer 12 and the first metal layer 1 formed on a substrate 13 containing an alkali metal.
2 and a second metal layer 16 containing a copper element formed on the group VI element simple layer 15.
The I-III-VI group compound semiconductor 14 is formed by performing a heat treatment of heating the precursor 24 having a predetermined temperature and a predetermined temperature in a predetermined atmosphere.

According to the fourth aspect of the present invention, the group VI elemental element layer 15 most reactive to an alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process contains an alkali metal. Since it can be arranged in the vicinity of the substrate 13, the alkali metal can be locally doped at a predetermined position by a predetermined amount with high accuracy by heat treatment. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, CIS based semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to a fifth aspect of the present invention, there is provided an I-III-VI group compound semiconductor 14 comprising an alkali supply layer 26 formed on a substrate 13 and a first supply layer 26 formed on the alkali supply layer 26. Metal layer 12 and formed on the first metal layer 12
A first III-VI element compound layer 11 having a III-VI element compound and a second III-VI element compound layer 20 having a III-VI element compound formed on the first III-VI element compound layer 11 The I-III-VI group compound semiconductor 14 is formed by performing a heat treatment of heating the precursor 24 having a predetermined temperature and a predetermined temperature in a predetermined atmosphere.

According to the fifth aspect of the present invention, the first III-VI element compound layer 11 or the second III-VI element compound layer which is highly reactive to alkali metals such as sodium which are excluded as heavy metal impurities in a semiconductor process. Since the group VI element compound layer 20 can be arranged in the order of high reactivity in the vicinity of the alkali supply layer 26 containing an alkali metal, the alkali metal is locally heat-treated from the alkali supply layer 26 by a predetermined amount at a predetermined position. Allows doping treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 degrees. A substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing a crystal grain system, a substrate 13 having a linear expansion coefficient close to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, the CuIn semiconductor, CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to a sixth aspect of the present invention, there is provided an I-III-VI compound semiconductor 14, wherein the alkali supply layer 26 is formed on the substrate 13 and the first metal is formed on the alkali supply layer 26. Layer 12 and the III- layer formed on the first metal layer 12.
First III-VI element compound layer 11 having group VI element compound
A precursor 2 having a copper element and a second metal layer 16 formed on the first group III-VI element compound layer 11
4 is a group I-III-VI group compound semiconductor 14 formed by performing a heat treatment of heating No. 4 in a predetermined atmosphere at a predetermined temperature.

According to the sixth aspect of the present invention, the first group III-VI element compound layer 11 having a high reactivity with an alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process is made of an alkali metal. Since it can be arranged in the vicinity of the contained alkali supply layer 26, it becomes possible to dope alkali metal from the alkali supply layer 26 locally at a predetermined position with high accuracy by a predetermined amount by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the alkali supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 ° C. A substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing a crystal grain system, a substrate 13 having a linear expansion coefficient close to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, CuIn which is a CIS based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to a seventh aspect of the present invention, there is provided an I-III-VI compound semiconductor 14, wherein the alkali supply layer 26 is formed on the substrate 13 and the first metal is formed on the alkali supply layer 26. A layer 12, a group VI element simple layer 15 formed on the first metal layer 12, and a first group III-VI element compound layer 11 having a group III-VI element compound formed on the group VI element single layer 15 The I-III-VI group compound semiconductor 14 is formed by performing a heat treatment of heating the precursor 24 having a predetermined temperature and a predetermined temperature in a predetermined atmosphere.

According to the seventh aspect of the present invention, the group VI elemental element layer 1 having a high reactivity with an alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process.
5 or the first III-VI element compound layer 11 can be arranged in the order of high reactivity in the vicinity of the alkali supply layer 26 containing an alkali metal. The doping process can be performed from the supply layer 26 by the heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer 26 that can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 degrees. A substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing a crystal grain system, a substrate 13 having a linear expansion coefficient close to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, the CuIn semiconductor, CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, a high photoelectric conversion efficiency of more than 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

The invention according to claim 8 is the I-III-VI group compound semiconductor 14, wherein the alkali supply layer 26 is formed on the substrate 13 and the first metal is formed on the alkali supply layer 26. A precursor 24 having a layer 12, a group VI element simple layer 15 formed on the first metal layer 12 and a second metal layer 16 containing a copper element formed on the group VI element simple layer 15 is exposed to a predetermined atmosphere. Formed by performing a heat treatment of heating at a predetermined temperature within the I-III-
Group VI compound semiconductor 14.

According to the eighth aspect of the present invention, the group VI element simple substance layer 15 most reactive to an alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process contains an alkali metal. Since it can be arranged in the vicinity of the alkali supply layer 26, it becomes possible to dope an alkali metal from the alkali supply layer 26 locally at a predetermined position by a predetermined amount with high accuracy by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the alkali supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 ° C. A substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing a crystal grain system, a substrate 13 having a linear expansion coefficient close to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, CuIn which is a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to a ninth aspect of the present invention, there is provided the I-III-VI group compound semiconductor 14, wherein the first
An alkali supply layer 26 formed on the first metal layer 12 in a state containing the metal layer 12 and the alkali metal, and a first group III-VI having a group III-VI element compound formed on the alkali supply layer 26 A precursor 24 having an element compound layer 11 and a second III-VI element compound layer 20 having a III-VI element compound formed on the first III-VI element compound layer 11 is heated at a predetermined temperature and in a predetermined atmosphere. I- characterized by being formed by performing a heat treatment of heating
III-VI group compound semiconductor 14.

According to the ninth aspect of the present invention, the first III-VI element compound layer 11 and the second III-VI element compound layer 11 which are highly reactive to alkali metals such as sodium which are excluded as heavy metal impurities in a semiconductor process. Since the group VI element compound layer 20 can be arranged in the order of high reactivity in the vicinity of the alkali supply layer 26 containing an alkali metal, the alkali metal is locally heat-treated from the alkali supply layer 26 by a predetermined amount at a predetermined position. Allows doping treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 degrees. A substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing a crystal grain system, a substrate 13 having a linear expansion coefficient close to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, CuIn which is a CIS based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to a tenth aspect of the present invention, there is provided the I-III-VI group compound semiconductor 14, wherein the first metal layer 12 formed on the substrate 13 and the first metal layer 12 contain the alkali metal.
The alkali supply layer 26 formed on the metal layer 12, the first III-VI element compound layer 11 having a III-VI element compound formed on the alkali supply layer 26, and the first III-VI
Second element having a copper element formed on group III element compound layer 11
I-III-VI group compound semiconductor 1 formed by performing a heat treatment of heating precursor 24 having metal layer 16 at a predetermined temperature in a predetermined atmosphere.
4.

According to the tenth aspect of the present invention, the first III-VI group element compound layer 11 having a high reactivity with an alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process is made of an alkali metal. Since it can be arranged in the vicinity of the contained alkali supply layer 26, the alkali metal can be locally and precisely placed at a predetermined position by a predetermined amount.
Thus, doping can be performed by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the alkali supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 ° C. A substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing a crystal grain system, a substrate 13 having a linear expansion coefficient close to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, CuIn which is a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

The invention according to claim 11 is the I-III-VI group compound semiconductor 14, wherein the first metal layer 12 formed on the substrate 13 and the first metal layer 12 containing the alkali metal are contained.
It has an alkali supply layer 26 formed on the metal layer 12, a group VI element single layer 15 formed on the alkali supply layer 26, and a group III-VI element compound formed on the group VI element single layer 15. I-III-VI compound semiconductor 14 formed by performing a heat treatment of heating precursor 24 having first III-VI element compound layer 11 at a predetermined temperature in a predetermined atmosphere. It is.

According to the eleventh aspect, the group VI element single layer 15 and the first group III-VI element which are highly reactive to alkali metals such as sodium which are excluded as heavy metal impurities in a semiconductor process. Since the compound layer 11 can be arranged in the order of high reactivity in the vicinity of the alkali supply layer 26 containing the alkali metal, the alkali metal is locally and precisely doped at a predetermined position by a predetermined amount from the alkali supply layer 26 by heat treatment. Be able to process.

Furthermore, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

Further, by providing the alkali supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 ° C. A substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing a crystal grain system, a substrate 13 having a linear expansion coefficient close to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, CuIn as a CIS semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to a twelfth aspect of the present invention, there is provided an I-III-VI group compound semiconductor 14, wherein the first metal layer 12 formed on the substrate 13 and the first metal layer 12 containing the alkali metal are contained.
The alkali supply layer 26 formed on the metal layer 12, the group VI element single layer 15 formed on the alkali supply layer 26, and the second metal layer having a copper element formed on the group VI element single layer 15 16. The I-III-VI group compound semiconductor 14 formed by performing a heat treatment of heating the precursor 24 having a temperature of 16 in a predetermined atmosphere at a predetermined temperature.

According to the twelfth aspect of the present invention, the group VI elemental element layer 15 most reactive to an alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process contains an alkali metal. Alkali supply layer 26
, The doping treatment of the alkali metal from the alkali supply layer 26 by a heat treatment can be locally performed at a predetermined position and precisely by a predetermined amount.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the alkali supply layer 26 that can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to the heat treatment requiring a process temperature of about 600 degrees. A substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing a crystal grain system, a substrate 13 having a linear expansion coefficient close to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, CuIn which is a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to a thirteenth aspect of the present invention, there is provided an I-III-VI group compound semiconductor according to any one of the first to twelfth aspects.
4. In the I-III-VI group compound semiconductor 14, the alkali metal is sodium.

According to the thirteenth aspect of the present invention, in addition to the effect of any one of the first to twelfth aspects, the most reactive to sodium which is eliminated as a heavy metal impurity in a semiconductor process. Group element element layer 15 rich in oxygen can be arranged near the alkali-containing layer 26 containing sodium, so that sodium can be doped from the alkali-supply layer 26 locally at a predetermined position by a predetermined amount with high accuracy by heat treatment. become.

Furthermore, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, CuIn which is a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to a fourteenth aspect of the present invention, there is provided an I-III-VI group compound semiconductor according to any one of the first to thirteenth aspects.
4, the group VI element is selenium (element symbol: S
e), sulfur (element symbol: S), or tellurium (element symbol: Te).

According to the fourteenth aspect of the present invention, in addition to the effects of any one of the first to thirteenth aspects, the use of a Group VI element such as selenium, sulfur, or tellurium provides This has the effect of achieving high photocarrier generation efficiency. In particular, selenium and its compounds have the effect that a highly crystalline I-III-VI group compound semiconductor thin film (sodium-containing CIS thin film) can be easily formed.

According to a fifteenth aspect of the present invention, there is provided an I-III-VI group compound semiconductor according to any one of the first to thirteenth aspects.
4. The I-III-VI compound semiconductor according to 4, wherein the group III element is gallium or indium.
4.

According to the fifteenth aspect of the present invention, in addition to the effects of any one of the first to thirteenth aspects, gallium (element symbol: Ga) or indium (element symbol: I
By using a group III element such as n), there is an effect that a high generation efficiency of photocarriers can be realized.

Further, gallium or indium or a compound thereof has an effect that a thin film of a group I-III-VI compound semiconductor having high crystallinity (a CIS thin film containing sodium) can be easily formed.

The invention according to claim 16 is the first invention.
2, 5, 6, 7, 9, 10, 11, 12, 13, 14,
Or in the I-III-VI group compound semiconductor 14 according to item 15, wherein the first III-VI element compound layer 11 is formed of InxSe (1-
x), and the second III-VI element compound layer 20 has G
An I-III-VI group compound semiconductor 14 having axSe (1-x).

According to the invention of claim 16, according to claims 1, 2, 5, 6, 7, 9, 10, 11, 12, 13, 1
In addition to the effects described in 4 or 15, InxSe (1-x) (0 ≦ x ≦), which is highly reactive with alkali metals such as sodium which are excluded as heavy metal impurities in a semiconductor process.
1) and GaxSe (1-x) (0 ≦ x ≦ 1) can be arranged in the order of high reactivity near the alkali supply layer 26 containing alkali metal and the substrate 13, so that they are locally located at predetermined positions. The doping treatment of the alkali metal from the alkali supply layer 26 by the heat treatment can be performed with high accuracy only by the quantitative determination.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

As a result, CuIn, which is a CIS semiconductor,
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

Further, by using a group III compound such as InxSe (1-x) or GaxSe (1-x), high photocarrier generation efficiency can be realized, and further, high crystallinity I-III The effect is that a group-VI compound semiconductor thin film (sodium-containing CIS thin film) can be easily formed.

The invention described in claim 17 is based on claim 1,
2, 5, 6, 7, 9, 10, 11, 12, 13, 14,
Or the I-III-VI group compound semiconductor 14 described in 15 or 15, wherein the first III-VI element compound layer 11 is GaxSe (1-
x), and the second III-VI element compound layer 20 has I
An I-III-VI group compound semiconductor 14 having nxSe (1-x).

According to the seventeenth aspect, the same effect as that of the sixteenth aspect can be obtained.

The invention described in claim 18 is the third invention.
I-II according to any one of 4, 7, 8, 11, or 12
In the I-VI group compound semiconductor 14, the group VI element single layer 15 is a layer formed using selenium element alone.

According to the eighteenth aspect of the invention, in addition to the effects of any one of the third, fourth, seventh, eighth, eleventh and twelfth aspects, in addition to being excluded as heavy metal impurities in a semiconductor process. Since the elemental selenium element, which is most reactive to an alkali metal such as sodium, can be arranged near the alkali supply layer 26 containing the alkali metal or the substrate 13.
Alkali metal can be doped from the alkali supply layer 26 by a heat treatment locally and precisely by a predetermined amount at a predetermined position.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

As a result, CuIn as a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

The invention according to claim 19 provides the I-III-VI group compound semiconductor 1 according to any one of claims 1 to 18.
4, the first metal layer 12 is made of molybdenum (element symbol: Mo), tungsten (element symbol: W), chromium (element symbol: Cr), polysilicon (SiO2), metal silicide, or aluminum (element symbol: Al-III-VI compound semiconductor 14 characterized by being a layer formed using Al).

The metal silicide of the present invention is
It means TiSi2, MoSi2, WSi2 and the like.

According to the nineteenth aspect of the present invention, in addition to the effect of any one of the first to eighteenth aspects, in addition to
Metal that has a high melting point,
A metal having a lattice constant or plane orientation capable of increasing the crystal grain system, and a coefficient of linear expansion of the substrate 13, the group VI element simple layer 15, the second
There is an effect that a metal or the like similar to the group III-VI element compound layer 20 can be used.

As a result, CuIn as a CIS based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

Further, the first metal layer (ie, the molybdenum metal layer) 12 containing a high melting point metal such as molybdenum, tungsten, chromium, etc., comprises a substrate 13, a first group III-VI element compound layer (selenium compound layer) 11, It is excellent in adhesion between the film of the group VI element simple substance layer 15 and the like, and does not cause peeling or cracking of the film even when the precursor 24 is exposed to a high temperature process. Can be formed.

Aluminum, which has the second highest conductivity next to noble metals, is a suitable amount of wiring material for a low-temperature process using CVD or the like.

Polysilicon and metal silicide commonly used in an LSI process have a suitable wiring material amount for a low-temperature process using CVD or the like. The use of such polysilicon or metal silicide for the first metal layer 12 makes it possible to use a Si semiconductor device or a GaAs semiconductor device.
I-III-VI group compound semiconductor (sodium-containing CIS layer)
14 can be connected using a conventional semiconductor process.
In other words, a process for fabricating an I-III-VI group compound semiconductor (sodium-containing CIS) 14 can be included in a process for fabricating an integrated circuit using Si or GaAs, and as a result, I-III-VI group compound semiconductor (sodium-containing CIS) 14 as a photoelectric conversion means
OEIC (Opto-Electronic Integrated Cir
cuit: an opto-electronic integrated circuit).

According to a twentieth aspect of the present invention, there is provided an I-III-VI group compound semiconductor according to any one of the first to nineteenth aspects.
4, wherein the first metal layer 12 is a molybdenum layer having a thickness of 1 to 2 μm.
Group VI compound semiconductor 14.

According to the twentieth aspect of the present invention, in addition to the effects of any one of the first to nineteenth aspects, in addition to the effects of alkali metals such as sodium which are excluded as heavy metal impurities in a semiconductor process. The most reactive group VI element simple substance layer 15 is formed into an alkali supply layer 26 containing an alkali metal.
, The doping process can be performed efficiently and controllably with the alkali metal from the alkali supply layer 26 through the molybdenum layer through the molybdenum layer through the molybdenum layer from the alkali supply layer 26 with high precision and locally at a predetermined position.

Further, by providing a molybdenum layer having a thickness of about 1 to 2 μm, it is possible to realize a structure of the precursor 24 that can prevent other processes from being adversely affected as impurities unless heat treatment is applied. This has the effect.

In addition, there is an effect that sufficient strength can be maintained for heat treatment requiring a process temperature of about 600 degrees.

As a result, CuIn as a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

[0138] According to a twenty-first aspect of the present invention, in the I-III-VI group compound semiconductor according to any one of the sixteenth to twentieth aspects, the heat treatment is performed in a selenium vapor atmosphere in the presence of the precursor. Is a selenization treatment of injecting selenium into the precursor 24 by heating the compound semiconductor.

According to the twenty-first aspect of the present invention, in addition to the effects of any one of the sixteenth to twentieth aspects, in addition to the effect of the selenium having a sufficient doping amount as a dopant, the precursor 2
4 and has an effect that a selenium-rich I-III-VI group compound semiconductor 14 can be obtained.

According to a twenty-second aspect of the present invention, in the I-III-VI group compound semiconductor according to the twenty-first aspect, instead of the selenization treatment, selenium is ionized and the ionized selenium and the selenium are combined. I-III-VI group compound semiconductor 14 characterized by using an ion implantation process in which a predetermined acceleration voltage is applied between the precursor 24 and the accelerated selenium ions are implanted into the precursor 24.
It is.

According to the twenty-second aspect of the present invention, in addition to the effect of the twenty-first aspect, by controlling the acceleration voltage, a predetermined amount of selenium having a sufficient doping amount as a dopant in the precursor 24 can be obtained. Selenium-rich high-quality I-III-VI
This has the effect that the group-based compound semiconductor 14 can be obtained.

According to a twenty-third aspect of the present invention, there is provided the I-III-VI group compound semiconductor 1 according to the first aspect.
4, a p-type semiconductor layer 32 using the I-III-VI group compound semiconductor 14 as a photocarrier generation layer, and at least the first type for extracting the photocarriers as a photocurrent. This is a thin-film solar cell 30 having an electrode 34 using one metal layer 12. .

According to the twenty-third aspect of the present invention, in addition to the effects of the first aspect, the CIS
Based semiconductors such as CuInSe2 or Cu (In, G
a) The crystal grain size can be increased with any of the precursors 24 of the Se2 series, and further, since a large crystal grain size can be obtained, high photoelectric conversion efficiency exceeding 10% can be achieved. As a result, the life of the photocarrier can be prolonged, and as a result, the photocurrent of the thin-film solar cell 30 can be increased in output.

[0144]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A first embodiment of an I-III-VI group compound semiconductor 14 will be described below before describing various embodiments with reference to the drawings.

FIG. 1A is a cross-sectional view for explaining the basic structure of a precursor 24 having a first III-VI group compound layer 11 and a second III-VI group compound layer 20.
FIG. 1B is a cross-sectional view for explaining the basic configuration of the I-III-VI group compound semiconductor 14 manufactured using the precursor 24 of FIG.

As shown in FIG. 1A, the precursor 24 includes a first metal layer 12 formed on a substrate 13 containing an alkali metal and a III-layer formed on the first metal layer 12.
First III-VI element compound layer 11 having group VI element compound
And III-VI formed on the first III-VI group compound layer 11
A second III-VI element compound layer 20 having a group element compound.

The I-III-VI group compound semiconductor 14 is shown in FIG.
As shown in FIG. 1B, the precursor 2 shown in FIG.
4 is formed by performing a heat treatment of heating the substrate 4 at a predetermined temperature in a predetermined atmosphere.

The heat treatment is, specifically, a selenization treatment in which the precursor 24 is heated in a selenium vapor atmosphere to inject selenium into the precursor 24.

Accordingly, selenium with a sufficient doping amount can be implanted into the precursor 24 as a dopant, and an effect is obtained that a selenium-rich I-III-VI group compound semiconductor 14 can be obtained.

Instead of the above-described selenium treatment, selenium is ionized, and selenium ions accelerated by applying a predetermined acceleration voltage between the ionized selenium and the precursor 24 are injected into the precursor 24. It is also possible to use an ion implantation process. By controlling the accelerating voltage, selenium with a sufficient doping amount can be implanted as a dopant into a predetermined position in the precursor 24 with a predetermined profile with a good controllability by controlling the accelerating voltage, and a selenium-rich high-quality I-III-VI This has the effect that the group-based compound semiconductor 14 can be obtained.

It is desirable to use sodium (element symbol: Na metal) as the alkali metal.

According to this, the group VI element single layer 15 having the highest reactivity with sodium which is excluded as a heavy metal impurity in the semiconductor process can be arranged near the alkali supply layer 26 containing sodium. It becomes possible to dope sodium from the alkali supply layer 26 by a heat treatment locally and precisely by a predetermined amount.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

In addition, the large crystal grain size can be obtained, so that a high photoelectric conversion efficiency exceeding 10% can be achieved, and the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

As the Group VI element, selenium (element symbol: S
e), sulfur (element symbol: S), tellurium (element symbol: Te), or the like is desirably used. In the present embodiment, it is desirable to use selenium.

By using a group VI element such as selenium, sulfur or tellurium, it is possible to achieve a high photocarrier generation efficiency. In particular, selenium and its compounds are highly crystalline I-III-VI
The effect is that a group III compound semiconductor thin film (sodium-containing CIS thin film) can be easily formed.

Examples of Group III elements include (element symbol: Ga)
Or I-III-VI group compound semiconductor 14, which is indium (element symbol: In).

According to this, by using a group III element such as gallium (Ga) or indium (In),
This has the effect of achieving high photocarrier generation efficiency.

Further, gallium or indium or a compound thereof has an effect that a thin film of a group I-III-VI compound semiconductor having high crystallinity (a CIS thin film containing sodium) can be easily formed.

As the first metal layer 12, molybdenum (element symbol: Mo), tungsten (element symbol: W), chromium (element symbol: Cr), polysilicon (SiO2), metal silicide (specifically, TiSi2 , MoSi2,
It is preferable to use WSi2 or the like) or aluminum (element symbol: Al).

According to this, in addition to the effects described in any one of the first to eighteenth aspects, the selectivity of the metal layer can be increased with respect to the heat treatment requiring a process temperature of about 600 ° C. A metal having a melting point, a metal having a lattice constant or plane orientation capable of increasing a crystal grain system, and a coefficient of linear expansion close to those of the substrate 13, the group VI element single layer 15, or the second III-VI element compound layer 20. This has the effect that a metal or the like can be used.

As a result, CuIn as a CIS semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

Further, a first metal layer 12 (that is, a molybdenum metal layer) containing a high melting point metal such as molybdenum, tungsten, and chromium comprises a substrate 13, a first group III-VI element compound layer (selenium compound layer) 11, It is excellent in adhesion between the film of the group VI element simple substance layer 15 and the like, and does not cause peeling or cracking of the film even when the precursor 24 is exposed to a high temperature process. Can be formed.

Aluminum, which has the second highest conductivity next to noble metals, is a suitable amount of wiring material for a low-temperature process using CVD or the like.

Polysilicon and metal silicide commonly used in an LSI process have a suitable wiring material amount for a low-temperature process using CVD or the like. The use of such polysilicon or metal silicide for the first metal layer 12 makes it possible to use a Si semiconductor device or a GaAs semiconductor device.
I-III-VI group compound semiconductor (sodium-containing CIS layer)
14 can be connected using a conventional semiconductor process.
In other words, a process for fabricating an I-III-VI group compound semiconductor (sodium-containing CIS) 14 can be included in a process for fabricating an integrated circuit using Si or GaAs, and as a result, I-III-VI group compound semiconductor (sodium-containing CIS) 14 as a photoelectric conversion means
OEIC (Opto-Electronic Integrated Cir
cuit: an opto-electronic integrated circuit).

When InxSe (1-x) (0 ≦ x ≦ 1), which is a selenium compound, is used as the first III-VI element compound layer 11, the selenium compound is used as the second III-VI element compound layer 20. It is desirable to use GaxSe (1-x).

When GaxSe (1-x) is used as the first III-VI element compound layer 11, it is preferable to use InxSe (1-x) as the second III-VI element compound layer 20.

Accordingly, InxSe (1-x) (0.ltoreq.x.ltoreq.1) and Gax, which are highly reactive with alkali metals such as sodium which are eliminated as heavy metal impurities in the semiconductor process.
Se (1-x) (0 ≦ x ≦ 1) can be arranged in the order of high reactivity in the vicinity of the alkali supply layer 26 containing the alkali metal and the substrate 13, so that it is locally accurate at a predetermined position by a predetermined amount. It becomes possible to dope an alkali metal from the alkali supply layer 26 by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

As a result, CuIn as a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

Further, by using a group III compound such as InxSe (1-x) or GaxSe (1-x), it is possible to realize high photocarrier generation efficiency, and furthermore, to achieve high crystallinity of I-III The effect is that a group-VI compound semiconductor thin film (sodium-containing CIS thin film) can be easily formed.

Specifically, in this embodiment, 10 −5 [T
orr] in a vacuum state, the substrate 13 containing Na metal.
(Specifically, an alkali glass substrate such as a soda glass substrate) is heated to 200 ° C., and a first metal layer (molybdenum (element symbol: Mo) layer) 12 and a first II
Group I-VI element compound layer (GaxSe (1-x)) 11, second III-
The precursor 24 is formed by vapor deposition (vapor deposition rate = 1 to 10 [angstrom / sec]) in the order of the group VI element compound layer (InxSe (1-x)) 20. Further, as shown in FIG. 1B, the I-III-VI group compound semiconductor 14 is formed by performing a heat treatment of heating the precursor 24 thus manufactured at a predetermined temperature in a predetermined atmosphere. Is done.

The thickness of the Mo layer 12 is 1 to 2 μm, and
The film thickness of xSe (1-x) 11 and InxSe (1-x) 20 is 10,000 [angstrom] in a state where two layers are laminated, and Cu
The thickness of the layer 16 is desirably about 2000 [angstrom].

Further, the film thickness of the I-III-VI group compound semiconductor 14 after the selenization treatment is approximately 20,000 [angstrom].

By forming the first metal layer 12 as a molybdenum layer having a thickness of 1 to 2 μm, the group VI which is most reactive to an alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process. Since the elemental element layer 15 can be disposed in the vicinity of the alkali supply layer 26 containing an alkali metal, the alkali metal is locally and precisely transferred to a predetermined position by a predetermined amount from the alkali supply layer 26 via a molybdenum layer, thereby improving the efficiency. Doping can be performed well and with good controllability. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied. Further, there is an effect that sufficient strength can be maintained for heat treatment requiring a process temperature of about 600 degrees.

As a result, the CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size. Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It works. As a result, there is an effect that the output of the photocurrent can be increased.

The I-III-VI group compound semiconductor 14 is subjected to a heat treatment (hereinafter abbreviated as selenization treatment) for heating the precursor 24 at 550 ° C. for 30 minutes in a selenium vapor atmosphere in a carbon box. Is formed.

According to this, the first III-VI which is highly reactive with alkali metals such as sodium (element symbol: Na metal) excluded as heavy metal impurities in the semiconductor process.
The group 11 element compound layer 11 and the second group III-VI element compound layer 20 can be arranged in the order of high reactivity near the substrate 13 containing an alkali metal. From the substrate 13 by a heat treatment. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, the CuIn semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

[0186] Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

It is also possible to use the second metal layer 16 instead of the second III-VI group element compound layer 20. In this case, as shown in FIG. 1A, the precursor 24 includes a first metal layer 12 formed on a substrate 13 containing an alkali metal and a group III-VI element formed on the first metal layer 12. The first III-VI group element compound layer 11 having a compound
A second metal layer 16 having a copper element (Cu) formed on the group VI element compound layer 11 may be formed. In this case, the I-III-VI group compound semiconductor 14 is formed by performing the above-mentioned selenization treatment on the precursor 24.

According to this, the first III-VI group element compound layer 11 having a high reactivity with alkali metals such as sodium which is eliminated as a heavy metal impurity in the semiconductor process is arranged near the substrate 13 containing alkali metals. So you can
Alkali metal can be doped from the substrate 13 by heat treatment locally and precisely by a predetermined amount at a predetermined position. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

Next, a second embodiment will be described.

FIG. 2A is a cross-sectional view for explaining the basic structure of the precursor 24 having the first III-VI element compound layer 11 and the group VI element simple layer 15, and FIG. FIG. 2B is a cross-sectional view for explaining the basic configuration of the I-III-VI group compound semiconductor 14 manufactured using the precursor 24 of FIG. Note that, for the same portions as those already described in the first embodiment (specifically, the film forming conditions, the final film thickness, and the like), redundant description will be omitted.

The precursor 24 is composed of a first metal layer 12 formed on a substrate 13 containing an alkali metal, a group VI element single layer 15 formed on the first metal layer 12, and a group VI element single layer 15 formed on the first metal layer 12. And a first III-VI element compound layer 11 having a III-VI element compound formed thereon.

The I-III-VI group compound semiconductor 14
Is formed by executing a heat treatment (that is, selenization treatment) for heating the precursor 24 at a predetermined temperature in a predetermined atmosphere.

According to this, the group VI element single layer 15 and the first group III-VI element compound layer 11, which are highly reactive to alkali metals such as sodium which are excluded as heavy metal impurities in the semiconductor process, contain alkali metals. Since it can be arranged in the order of high reactivity in the vicinity of the substrate 13 to be formed, the alkali metal can be locally doped at a predetermined amount by a predetermined amount from the substrate 13 by heat treatment. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, the CIS based semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

In addition, since a large crystal grain size is obtained, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

The group VI element simple substance layer 15 is preferably a layer formed using selenium element simple substance.

According to this, a single element of selenium which is most reactive with alkali metals such as sodium which is excluded as a heavy metal impurity in a semiconductor process is arranged near the alkali supply layer 26 containing the alkali metal and the substrate 13. Therefore, the alkali metal can be locally doped at a predetermined position by a predetermined amount with high precision from the alkali supply layer 26 by a heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

As a result, the CIS based semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, the large crystal grain size can be obtained, so that the high photoelectric conversion efficiency exceeding 10% can be achieved, and the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

Specifically, the precursor 24 is made of Mo formed on a soda glass substrate 13 containing Na metal.
Layer 12 and a single Se layer 15 formed on Mo layer 12 and S
It is desirable to have the Se compound layer 11 formed on the e simple substance layer 15.

The I-III-VI group compound semiconductor 14
Is desirably formed by performing the above-described selenization processing on such a precursor 24.

Further, as shown in FIG. 2A, the precursor 24 is made of a soda glass substrate 13 containing Na metal.
It is also possible to comprise the Mo layer 12 formed thereon, the Se single layer 15 formed on the Mo layer 12, and the Cu layer 16 formed on the Se single layer 15.

In this case, the I-III-VI group compound semiconductor 14
2 is preferably formed by executing the above-described selenization process on the precursor 24, as shown in FIG.

According to this, the group VI elemental element layer 15 most reactive to alkali metals such as sodium which is eliminated as a heavy metal impurity in the semiconductor process can be arranged near the substrate 13 containing alkali metals. In addition, the alkali metal can be locally doped at a predetermined position by a predetermined amount from the substrate 13 by heat treatment. Further, a precursor 2 which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.
4 is realized.

As a result, CuIn as a CIS based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

[0213] Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

Next, a third embodiment will be described.

FIG. 3A is a cross-sectional view for explaining a basic structure of a precursor 24 in which a Mo layer 12, an alkali supply layer (Na metal supply layer) 26, and a first III-VI element compound layer 11 are laminated in this order. FIG. It should be noted that, for the same portions as those already described in the first embodiment or the second embodiment (specifically, film formation conditions, final film thickness, and the like),
Duplicate description is omitted.

The I-III-VI group compound semiconductor 14 is composed of a Mo layer 1 formed on a substrate 13 such as silicon or quartz glass.
2 and an alkali supply layer (Na metal supply layer) 26 formed on the Mo layer 12 in a state containing Na metal and a first III-VI having a Se compound formed on the Na metal supply layer 26
Group II element compound layer (Se compound layer) 11 and second III-VI compound layer formed on first III-VI element compound layer 11
A precursor 24 having a group III-VI element compound layer 20;
Is formed by executing the above-described selenization process.

At this time, the first III-VI group element compound layer 11
Is a selenium compound InxSe (1-x) (0 ≦ x ≦
When 1) is used, it is preferable to use GaxSe (1-x), which is a selenium compound, as the second III-VI group element compound layer 20.

When GaxSe (1-x) is used as the first III-VI element compound layer 11, it is preferable to use InxSe (1-x) as the second III-VI element compound layer 20.

According to this, the first III-VI group element compound layer 11 and the second group III, which are highly reactive to alkali metals such as sodium which are excluded as heavy metal impurities in the semiconductor process.
The III-VI element compound layer 20 is made of N containing alkali metal.
Since it can be arranged in the order of high reactivity near the a metal supply layer 26, the alkali metal can be locally and precisely doped by a predetermined amount at a predetermined position from the Na metal supply layer 26 by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

Further, by providing the Na metal supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be reduced with respect to a heat treatment requiring a process temperature of about 600 degrees. The substrate 13 can be expanded and has a high softening point, the crystal substrate 13 has a lattice constant and a plane orientation that can enlarge the crystal grain system, and the coefficient of linear expansion is M
There is an effect that various substrates 13 such as the substrate 13 similar to the o-layer 12 can be used.

As a result, the CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

For the same purpose, the I-III-VI group compound semiconductor 14 is composed of a Mo layer 12 formed on a substrate 13 such as silicon or quartz glass and a Mo layer 12 containing Na metal.
Na metal supply layer 26 and Na metal supply layer 2 formed thereon
6, a first III-VI element compound layer (InxSe (1-x) or GaxSe (1-x)) 11 having an Se compound and a copper formed on the first III-VI element compound layer 11 The precursor 24 having the second metal layer 16 having an element may be formed by performing the above-described selenization treatment.

According to this, the first III-VI group element compound layer 11 which is highly reactive to alkali metals such as sodium which is excluded as a heavy metal impurity in the semiconductor process is formed by the Na metal supply layer 26 containing alkali metals. Since it can be disposed in the vicinity, the alkali metal can be locally doped at a predetermined position and precisely by a predetermined amount from the Na metal supply layer 26 by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

Further, by providing the Na metal supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be reduced with respect to a heat treatment requiring a process temperature of about 600 ° C. The substrate 13 can be expanded and has a high softening point, the crystal substrate 13 has a lattice constant and a plane orientation that can enlarge the crystal grain system, and the coefficient of linear expansion is M
There is an effect that various substrates 13 such as the substrate 13 similar to the o-layer 12 can be used.

As a result, CIS based semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

Next, a fourth embodiment will be described.

FIG. 3 (b) shows the Na metal supply layer 26, Mo
FIG. 3 is a cross-sectional view for explaining a basic configuration of a precursor 24 in which a layer 12, a first III-VI element compound layer 11, and a second III-VI element compound layer 20 are stacked in this order. Note that the same parts as those already described in the first to third embodiments (specifically, film formation conditions, final film thickness, and the like)
For, the duplicate description will be omitted.

The I-III-VI group compound semiconductor 14 is formed on the substrate 1
3 is formed on the Na metal supply layer 26, the Na metal supply layer 26, the Mo layer 12 formed on the Na metal supply layer 26, and the first III- layer including the Se compound formed on the Mo layer 12.
Group VI element compound layer (InxSe (1-x) or GaxSe (1-x))
11 and S formed on the first III-VI group compound layer 11
The precursor 24 having the second III-VI element compound layer 20 having the e-compound is formed by performing the above-described selenization treatment.

At this time, the first III-VI group element compound layer 11
Is a selenium compound InxSe (1-x) (0 ≦ x ≦
When 1) is used, it is preferable to use GaxSe (1-x), which is a selenium compound, as the second III-VI group element compound layer 20.

When GaxSe (1-x) is used for the first III-VI element compound layer 11, it is preferable to use InxSe (1-x) for the second III-VI element compound layer 20.

According to this, the first III-VI group element compound layer 11 and the second group III, which are highly reactive to alkali metals such as sodium which are excluded as heavy metal impurities in the semiconductor process.
The III-VI element compound layer 20 is made of N containing alkali metal.
Since it can be arranged in the order of high reactivity near the a metal supply layer 26, the alkali metal can be locally and precisely doped by a predetermined amount at a predetermined position from the Na metal supply layer 26 by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the Na metal supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be reduced with respect to a heat treatment requiring a process temperature of about 600 ° C. The substrate 13 can be expanded and has a high softening point, the crystal substrate 13 has a lattice constant and a plane orientation that can enlarge the crystal grain system, and the coefficient of linear expansion is M
There is an effect that various substrates 13 such as the substrate 13 similar to the o-layer 12 can be used.

As a result, CuIn as a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

[0242] Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

To the same effect, the I-III-VI group compound semiconductor 14 is composed of the Na metal supply layer 26 formed on the substrate 13, the Mo layer 12 formed on the Na metal supply layer 26, and the Mo layer 12. A first III-VI group compound layer (InxSe (1-x) or GaxSe (1-x)) having a Se compound formed thereon and a copper element formed on the first III-VI group compound layer 11 The precursor 24 having the second metal layer 16 having the above structure may be formed by performing the above-described selenization process.

According to this, the first III-VI group element compound layer 11 which is highly reactive to alkali metals such as sodium which is eliminated as a heavy metal impurity in the semiconductor process is formed by the Na metal supply layer 26 containing alkali metals. Since it can be disposed in the vicinity, the alkali metal can be locally doped at a predetermined position and precisely by a predetermined amount from the Na metal supply layer 26 by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the Na metal supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be reduced with respect to a heat treatment requiring a process temperature of about 600 ° C. The substrate 13 can be expanded and has a high softening point, the crystal substrate 13 has a lattice constant and a plane orientation that can enlarge the crystal grain system, and the coefficient of linear expansion is M
There is an effect that various substrates 13 such as the substrate 13 similar to the o-layer 12 can be used.

As a result, the CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

Next, a fifth embodiment will be described.

FIG. 3C is a cross-sectional view for explaining the basic structure of the precursor 24 in which the Mo layer 12, the Na metal supply layer 26, and the group VI element simple layer 15 are laminated in this order. In the first to fourth embodiments, the same parts as those already described in the first to fourth embodiments (specifically, film formation conditions, final film thickness, and the like) are not described repeatedly.

The I-III-VI group compound semiconductor 14 is composed of a Mo layer 12 formed on a substrate 13 such as silicon or quartz glass.
And a Na metal supply layer 26 formed on the Mo layer 12 in a state containing the Na metal and a group VI element single layer 15 formed on the Na metal supply layer 26 and a group VI element single layer 15 formed on the Na metal supply layer 26. Group III-VI element compound layer containing Se compound (I
The precursor 24 having nxSe (1-x) and GaxSe (1-x) 11 is formed by executing the above-described selenization process.

According to this, the group VI element simple substance layer 15 and the first III-VI element compound layer 11, which are highly reactive to alkali metals such as sodium which are excluded as heavy metal impurities in the semiconductor process, contain alkali metals. In this case, the alkali metal can be disposed in the vicinity of the Na metal supply layer 26 in the order of high reactivity, so that an alkali metal can be locally and precisely doped at a predetermined position by a predetermined amount from the Na metal supply layer 26 by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the Na metal supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be reduced with respect to a heat treatment requiring a process temperature of about 600 degrees. The substrate 13 can be expanded and has a high softening point, the crystal substrate 13 has a lattice constant and a plane orientation that can enlarge the crystal grain system, and the coefficient of linear expansion is M
There is an effect that various substrates 13 such as the substrate 13 similar to the o-layer 12 can be used.

As a result, the CIS based semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

With the same principle, as shown in FIG.
The I-III-VI group compound semiconductor 14 is composed of a Na metal supply layer 26 formed on a substrate 13 such as silicon
aMo layer 12 and Mo layer 1 formed on metal supply layer 26
The precursor 24 having the group VI element single layer 15 formed on the second element layer 2 and the second metal layer 16 having a copper element formed on the group VI element single layer 15 is formed by performing the above-described selenization treatment. It may be formed.

According to this, the group VI element single layer 15 most reactive to alkali metals such as sodium which is eliminated as a heavy metal impurity in the semiconductor process is placed near the Na metal supply layer 26 containing alkali metals. Since it can be arranged, it becomes possible to dope an alkali metal locally at a predetermined position by a predetermined amount with high precision from the Na metal supply layer 26 by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the Na metal supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be reduced with respect to a heat treatment requiring a process temperature of about 600 degrees. The substrate 13 can be expanded and has a high softening point, the crystal substrate 13 has a lattice constant and a plane orientation that can enlarge the crystal grain system, and the coefficient of linear expansion is M
There is an effect that various substrates 13 such as the substrate 13 similar to the o-layer 12 can be used.

As a result, the CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

Next, an embodiment of a manufacturing process of the I-III-VI group compound semiconductor 14 will be described with reference to the drawings.

FIG. 4A shows the first metal layer 1 on the substrate 13.
FIG. 4 is a cross-sectional view for explaining a state where
(2) First III-VI is formed on the first metal layer 12 of FIG.
FIG. 4C is a cross-sectional view for explaining a state in which the group III element compound layer 11 is stacked. FIG. 4C is a cross-sectional view of the first group III-VI element compound layer 11 shown in FIG. FIG. 4 is a cross-sectional view for explaining a state in which layers 20 are stacked, and FIG.
(4) shows the second III-VI group element compound layer 20 shown in FIG.
FIG. 4 (5) is a cross-sectional view for explaining a precursor 24 configured by laminating the second metal layer 16 thereon. FIG. 4 (5) is a cross-sectional view of an I fabricated by selenizing the precursor 24 of FIG. 4 (4). FIG. 4 is a cross-sectional view for explaining a -III-VI group compound semiconductor 14.

First, as shown in FIG.
Substrate 1 containing Na metal under vacuum of [Torr]
3 (alkaline glass substrate such as soda glass substrate) 20
The substrate was heated to 0 degree, and the Mo layer 12 was
Sputter deposition is performed to a thickness of [μm].

Subsequently, as shown in FIG.
In a vacuum state of [Torr], GaxSe (1-x) (InxSe (1-x)) 11 is deposited on the Mo layer 12 heated to 200 degrees.

Subsequently, as shown in FIG.
Gax heated to 200 degrees in a vacuum of [Torr]
InxSe (1-x) on Se (1-x) (InxSe (1-x)) 11
(GaxSe (1-x)) 20 is deposited. Where GaxS
e (1-x) (InxSe (1-x)) 11 and InxSe (1-x)
x) (GaxSe (1-x)) 20 and a total of 10,000
It is desirable to be about [angstrom].

Subsequently, as shown in FIG.
Inx heated to 200 degrees in a vacuum of [Torr]
A Cu layer 16 is formed on Se (1-x) (GaxSe (1-x)) 20 by two layers.
Deposit with a film thickness of 000 [angstrom]. By the above process, the precursor 24 can be formed.

Finally, as shown in FIG. 4 (5), the precursor 24 was subjected to the above-described selenization treatment to obtain I-III-
The group VI compound semiconductor 14 can be formed. At this time, the I-III-VI group compound semiconductor 14 after selenization treatment
Is preferably about 20,000 [angstrom].

Next, the crystal grain size and the sodium content of the conventional I-III-VI group compound semiconductor and the I-III-VI group compound semiconductor produced in this embodiment will be compared.

FIG. 5 (a) is a chart for explaining the relationship between the crystal grain size and the sodium content in the I-III-VI group compound semiconductor 14 produced using various precursors 24 of CuInSe2 type. , Chart 5 (b) shows C
5 is a table for explaining the relationship between the crystal grain size and the sodium content in an I-III-VI group compound semiconductor 14 manufactured using various precursors 24 based on u (In, Ga) Se2.

As shown in FIG. 5 (a), CuInSe
Any II prepared using various precursors 24 of type 2
Also in the II-VI group compound semiconductor 14, a crystal grain size of 1.3 to 2.0 μm was obtained, and a larger crystal grain size was obtained as compared with the crystal grain size shown in FIG. I understand that there is. At the same time, it can be seen that the sodium content is as high as 1.0 to 1.8.

The measurement of the crystal grain size was derived from observation using a scanning electron microscope, and the sodium content was determined by SIMS (Se
condary Ionization Mass Spectroscopy).

Similarly, as shown in FIG.
It can be seen that any of the I-III-VI group compound semiconductors 14 produced using the (In, Ga) Se 2 -based precursors 24 has a crystal grain size of 1.3 to 1.7 μm. . At the same time, it can be seen that the sodium content is as large as 1.0 to 1.9.

From the above results, in order to increase the crystal grain size of the I-III-VI group compound semiconductor, the precursor 24
It is thought that the sodium content in the steel contributes. That is,
It is thought that sodium-rich precursor 24 shows higher crystallinity.

As described above, the I-III-VI group compound semiconductor 14 described in the first to sixth embodiments is used as the p-type semiconductor layer 32 as a photocarrier generation layer, and photocarriers are extracted as photocurrents. The first metal layer 12
Is used as the electrode 34, the thin-film solar cell 30
Can be configured.

According to this, CIS based semiconductor CuI
The crystal grain size can be increased in either the nSe 2 -based or Cu (In, Ga) Se 2 -based precursor 24,
Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. This has the effect of increasing the photocurrent output of the thin-film solar cell 30.

[0282]

According to the first aspect of the present invention, the first III-VI element compound layer and the second III-VI element layer which are highly reactive to alkali metals such as sodium which are excluded as heavy metal impurities in a semiconductor process. Since the group-VI element compound layer can be arranged in the order of high reactivity near the substrate containing the alkali metal, the alkali metal can be locally and precisely doped at a predetermined amount from the substrate at a predetermined position by a heat treatment. become. Further, there is an effect that a precursor structure can be realized that can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

[0284] Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to the second aspect of the present invention, the group III-VI element compound layer having a high reactivity with an alkali metal such as sodium which is eliminated as a heavy metal impurity in a semiconductor process contains an alkali metal. Therefore, the alkali metal can be locally doped at a predetermined amount by a predetermined amount at a predetermined position from the substrate by a heat treatment. Further, there is an effect that a precursor structure can be realized that can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

[0288] Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to the third aspect of the present invention, a group VI element single layer or a group III-VI element compound which is highly reactive to an alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process. Since the layers can be arranged in the order of high reactivity in the vicinity of the substrate containing the alkali metal, the alkali metal can be locally and precisely doped by a predetermined amount at a predetermined position from the substrate by heat treatment. Further, there is an effect that a precursor structure can be realized that can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to the fourth aspect of the present invention, a substrate containing a group VI element simple substance which is most reactive to an alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process is used. , The alkali metal can be locally doped at a predetermined amount by a predetermined amount at a predetermined position from the substrate by heat treatment. Further, there is an effect that a precursor structure can be realized that can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Also, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to the fifth aspect of the present invention, the first III-VI group compound layer and the second III-VI element layer which are highly reactive to alkali metals such as sodium which are excluded as heavy metal impurities in a semiconductor process. A group element compound layer can be arranged in the order of high reactivity near an alkali supply layer containing an alkali metal, so that a predetermined amount of an alkali metal is locally localized at a predetermined position with high precision from the alkali supply layer by a heat treatment. become able to.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer, which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or a plane orientation capable of increasing a crystal grain system, a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, CuIn as a CIS-based semiconductor
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, a high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to the sixth aspect of the present invention, the first III-VI element compound layer which is highly reactive to alkali metals such as sodium which is excluded as a heavy metal impurity in a semiconductor process contains an alkali metal. Since it can be arranged in the vicinity of the alkali supply layer to be formed, the alkali metal can be locally doped at a predetermined position and precisely by a predetermined amount from the alkali supply layer by heat treatment.

Furthermore, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Also, by providing an alkali supply layer which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or a plane orientation capable of increasing a crystal grain system, a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, the CuIn semiconductor CuIn
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to the seventh aspect of the present invention, a group VI element single layer or a group III-VI element compound which is highly reactive to an alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process. Since the layers can be arranged in the order of high reactivity in the vicinity of the alkali supply layer containing the alkali metal, the alkali metal can be locally doped at a predetermined position by a predetermined amount with high precision by heat treatment from the alkali supply layer. Become.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Also, by providing an alkali supply layer which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or a plane orientation capable of increasing a crystal grain system, a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, the CIS semiconductor CuIn
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to the eighth aspect of the present invention, a group VI element single layer most reactive with an alkali metal such as sodium, which is excluded as a heavy metal impurity in a semiconductor process, is formed of an alkali metal-containing alkali metal. Since it can be disposed near the supply layer, the alkali metal can be locally doped at a predetermined position by a predetermined amount with high accuracy by a heat treatment.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer, which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or a plane orientation capable of increasing a crystal grain system, a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, CuIn as a CIS-based semiconductor
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to the ninth aspect of the present invention, the first III-VI element compound layer or the second III-VI compound layer which is highly reactive to alkali metals such as sodium which are excluded as heavy metal impurities in a semiconductor process. A group element compound layer can be arranged in the order of high reactivity near an alkali supply layer containing an alkali metal, so that a predetermined amount of an alkali metal is locally localized at a predetermined position with high precision from the alkali supply layer by a heat treatment. become able to.

Further, there is an effect that it is possible to realize a precursor structure that can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer, which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or a plane orientation capable of increasing a crystal grain system, a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, CuIn as a CIS based semiconductor
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to the tenth aspect of the present invention, the first III-VI group element compound layer which is highly reactive to alkali metals such as sodium which is excluded as a heavy metal impurity in a semiconductor process contains an alkali metal. Since it can be arranged in the vicinity of the alkali supply layer to be formed, the alkali metal can be locally doped at a predetermined position and precisely by a predetermined amount from the alkali supply layer by heat treatment.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Also, by providing an alkali supply layer, which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or a plane orientation capable of increasing a crystal grain system, a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, CuIn as a CIS based semiconductor
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to the eleventh aspect of the present invention, a group VI element single layer or a group III-VI element compound which is highly reactive to an alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process. Since the layers can be arranged in the order of high reactivity in the vicinity of the alkali supply layer containing the alkali metal, the alkali metal can be locally doped at a predetermined position by a predetermined amount with high precision by heat treatment from the alkali supply layer. Become.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

In addition, by providing an alkali supply layer which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or a plane orientation capable of increasing a crystal grain system, a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, CuIn as a CIS-based semiconductor
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to the twelfth aspect of the present invention, the group VI element single layer most reactive with an alkali metal such as sodium, which is excluded as a heavy metal impurity in a semiconductor process, is formed of an alkali metal-containing alkali metal. Since it can be disposed near the supply layer, the alkali metal can be locally doped at a predetermined position by a predetermined amount with high accuracy by a heat treatment.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer, which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or a plane orientation capable of increasing a crystal grain system, a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, the CIS semiconductor CuIn
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to the thirteenth aspect of the present invention, in addition to the effect of any one of the first to twelfth aspects, the most reactive to sodium which is eliminated as a heavy metal impurity in a semiconductor process. Can be disposed in the vicinity of the alkali-containing layer containing sodium, so that a predetermined amount of sodium can be locally and precisely doped at a predetermined position from the alkali-supplying layer by heat treatment.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS based semiconductor CuIn
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to the fourteenth aspect of the present invention, in addition to the effects of any one of the first to thirteenth aspects, the use of a Group VI element such as selenium, sulfur, or tellurium provides This has the effect of achieving high photocarrier generation efficiency. In particular, selenium and its compounds have the effect that a highly crystalline I-III-VI group compound semiconductor thin film (sodium-containing CIS thin film) can be easily formed.

According to the fifteenth aspect of the present invention, in addition to the effects described in any one of the first to thirteenth aspects, the use of a group III element such as gallium or indium allows a high photocarrier to be obtained. There is an effect that the generation efficiency can be realized.

Further, gallium or indium or a compound thereof has an effect that a thin film of a group I-III-VI compound semiconductor having high crystallinity (sodium-containing CIS thin film) can be easily formed.

According to the invention of claim 16, claims 1, 2, 5, 6, 7, 9, 10, 11, 12, 13, 1
In addition to the effects described in 4 or 15, InxSe (1-x) and GaxS that are highly reactive with alkali metals such as sodium which are excluded as heavy metal impurities in a semiconductor process.
Since e (1-x) can be arranged in the order of high reactivity near the alkali supply layer containing the alkali metal or the substrate, the alkali metal is heat-treated from the alkali supply layer by a predetermined amount locally at a predetermined position with high accuracy. Allows doping treatment.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, a high photoelectric conversion efficiency of more than 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

Further, by using a group III compound such as InxSe (1-x) or GaxSe (1-x), high photocarrier generation efficiency can be realized, and further, high crystallinity of I-III The effect is that a group-VI compound semiconductor thin film (sodium-containing CIS thin film) can be easily formed.

According to the seventeenth aspect, an effect similar to that of the sixteenth aspect is obtained.

According to the eighteenth aspect of the invention, in addition to the effects of any one of the third, fourth, seventh, eighth, eleventh and twelfth aspects, in addition to being eliminated as heavy metal impurities in a semiconductor process. The elemental selenium element, which is most reactive with alkali metals such as sodium, can be placed near the alkali supply layer or the substrate containing alkali metals, so that the alkali metal can be precisely localized at a predetermined position by a predetermined amount. Can be doped from the alkali supply layer by heat treatment.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of photocarriers can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to the nineteenth aspect of the present invention, in addition to the effect of any one of the first to eighteenth aspects, it is possible to add 600
Metal that has a high melting point,
Metals with lattice constants and plane orientations that can enlarge the crystal system, metals with a linear expansion coefficient close to those of the substrate, the group VI element simple substance layer, and the second III-VI element compound layer can be used. It has the effect of becoming.

As a result, CuIn which is a CIS-based semiconductor
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

[0368] Also, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

Further, the first metal layer (that is, the molybdenum metal layer) 12 containing a high melting point metal such as molybdenum, tungsten, and chromium comprises a substrate, a first group III-VI element compound layer (selenium compound layer) 11, a VI It has excellent adhesion between group-element elemental layers and the film, and does not cause film peeling or cracking even when the precursor is exposed to a high-temperature process.
This has an effect that an I-VI group compound semiconductor can be formed.

Aluminum, which has the second highest conductivity next to the noble metal, is a suitable amount of wiring material for a low-temperature process using CVD or the like.

[0372] Polysilicon or metal silicide commonly used in the LSI process is an amount of wiring material suitable for a low-temperature process using CVD or the like. By using such polysilicon or metal silicide for the first metal layer, Si- and GaAs-semiconductor devices have been
III-VI compound semiconductor (sodium-containing CIS layer) 1
4 can be connected using a conventional semiconductor process. In other words, a process for fabricating an I-III-VI group compound semiconductor (sodium-containing CIS) 14 can be included in a process for fabricating an integrated circuit using Si or GaAs, and as a result, LSI using I-III-VI compound semiconductor (sodium-containing CIS) 14 as photoelectric conversion means
This has the effect of realizing a simplified OEIC.

According to the twentieth aspect of the present invention, in addition to the effects of any one of the first to nineteenth aspects, the present invention also provides a method for reducing alkali metal such as sodium which is excluded as a heavy metal impurity in a semiconductor process. Since the most reactive group VI element simple substance layer can be arranged near the alkali supply layer containing the alkali metal, the alkali metal is locally and precisely removed at a predetermined position by a predetermined amount from the alkali supply layer through the molybdenum layer. Thus, the doping process can be performed efficiently and with good controllability by the heat treatment.

Further, by providing a molybdenum layer having a thickness of about 1 to 2 μm, it is possible to realize a precursor structure which can prevent other processes from being adversely affected as impurities unless heat treatment is applied. It works.

In addition, there is an effect that sufficient strength can be maintained for heat treatment requiring a process temperature of about 600 degrees.

As a result, CuIn as a CIS based semiconductor
Either the Se2 or Cu (In, Ga) Se2 precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to the twenty-first aspect of the present invention, in addition to the effects of any one of the sixteenth to twentieth aspects, selenium having a sufficient doping amount can be implanted as a dopant into the precursor, and selenium-rich It is possible to obtain an effective I-III-VI group compound semiconductor.

According to the twenty-second aspect of the present invention, in addition to the effect of the twenty-first aspect, by controlling the acceleration voltage, a sufficiently doped amount of selenium can be used as a dopant at a predetermined position in the precursor. Injection can be performed with a predetermined profile with good controllability, and an effect that a high-quality selenium-rich I-III-VI group compound semiconductor can be obtained can be obtained.

According to the twenty-third aspect of the present invention, in addition to the effects of the first aspect, the CIS
Based semiconductors such as CuInSe2 or Cu (In, G
a) The crystal grain size can be increased in any of the precursors of the Se2 series, and furthermore, the high photoelectric conversion efficiency exceeding 10% can be achieved by obtaining a large crystal grain size. As a result, the life of the photocarrier can be prolonged, and as a result, the output of the photocurrent in the thin-film solar cell can be increased.

[Brief description of the drawings]

FIG. 1A is a cross-sectional view for explaining a basic configuration of a precursor having a first III-VI element compound layer and a second III-VI element compound layer, and FIG. FIG. 2 is a cross-sectional view for explaining a basic configuration of an I-III-VI group compound semiconductor manufactured using the precursor of FIG.

FIG. 2 (a) shows a first III-VI group element compound layer and
FIG. 2B is a cross-sectional view for explaining a basic configuration of a precursor having a group VI element simple substance layer. FIG. 2B is a cross-sectional view of an I-III-VI group compound semiconductor manufactured using the precursor of FIG. FIG. 2 is a cross-sectional view for explaining a basic configuration.

FIG. 3A shows a first metal layer, an alkali supply layer,
FIG. 3 is a cross-sectional view for explaining a basic configuration of a precursor laminated in the order of the first III-VI element compound layers, and FIG.
(B) is a cross-sectional view for explaining a basic configuration of a precursor in which an alkali supply layer, a first metal layer, a first III-VI element compound layer, and a second III-VI element compound layer are stacked in this order; FIG. 3C shows the first metal layer, the alkali supply layer, and the VI
FIG. 3D is a cross-sectional view for explaining a basic configuration of a precursor laminated in the order of a group element element single layer, and FIG. 3D shows a precursor laminated in the order of an alkali supply layer, a first metal layer, and a group VI element element layer. FIG. 3 is a cross-sectional view for describing a basic configuration of FIG.

FIG. 4A is a cross-sectional view for explaining a state in which a first metal layer is stacked on a substrate, and FIG. 4B is a cross-sectional view of FIG. FIG. 4 is a cross-sectional view for explaining a state where a first III-VI group element compound layer is laminated on FIG.
FIG. 4C is a cross-sectional view for explaining a state in which a second III-VI element compound layer is stacked on the first III-VI element compound layer in FIG. 4B, and FIG. Second II in FIG. 4 (3)
FIG. 4 is a cross-sectional view for explaining a precursor constituted by laminating a second metal layer on a group I-VI element compound layer,
FIG. 5 (5) is a cross-sectional view for explaining an I-III-VI group compound semiconductor manufactured by selenizing the precursor of FIG. 4 (4).

FIG. 5A is a table for explaining the relationship between the crystal grain size and the sodium content in an I-III-VI group compound semiconductor manufactured using various CuInSe 2 -based precursors, FIG. 5B shows Cu (In, Ga).
I-III-VI fabricated using various Se2 precursors
3 is a table for explaining a relationship between a crystal grain size and a sodium content in a group III compound semiconductor.

FIG. 6 is a view for explaining the first conventional example, and is a cross-section for explaining a precursor using solid-phase selenization technology and an I-III-VI-based compound semiconductor manufactured using the precursor. FIG.

FIG. 7 is a view for explaining a second conventional example, and is a cross-section for explaining a precursor using a vapor-phase selenization technique and an I-III-VI-based compound semiconductor manufactured using the precursor. FIG.

FIG. 8 (a) shows CuInS using the solid-state selenization technology of the first conventional example or the gas-phase selenization technology of the second conventional example.
FIG. 8 (b) is a table for explaining the relationship between the crystal grain size and the sodium content in the I-III-VI group compound semiconductors manufactured using various precursors of the e2 type.
Various precursors of Cu (In, Ga) Se2 based on the solid-phase selenization technology of the first conventional example or the gas-phase selenization technology of the second conventional example, and fabricated using the precursors.
4 is a table for explaining a relationship between a crystal grain size and a sodium content in an I-III-VI group compound semiconductor.

[Explanation of symbols]

Reference Signs List 11 1st III-VI group compound layer (selenium compound layer) 12 1st metal layer (molybdenum metal layer) 13 substrate (alkali glass substrate) 14 I-III-VI group compound semiconductor (sodium-containing C)
IS layer) 15 Group VI element simple layer (Selenium simple layer) 16 Second metal layer (Cu) 20 Second III-VI group element compound layer (Selenium compound layer) 24 Precursor 26 Alkali supply layer 30 Thin film solar cell 32 P-type semiconductor Layer (I-III-VI compound semiconductor) 34 electrode

[Procedure amendment]

[Submission date] May 26, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction contents]

[Document Name] Statement

Patent application title: I-III-VI compound semiconductor and thin-film solar cell using the same

[Claims]

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device, and more particularly to a precursor of a group I-III-VI compound semiconductor and a thin-film solar cell manufactured using the same.

[0002]

2. Description of the Related Art FIG. 6 is a diagram for explaining a first conventional example, in which a precursor using solid-phase selenization technology and an I-III-VI group compound semiconductor manufactured using the same are used. It is sectional drawing for demonstrating.

A first example of this type of I-III-VI group compound semiconductor is disclosed in, for example, Japanese Patent Application Laid-Open No. 1-2313.
No. 13 (Title of Invention: Production method of semiconductor film,
(Filing date: November 28, 1988) (see FIG. 6).

In a precursor 6 according to a first conventional example, a molybdenum (Mo) metal electrode layer 2, a copper layer 3, an indium (In) layer 4, and a selenium (Se) layer 5 are laminated on a glass substrate 1 in this order. It was composed.

[0005] The precursor 6 having such a laminated structure
By using a solid-phase selenization method of heat-treating Cu
I-III-VI group compound semiconductors 7, 2 such as InGaSe2 were produced.

FIG. 7 is a view for explaining a second conventional example, and illustrates a precursor using a vapor phase selenization method and an I-III-VI group compound semiconductor manufactured using the precursor. FIG.

FIG. 7 shows a second conventional example of producing a group I-III-VI compound semiconductor using a vapor-phase selenization technique in which a precursor of Cu-In is reacted in a vapor phase of selenium such as Se or H2Se. Shown in

The precursor in the second prior art example is configured such that a molybdenum (Mo) metal electrode layer 2, a copper (Cu) layer 3, and an indium (In) layer 4 are laminated on a glass substrate 1 in this order. .

The precursor having such a laminated structure is prepared by using the vapor-phase selenization method described above to obtain CuI.
I-III-VI group compound semiconductors 7, 2 such as nGaSe2 were produced.

FIG. 8A shows a CuI using the solid-state selenization technique of the first conventional example or the gas-phase selenization technique of the second conventional example.
II prepared using various precursors of nSe2 series
FIG. 8B is a table for explaining the relationship between the crystal grain size and the sodium content in the II-VI group compound semiconductor, and FIG. 8B is a diagram illustrating a solid-state selenization technique of the first conventional example or a solid-state selenization technique of the second conventional example. Cu (In, Ga) S using vapor-phase selenization technology
e2 system of various precursor over, and is a table for explaining a relationship between a grain size and a sodium content in the group I-III-VI compound semiconductor fabricated by using the same.

As shown in FIG. 8 (a), any of the CuInSe2-based precursors using the solid state selenization technology of the first conventional example or the gas phase selenization technology of the second conventional example is used. Also in I-III-VI group compound semiconductors, a crystal grain size of 1 μm or less was obtained.

[0012] Similarly, as shown in FIG.
In any of the I-III-VI group compound semiconductors manufactured using various precursors of Cu (In, Ga) Se2 based on the conventional solid-phase selenization technology or the second conventional gas-phase selenization technology. Also, a crystal grain size of 0.5 μm or less was obtained.

[0013]

However, in such a first conventional example or a second conventional example, the I-III-VI group compound semiconductor is CuInSe which is a CIS semiconductor.
Even if a precursor of either 2 type or Cu (In, Ga) Se 2 type is used, only a crystal grain size of about 1 to 0.5 μm can be obtained, so that high photoelectric conversion efficiency exceeding 10% can be realized. And it is difficult to extend the life of the photocarrier.

In other words, it is difficult to extract a large photocurrent from such an I-III-VI group compound semiconductor.
As a result, there has been a technical problem that it is difficult to extract a large photocurrent in a thin-film solar cell manufactured using such an I-III-VI group compound semiconductor.

On the other hand, CuInSe, which is a CIS semiconductor,
In order to increase the crystal grain size in the precursor of either the 2 type or the Cu (In, Ga) Se 2 type, an alkali metal such as sodium is doped into the precursor, and the precursor after the doping is selenized. Accordingly, it is known that the crystal grain size can be increased.

[0016] However, the alkali metal such as sodium to be eliminated as not neat in the semiconductor process, locally be accurately implantation or diffusion by a predetermined amount in a predetermined position, and adversely affect the impurity other processes There was a need for a precursor structure that could be eliminated.

An object of the present invention is to solve such conventional problems, and in particular, to a substrate containing an alkali metal or an alkali supply layer, a group III-VI element compound layer (or a group VI element alone). Layer), second III-VI
I- formed by performing a heat treatment (selenization treatment) of heating at a predetermined temperature in a predetermined atmosphere to a precursor formed by laminating a group III element compound layer (or a second metal layer) in this order. depending on the III-VI group compound semiconductor, an alkali metal such as sodium to be eliminated as not neat in the semiconductor process, locally precisely doped by a predetermined amount in a predetermined position, and impurities other processes As a result, a structure of a precursor that can be prevented from being adversely affected is realized.
It is an object of the present invention to increase the crystal grain size of either an InSe2 or Cu (In, Ga) Se2 precursor.

[0018] Also, depending to a large grain size is obtained, Ri FIG high photoelectric conversion efficiency that exceeds 10%, further, it aims to extend the life of the photocarriers, as a result, higher output photocurrent The challenge is to achieve the goal.

Another object is to increase the photocurrent output of the thin-film solar cell by manufacturing a thin-film solar cell using such an I-III-VI group compound semiconductor.

[0020]

According to a first aspect of the present invention, there is provided an I-III-VI group compound semiconductor 14,
A first metal layer 12 formed on a substrate 13 containing an alkali metal and a III-layer formed on the first metal layer 12
A first III-VI element compound layer 11 having a group VI element compound and a second I-II compound having a III-VI element compound formed on the first III-VI element compound layer 11
I-II formed by performing a heat treatment of heating the precursor 24 having the II-VI group element compound layer 20 at a predetermined temperature in a predetermined atmosphere.
It is an I-VI group compound semiconductor 14.

[0021] According to the invention of claim 1, sodium (element symbol: Na) to be eliminated as not neat in a semiconductor process first highly reactive with respect to alkali metals, such as
The group III-VI element compound layer 11 and the second group III-VI element compound layer 20 can be arranged in the order of high reactivity near the substrate 13 containing an alkali metal. Good alkali metal substrate 13
Thus, doping can be performed by heat treatment. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

[0025] The invention according to claim 2 is characterized in that I-III-V
A first metal layer 12 formed on a substrate 13 containing an alkali metal;
A first III-VI element compound layer 11 having a III-VI element compound formed on a metal layer 12;
By performing a heat treatment of heating a precursor 24 having a second metal layer 16 having a copper element (element symbol: Cu) formed on the III-VI group element compound layer 11 at a predetermined temperature in a predetermined atmosphere. The I-III-VI group compound semiconductor 14 thus formed.

[0026] According to the invention of claim 2, alkali metal first group III-VI group element compound layer 11 highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Can be disposed in the vicinity of the substrate 13 containing, so that the alkali metal can be locally doped at a predetermined position by a predetermined amount with high precision by heat treatment. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, CIS based semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

In addition, since a large crystal grain size is obtained, a high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

[0030] The invention according to claim 3 is characterized in that I-III-V
A first metal layer 12 formed on a substrate 13 containing an alkali metal;
Group VI element single layer 15 formed on metal layer 12 and first III-VI group element compound layer 11 having group III-VI element compound formed on group VI element single layer 15
I-III-VI group compound semiconductor 14 formed by performing a heat treatment for heating precursor 24 having a predetermined temperature in a predetermined atmosphere at a predetermined temperature.
It is.

[0031] According to the invention of claim 3, VI group element alone layer 15 and the second group III-VI group highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Since the elemental compound layer 11 can be arranged in the order of high reactivity in the vicinity of the substrate 13 containing the alkali metal, the alkali metal can be locally and precisely doped at a predetermined position from the substrate 13 by a predetermined amount by a heat treatment. become. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, CuIn which is a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

In addition, since a large crystal grain size is obtained, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

The invention according to claim 4 is characterized in that I-III-V
A first metal layer 12 formed on a substrate 13 containing an alkali metal;
A precursor 24 having a group VI element single layer 15 formed on the metal layer 12 and a second metal layer 16 having a copper element formed on the group VI element single layer 15 is heated at a predetermined temperature in a predetermined atmosphere. The I-III-VI group compound semiconductor 14 is formed by performing a heat treatment.

The claimed According to the invention described in claim 4, VI group element alone layer rich in most reactive to alkali metals such as sodium to be eliminated as not neat in a semiconductor process 1
Since 5 can be arranged in the vicinity of the substrate 13 containing the alkali metal, the alkali metal can be locally doped at a predetermined amount by a predetermined amount at a predetermined position from the substrate 13 by a heat treatment. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, CIS based semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

The invention according to claim 5 is characterized in that I-III-V
An alkali supply layer 26 formed on the substrate 13, a first metal layer 12 formed on the alkali supply layer 26, and a III layer formed on the first metal layer 12; -III having Group VI elemental compound
A precursor 24 having a group VI element compound layer 11 and a second III-VI element compound layer 20 having a III-VI element compound formed on the first III-VI element compound layer 11 in a predetermined atmosphere. The I-III-VI group compound semiconductor 14 formed by performing a heat treatment of heating at a predetermined temperature.

[0041] According to the invention of claim 5, the group III-VI group element compound layer 11 and the second 2III rich in reactivity to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Since the group VI element compound layer 20 can be arranged in the order of high reactivity in the vicinity of the alkali supply layer 26 containing an alkali metal, the alkali metal can be locally and precisely added to a predetermined position by a predetermined amount in the alkali supply layer 2.
From step 6, doping can be performed by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 degrees. Substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate 13 having a linear expansion coefficient similar to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, the CuIn semiconductor, CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

[0047] The invention according to claim 6 is characterized in that I-III-V
An alkali supply layer 26 formed on the substrate 13, a first metal layer 12 formed on the alkali supply layer 26, and a III-type compound semiconductor formed on the first metal layer 12. First III-V having Group VI elemental compound
Group I element compound layer 11 and second metal layer 1 having a copper element formed on first III-VI group element compound layer 11
6 is formed by performing a heat treatment of heating the precursor 24 having a predetermined temperature and a predetermined temperature in a predetermined atmosphere.
I-III-VI compound semiconductor 1
4.

[0048] According to the invention of claim 6, alkali metal first group III-VI group element compound layer 11 highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Can be disposed in the vicinity of the alkali supply layer 26 containing, so that the alkali metal can be locally doped at a predetermined position by a predetermined amount with high accuracy by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the alkali supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 ° C. Substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate 13 having a linear expansion coefficient similar to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, CuIn which is a CIS based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

The invention according to claim 7 is characterized in that I-III-V
An alkali supply layer formed on the substrate, a first metal layer formed on the alkali supply layer, and a group VI compound formed on the first metal layer; Element simple substance layer 15 and group VI element simple substance layer 15
First having a III-VI compound formed thereon
II formed by performing a heat treatment of heating the precursor 24 having the III-VI group element compound layer 11 at a predetermined temperature in a predetermined atmosphere.
II-VI group compound semiconductor 14.

[0055] According to the invention of claim 7, VI group element alone layer 15 and the second group III-VI group highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Since the elemental compound layer 11 can be arranged in the order of high reactivity near the alkali supply layer 26 containing the alkali metal, the alkali metal is locally and precisely removed from the alkali supply layer 26 by a predetermined amount at a predetermined position. Doping processing can be performed.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer 26 that can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 degrees. Substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate 13 having a linear expansion coefficient similar to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, the CuIn semiconductor, CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, a high photoelectric conversion efficiency of more than 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

[0061] The invention according to claim 8 is characterized in that I-III-V
An alkali supply layer formed on the substrate, a first metal layer formed on the alkali supply layer, and a group VI compound formed on the first metal layer; Element simple substance layer 15 and group VI element simple substance layer 15
I-III-VI formed by performing a heat treatment of heating a precursor 24 having a second metal layer 16 having a copper element formed thereon at a predetermined temperature in a predetermined atmosphere. Group 14 compound semiconductor.

[0062] According to the invention of claim 8, rich in most reactive to alkali metals such as sodium to be eliminated as not neat in a semiconductor process VI element alone layer 1
Since 5 can be arranged near the alkali supply layer 26 containing an alkali metal, the alkali metal can be locally and precisely doped at a predetermined position by a predetermined amount from the alkali supply layer 26 by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the alkali supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 ° C. Substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate 13 having a linear expansion coefficient similar to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, CuIn which is a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to the ninth aspect of the present invention, there is provided the method of I-III-V
A group I-based compound semiconductor 14, wherein the first metal layer 12 formed on the substrate 13 and the alkali supply layer 26 and the alkali supply layer formed on the first metal layer 12 while containing an alkali metal First III-VI element compound layer 1 having a III-VI element compound formed on 26
1 and a second III-VI having a III-VI group compound formed on the first III-VI group compound layer 11.
I-III-V formed by performing a heat treatment of heating the precursor 24 having the group VI element compound layer 20 at a predetermined temperature in a predetermined atmosphere.
It is a Group I compound semiconductor 14.

[0069] According to the invention of claim 9, the first and second group III-VI group element compound layer 11 rich in reactivity to alkali metals such as sodium to be eliminated as not neat in a semiconductor process 2III Since the group VI element compound layer 20 can be arranged in the order of high reactivity in the vicinity of the alkali supply layer 26 containing an alkali metal, the alkali metal can be locally and precisely added to a predetermined position by a predetermined amount in the alkali supply layer 2.
From step 6, doping can be performed by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 degrees. Substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate 13 having a linear expansion coefficient similar to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, CuIn which is a CIS based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

The tenth aspect of the present invention relates to I-III-
A group VI compound semiconductor 14 comprising a first metal layer 12 formed on a substrate 13 and an alkali supply layer 26 formed on the first metal layer 12 while containing an alkali metal;
And III-VI formed on the alkali supply layer 26
A precursor 24 having a first III-VI element compound layer 11 having a group III element compound and a second metal layer 16 having a copper element formed on the first III-VI element compound layer 11 is formed in a predetermined atmosphere in a predetermined atmosphere. An I-III-VI group compound semiconductor 14 formed by performing a heat treatment of heating at a temperature.

[0076] According to the invention described in claim 10, an alkali metal first group III-VI group element compound layer 11 highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Can be disposed in the vicinity of the alkali supply layer 26 containing the alkali metal.
Thus, doping can be performed by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the alkali supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 ° C. Substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate 13 having a linear expansion coefficient similar to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, CuIn which is a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

The eleventh aspect of the present invention relates to I-III-
A group VI compound semiconductor 14 comprising a first metal layer 12 formed on a substrate 13 and an alkali supply layer 26 formed on the first metal layer 12 while containing an alkali metal;
And the group VI element single layer 15 formed on the alkali supply layer 26 and the group I element formed on the group VI element single layer 15.
I- is formed by performing a heat treatment of heating a precursor 24 having a first III-VI group compound layer 11 having a II-VI group compound at a predetermined temperature in a predetermined atmosphere. III-VI group compound semiconductor 14.

[0083] according According to the invention described in claim 11, VI group element alone layer rich in reactivity to alkali metals such as sodium to be eliminated as not neat in a semiconductor process 15
And the first III-VI group element compound layer 11 can be arranged near the alkali supply layer 26 containing an alkali metal in the order of high reactivity, so that the alkali metal is locally supplied to a predetermined position by a predetermined amount with high accuracy. The layer 26 can be doped by a heat treatment.

Furthermore, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

Further, by providing the alkali supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to a heat treatment requiring a process temperature of about 600 ° C. Substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate 13 having a linear expansion coefficient similar to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, CuIn as a CIS semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

The twelfth aspect of the present invention relates to I-III-
A group VI compound semiconductor 14 comprising a first metal layer 12 formed on a substrate 13 and an alkali supply layer 26 formed on the first metal layer 12 while containing an alkali metal.
A precursor having a group VI element single layer formed on the alkali supply layer and a second metal layer having a copper element formed on the group VI element single layer;
I-III formed by performing a heat treatment of heating C.4 at a predetermined temperature in a predetermined atmosphere.
-VI group compound semiconductor 14.

[0090] According to the invention of claim 12, containing an alkali metal to Group VI element alone layer 15 rich in most reactive to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Since it can be arranged in the vicinity of the alkali supply layer 26, the alkali metal can be locally doped at a predetermined position by a predetermined amount with high precision by a heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the alkali supply layer 26 that can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be increased with respect to the heat treatment requiring a process temperature of about 600 degrees. Substrate 13 having a high softening point, a crystal substrate 13 having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate 13 having a linear expansion coefficient similar to that of the first metal layer 12, and the like. There is an effect that the substrate 13 can be used.

As a result, CuIn which is a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

According to a thirteenth aspect of the present invention, in the I-III-VI group compound semiconductor according to any one of the first to twelfth aspects, the alkali metal is sodium. -III-VI group compound semiconductor 14.

[0097] According to the invention of claim 13, in addition to the effects according to any one of claims 1 to 12, most reactions to sodium to be eliminated as not neat in a semiconductor process Since the group VI elemental element layer 15 having a high property can be arranged in the vicinity of the alkali-containing layer 26 containing sodium, it is possible to locally dope a predetermined amount of sodium from the alkali-supplying layer 26 at a predetermined position by a heat treatment. Become like

Furthermore, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, CuIn which is a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to a fourteenth aspect of the present invention, in the I-III-VI group compound semiconductor according to any one of the first to thirteenth aspects, the group VI element is selenium (element symbol: Se). , Sulfur (element symbol: S), or tellurium (element symbol: Te)
-III-VI group compound semiconductor 14.

According to the fourteenth aspect of the present invention, in addition to the effects of any one of the first to thirteenth aspects, the use of a group VI element such as selenium, sulfur, or tellurium provides This has the effect of achieving high photocarrier generation efficiency. In particular, selenium and its compounds have the effect that a highly crystalline I-III-VI group compound semiconductor thin film (sodium-containing CIS thin film) can be easily formed.

According to a fifteenth aspect of the present invention, in the I-III-VI group compound semiconductor according to any one of the first to thirteenth aspects, the group III element is gallium or indium. Characteristic I-III-VI
Group 14 compound semiconductor.

According to the fifteenth aspect of the present invention, in addition to the effects of any one of the first to thirteenth aspects, gallium (element symbol: Ga) or indium (element symbol: I
By using a group III element such as n), there is an effect that a high generation efficiency of photocarriers can be realized.

Further, gallium or indium or a compound thereof has an effect that it is possible to easily form a group I-III-VI group compound semiconductor thin film (sodium-containing CIS thin film) having high crystallinity.

The invention according to claim 16 is the first invention.
2, 5, 6, 7, 9, 10, 11, 12, 13, 14,
Or I-III-VI group compound semiconductor 1 described in 15 or
4, the first group III-VI element compound layer 11
Has InxSe (1-x), and the second III-
The I-III-VI group compound semiconductor 14, wherein the group VI element compound layer 20 has GaxSe (1-x).

According to the invention of claim 16, according to claims 1, 2, 5, 6, 7, 9, 10, 11, 12, 13, 1
In addition to the effects described in the item 4 or 15, a semiconductor
In InxSe highly reactive with respect to alkali metals such as sodium to be eliminated as not neat (1-x) (0 ≦ x ≦
1) and GaxSe (1-x) (0 ≦ x ≦ 1) can be arranged in the order of high reactivity near the alkali supply layer 26 containing the alkali metal and the substrate 13. The doping treatment of the alkali metal from the alkali supply layer 26 by the heat treatment can be performed with high accuracy only by the quantitative determination.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

As a result, CuIn, which is a CIS semiconductor,
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

In addition, InxSe (1-x) and GaxSe
By using a group III compound such as (1-x), high photocarrier generation efficiency can be realized, and further, a highly crystalline I-III-VI group compound semiconductor thin film (sodium-containing CIS thin film) Can be easily formed.

The invention described in claim 17 is based on claim 1,
2, 5, 6, 7, 9, 10, 11, 12, 13, 14,
Or I-III-VI group compound semiconductor 1 described in 15 or
4, the first group III-VI element compound layer 11
Has GaxSe (1-x), and the second III-
The I-III-VI group compound semiconductor 14, wherein the group VI element compound layer 20 has InxSe (1-x).

According to the seventeenth aspect, the same effect as that of the sixteenth aspect can be obtained.

The invention described in claim 18 is the third invention.
I- described in any one of 4, 7, 8, 11, or 12
In the III-VI compound semiconductor 14,
The group I element element layer 15 is a layer formed using a selenium element element alone.

[0117] According to the invention of claim 18, in addition to the effects described in any one of claims 3,4,7,8,11, or 12, as not neat in a semiconductor process A single element of selenium, which is most reactive to an alkali metal such as sodium to be excluded, can be arranged near the alkali supply layer 26 containing the alkali metal or the substrate 13, so that a predetermined amount of accuracy is locally obtained at a predetermined position. It becomes possible to dope an alkali metal from the alkali supply layer 26 by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

As a result, CuIn as a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to a nineteenth aspect of the present invention, in the I-III-VI group compound semiconductor according to any one of the first to eighteenth aspects, the first metal layer 12 is formed of molybdenum (element symbol: Mo), tungsten (element symbol:
W), chromium (element symbol: Cr), polysilicon (Si
The I-III-VI group compound semiconductor 14, which is a layer formed using O2), metal silicide, or aluminum (element symbol: Al).

The metal silicide of the present invention is
TiSi2, MoSi2, WSi2, etc.

According to the nineteenth aspect of the present invention, in addition to the effect of any one of the first to eighteenth aspects, in addition to
Metal that has a high melting point,
It is possible to use a metal having a lattice constant or a plane orientation capable of increasing the crystal grain size , a metal having a linear expansion coefficient close to that of the substrate 13, the group VI element single layer 15, or the second III-VI element compound layer 20, or the like. It has the effect of being able to do so.

As a result, CuIn as a CIS based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

Further, the first metal layer (that is, the molybdenum metal layer) 12 containing a high melting point metal such as molybdenum, tungsten, chromium, etc. It is excellent in adhesion between the film of the group VI element element layer 15 and the like and the film of the I-III-VI compound semiconductor 1 without peeling or cracking of the film even when the precursor 24 is exposed to a high-temperature process.
4 can be formed.

Aluminum, which has the second highest conductivity next to noble metals, is a suitable amount of wiring material for a low-temperature process using CVD or the like.

Polysilicon and metal silicide commonly used in an LSI process have a suitable wiring material amount for a low-temperature process using CVD or the like. By using such polysilicon or metal silicide for the first metal layer 12, a Si semiconductor device or a GaAs semiconductor device and an I-III-VI group compound semiconductor (sodium-containing C
IS layer 14 can be connected using a conventional semiconductor process. In other words, a process for fabricating an I-III-VI group compound semiconductor (sodium-containing CIS) 14 can be included in a process for fabricating an integrated circuit using Si or GaAs, and as a result, I-III
-Group VI compound semiconductor (sodium-containing CIS) 14
OEIC (Opto Optoelectronics) as a photoelectric conversion means
-Electronic Integrated Ci
rcuit: optoelectronic integrated circuit).

According to a twentieth aspect of the present invention, in the I-III-VI group compound semiconductor according to any one of the first to nineteenth aspects, the first metal layer 12 has a thickness of one to two.
The I-III-VI group compound semiconductor 14 is a molybdenum layer having a thickness of μm.

[0132] According to the invention of claim 20, in addition to the effects according to any one of claims 1 to 19, an alkali metal such as sodium to be eliminated as not neat in a semiconductor process On the other hand, since the group VI elemental element layer 15 having the highest reactivity can be arranged near the alkali supply layer 26 containing an alkali metal, the alkali metal is locally and precisely removed from the alkali supply layer 26 by a predetermined amount at a predetermined position. Through the molybdenum layer, the doping can be performed efficiently and with good controllability by the heat treatment.

Further, by providing a molybdenum layer having a thickness of about 1 to 2 μm, it is possible to realize a structure of the precursor 24 that can prevent other processes from being adversely affected as impurities unless heat treatment is applied. This has the effect.

In addition, there is an effect that sufficient strength can be maintained for heat treatment requiring a process temperature of about 600 degrees.

As a result, CuIn as a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to a twenty-first aspect of the present invention, in the I-III-VI-based compound semiconductor according to any one of the sixteenth to twentieth aspects, the heat treatment is performed in a selenium vapor atmosphere in the presence of the precursor. Is a selenization treatment for injecting selenium into the precursor 24 by heating selenium to form the I-III-VI group compound semiconductor 14.

According to the twenty-first aspect of the present invention, in addition to the effects of any one of the sixteenth to twentieth aspects, in addition to the effect of the selenium having a sufficient doping amount as a dopant, the precursor 2
4 to provide an effect that a selenium-rich I-III-VI group compound semiconductor 14 can be obtained.

According to a twenty-second aspect of the present invention, in the I-III-VI group compound semiconductor according to the twenty-first aspect, instead of the selenization treatment, selenium is ionized and the ionized selenium and the ionized selenium are combined. Precursor 24
And I-III-VI compound semiconductor 14 characterized by using an ion implantation process in which a predetermined acceleration voltage is applied between the above and the accelerated selenium ions to be implanted into the precursor 24.

According to the twenty-second aspect of the present invention, in addition to the effect of the twenty-first aspect, by controlling the acceleration voltage, a predetermined amount of selenium having a sufficient doping amount as a dopant in the precursor 24 can be obtained. Selenium-rich high-quality I-II
There is an effect that the I-VI group compound semiconductor 14 can be obtained.

According to a twenty-third aspect of the present invention, in a thin-film solar cell 30 using the I-III-VI group compound semiconductor 14 according to any one of the first to twenty-second aspects, a photocarrier generation layer is provided. A thin-film solar cell 30 having a p-type semiconductor layer 32 using the I-III-VI group compound semiconductor 14 and an electrode 34 using at least the first metal layer 12 to extract the photocarriers as a photocurrent. It is.

According to the twenty-third aspect of the present invention, in addition to the effects of the first aspect, the CIS
CuInSe2 or Cu (In, G)
a) The crystal grain size can be increased in any of the precursors 24 of the Se2 series, and further, since a large crystal grain size is obtained, a high photoelectric conversion efficiency exceeding 10% can be achieved. As a result, the life of the photocarrier can be prolonged, and as a result, the photocurrent of the thin-film solar cell 30 can be increased in output.

[0144]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a group I-III-VI compound semiconductor according to a first embodiment of the present invention;

FIG. 1A shows a first III-VI group compound layer 11 and a second III-VI group compound layer 20.
FIG. 1B is a cross-sectional view for explaining a basic configuration of a precursor 24 having the following formula. FIG. 1B is a cross-sectional view of a basic configuration of an I-III-VI group compound semiconductor 14 manufactured using the precursor 24 of FIG. FIG. 6 is a cross-sectional view for explaining the method.

As shown in FIG. 1A, the precursor 24 includes a first metal layer 12 formed on a substrate 13 containing an alkali metal and a II metal layer formed on the first metal layer 12.
A first III-VI element compound layer 11 having a I-VI element compound and a second I-III compound having a III-VI element compound formed on the first III-VI element compound layer 11
A group II-VI element compound layer 20.

I-III-VI Group Compound Semiconductor 14
1B is formed by performing a heat treatment for heating the precursor 24 shown in FIG. 1A at a predetermined temperature in a predetermined atmosphere, as shown in FIG. 1B.

The heat treatment is, specifically, a selenization treatment in which the precursor 24 is heated in a selenium vapor atmosphere to inject selenium into the precursor 24.

Accordingly, selenium with a sufficient doping amount can be implanted into the precursor 24 as a dopant, and an effect is obtained that a selenium-rich I-III-VI group compound semiconductor 14 can be obtained.

Instead of the above-described selenium treatment, selenium is ionized, and selenium ions accelerated by applying a predetermined acceleration voltage between the ionized selenium and the precursor 24 are injected into the precursor 24. It is also possible to use an ion implantation process. By controlling the accelerating voltage, selenium with a sufficient doping amount can be implanted as a dopant into a predetermined position in the precursor 24 with a predetermined profile with a good controllability by controlling the accelerating voltage, and a selenium-rich high-quality I-III-VI Group compound semiconductor 14
Is obtained.

It is desirable to use sodium (element symbol: Na metal) as the alkali metal.

[0152] Depending on this, V-rich and most reactive towards sodium to be eliminated as not neat in a semiconductor process
Since the group-I element simple substance layer 15 can be arranged in the vicinity of the alkali-containing layer 26 containing sodium, the sodium-containing layer 26 is locally and precisely added to a predetermined position by a predetermined amount.
Thus, doping can be performed by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

In addition, the large crystal grain size can be obtained, so that a high photoelectric conversion efficiency exceeding 10% can be achieved, and the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

As the Group VI element, selenium (element symbol:
It is preferable to use Se), sulfur (element symbol: S), tellurium (element symbol: Te), or the like. In the present embodiment, it is desirable to use selenium.

According to this, the use of a group VI element such as selenium, sulfur, or tellurium has an effect that high photocarrier generation efficiency can be realized. In particular, selenium and its compounds have high crystallinity II.
II-VI compound semiconductor thin film (sodium-containing CI
(S thin film) can be easily formed.

The group III element is gallium (element symbol: Ga) or indium (element symbol: In).
It is.

According to this, by using a group III element such as gallium (Ga) or indium (In), it is possible to achieve an effect that high photocarrier generation efficiency can be realized.

Further, gallium or indium or a compound thereof has an effect of easily forming a group I-III-VI group compound semiconductor thin film (sodium-containing CIS thin film) having high crystallinity.

As the first metal layer 12, molybdenum (element symbol: Mo), tungsten (element symbol: W), chromium (element symbol: Cr), polysilicon (SiO2), metal silicide (specifically, TiSi2 , MoSi
2, WSi2, etc.) or aluminum (element symbol: A
It is desirable to use l).

According to this, in addition to the effects described in any one of the first to eighteenth aspects, the selectivity of the metal layer can be increased with respect to the heat treatment requiring a process temperature of about 600 ° C. A metal having a melting point, a metal having a lattice constant or plane orientation capable of increasing the crystal grain size , and a linear expansion coefficient close to those of the substrate 13, the group VI element simple substance layer 15, or the second III-VI element compound layer 20. This has the effect that a metal or the like can be used.

As a result, CuIn as a CIS semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

Further, a first metal layer (that is, a molybdenum metal layer) 12 containing a high melting point metal such as molybdenum, tungsten, chromium, etc. It is excellent in adhesion between the film of the group VI element element layer 15 and the like and the film of the I-III-VI compound semiconductor 1 without peeling or cracking of the film even when the precursor 24 is exposed to a high-temperature process.
4 can be formed.

Aluminum, which has the second highest conductivity next to noble metals, is a suitable amount of wiring material for a low-temperature process using CVD or the like.

Polysilicon and metal silicide commonly used in an LSI process have a suitable wiring material amount for a low-temperature process using CVD or the like. By using such polysilicon or metal silicide for the first metal layer 12, a Si semiconductor device or a GaAs semiconductor device and an I-III-VI group compound semiconductor (sodium-containing C
IS layer 14 can be connected using a conventional semiconductor process. In other words, a process for fabricating an I-III-VI group compound semiconductor (sodium-containing CIS) 14 can be included in a process for fabricating an integrated circuit using Si or GaAs, and as a result, I-III
-Group VI compound semiconductor (sodium-containing CIS) 14
OEIC (Opto Optoelectronics) as a photoelectric conversion means
-Electronic Integrated Ci
rcuit: optoelectronic integrated circuit).

The first III-VI element compound layer 1
1 is a selenium compound, InxSe (1-x) (0
≦ x ≦ 1), the second III-VI group element compound layer 20 is made of GaxSe (1-
It is desirable to use x).

The first III-VI element compound layer 1
When GaxSe (1-x) is used as 1, the second
As the III-VI group element compound layer 20, InxSe (1
It is desirable to use -x).

[0172] Depending on this, InxSe highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process (1-x) (0 ≦ x ≦ 1) and Ga
Since xSe (1-x) (0 ≦ x ≦ 1) can be arranged in the order of high reactivity in the vicinity of the alkali supply layer 26 containing the alkali metal and the substrate 13, the accuracy is locally increased by a predetermined amount at a predetermined position. It becomes possible to dope an alkali metal from the alkali supply layer 26 by heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

As a result, CuIn as a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

In addition, InxSe (1-x) and GaxSe
By using a group III compound such as (1-x), high photocarrier generation efficiency can be realized, and further, a highly crystalline I-III-VI group compound semiconductor thin film (sodium-containing CIS thin film) Can be easily formed.

More specifically, in this embodiment, 10-5
Substrate 1 containing Na metal under vacuum of [Torr]
3 (specifically, an alkali glass substrate such as a soda glass substrate) is heated to 200 ° C.
Metal layer (molybdenum (element symbol: Mo) layer) 12, first
III-VI group element compound layer (GaxSe (1-x))
11, the second III-VI group element compound layer (InxSe
(1-x)) evaporation in the order of 20 (evaporation rate = 1 to 10)
[Angstrom / sec]) to form the precursor 24. Further, as shown in FIG. 1B, the I-III-VI group compound semiconductor 14 is formed by performing a heat treatment of heating the precursor 24 thus manufactured at a predetermined temperature in a predetermined atmosphere. Is done.

The thickness of the Mo layer 12 is 1 to 2 μm, and
The film thickness of xSe (1-x) 11 and InxSe (1-x) 20 is desirably about 10,000 [angstrom] in a state where two layers are laminated, and the film thickness of the Cu layer 16 is about 2000 [angstrom].

The thickness of the I-III-VI group compound semiconductor 14 after the selenization treatment is approximately 20,000 [angstrom].

By forming the first metal layer 12 as a molybdenum layer having a thickness of 1 to 2 μm,
In so a VI group element alone layer 15 rich in most reactive to alkali metals such as sodium to be eliminated as not neat can be arranged in the vicinity of the alkali supply layer 26 containing an alkali metal, localized in position Then, the alkali metal can be efficiently and controlledly doped by the heat treatment from the alkali supply layer 26 through the molybdenum layer by a predetermined amount with high precision. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied. Further, there is an effect that sufficient strength can be maintained for heat treatment requiring a process temperature of about 600 degrees.

As a result, the CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size. Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It works. As a result, there is an effect that the output of the photocurrent can be increased.

I-III-VI Group Compound Semiconductor 14
Is 550 in the selenium vapor atmosphere in the carbon box.
The heat treatment is performed by heating the precursor 24 for 30 minutes at a temperature (hereinafter, abbreviated as selenization treatment).

[0184] Depending on this, the sodium to be eliminated as not neat in a semiconductor process (symbol of element: Na metal) The group III-VI group element compound rich in reactivity to alkali metals, such as layer 11 and second 2III- Group VI element compound layer 2
Since 0 can be arranged in the order of high reactivity in the vicinity of the substrate 13 containing the alkali metal, the alkali metal can be locally and precisely doped by a predetermined amount at a predetermined position from the substrate 13 by a heat treatment. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, the CuIn semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

[0186] Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

The second III-VI element compound layer 2
It is also possible to use the second metal layer 16 instead of 0.
In this case, as shown in FIG. 1A, the precursor 24 includes a first metal layer 12 formed on a substrate 13 containing an alkali metal and a III-layer formed on the first metal layer 12.
It is formed to have a first III-VI element compound layer 11 having a group VI element compound and a second metal layer 16 having a copper element (Cu) formed on the first III-VI element compound layer 11. May be. In this case, I-III-V
The group I-based compound semiconductor 14 has such a precursor 2
4 is formed by performing the above-described selenization treatment on the heat treatment.

[0189] Depending on this, in the vicinity of the substrate 13 containing an alkali metal to the group III-VI group element compound layer 11 highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Can be placed,
Alkali metal can be doped from the substrate 13 by heat treatment locally and precisely by a predetermined amount at a predetermined position. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

Next, a second embodiment will be described.

FIG . 2A is a cross-sectional view for explaining the basic structure of a precursor 24 having a group III-VI element compound layer 11 and a group VI element single layer 15, and FIG. FIG. 3 is a cross-sectional view for explaining a basic configuration of an I-III-VI group compound semiconductor 14 manufactured using a precursor 24 of FIG. Note that, for the same portions as those already described in the first embodiment (specifically, the film forming conditions, the final film thickness, and the like), redundant description will be omitted.

The precursor 24 comprises a first metal layer 12 formed on a substrate 13 containing an alkali metal, a group VI element single layer 15 formed on the first metal layer 12, and a group VI element single layer 15 formed on the first metal layer 12. And a first III-VI element compound layer 11 having a III-VI element compound formed thereon.

The I-III-VI group compound semiconductor 14 is formed by performing a heat treatment (ie, a selenization treatment) for heating the precursor 24 at a predetermined temperature in a predetermined atmosphere.

[0197] Depending on this, the group VI element alone layer 15 and alkali metal first group III-VI elements compound layer 11 highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Since it can be arranged in the order of high reactivity in the vicinity of the containing substrate 13, the alkali metal is locally and precisely placed at a predetermined position by a predetermined amount.
Thus, doping can be performed by heat treatment. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, the CIS based semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

In addition, since a large crystal grain size is obtained, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

The group VI element simple substance layer 15 is desirably a layer formed using selenium element simple substance.

[0202] Depending on this, in the vicinity of the alkali supply layer 26 and the substrate 13 containing the most reactive elemental selenium elemental alkali metal-rich relative to the alkali metal such as sodium to be eliminated as not neat in a semiconductor process Since it can be arranged, it becomes possible to dope the alkali metal from the alkali supply layer 26 by heat treatment locally and precisely by a predetermined amount at a predetermined position.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

As a result, the CIS based semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, the large crystal grain size can be obtained, so that the high photoelectric conversion efficiency exceeding 10% can be achieved, and the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

Specifically, the precursor 24 is made of Mo formed on a soda glass substrate 13 containing Na metal.
Layer 12 and a single Se layer 15 formed on Mo layer 12 and S
It is desirable to have the Se compound layer 11 formed on the e simple substance layer 15.

It is desirable that the present I-III-VI group compound semiconductor 14 is formed by performing the above-described selenization treatment on such a precursor 24.

Further, as shown in FIG. 2A, the precursor 24 is made of a soda glass substrate 13 containing Na metal.
It is also possible to comprise the Mo layer 12 formed thereon, the Se single layer 15 formed on the Mo layer 12, and the Cu layer 16 formed on the Se single layer 15.

In this case, as shown in FIG. 2B, the I-III-VI group compound semiconductor 14 may be formed by performing the above-described selenization process on the precursor 24. desirable.

[0211] Depending on this, it can be arranged in the vicinity of the substrate 13 containing the most reactive alkali metal group VI element alone layer 15 rich in an alkali metal such as sodium to be eliminated as not neat in a semiconductor process Therefore, the alkali metal is locally and precisely deposited at a predetermined position by a predetermined amount on the substrate 13.
Thus, doping can be performed by heat treatment. Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

As a result, CuIn as a CIS based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

[0213] Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

Next, a third embodiment will be described.

FIG. 3A is a cross-sectional view for explaining a basic structure of a precursor 24 in which a Mo layer 12, an alkali supply layer (Na metal supply layer) 26, and a first III-VI element compound layer 11 are laminated in this order. FIG. Note that, for the same portions as those already described in the first embodiment or the second embodiment (specifically, the film forming conditions, the final film thickness, and the like), the repeated description will be omitted.

The I-III-VI Group Compound Semiconductor 14
Are a Mo layer 12 formed on a substrate 13 such as silicon or quartz glass and an alkali supply layer (Na metal supply layer) 26 formed on the Mo layer 12 while containing Na metal.
a III-VI group element compound layer (Se compound layer) 11 having a Se compound formed on a metal supply layer 26 and S formed on first III-VI element compound layer 11
Group II III-VI element compound layer 20 containing an e-compound
Is formed by executing the above-described selenization process on the precursor 24 having

At this time, InxSe (1-x), which is a selenium compound, is used as the first III-VI group element compound layer 11.
In the case where (0 ≦ x ≦ 1) is used, GaxSe which is a selenium compound is used as the second III-VI group element compound layer 20.
It is desirable to use (1-x).

The first III-VI element compound layer 1
When GaxSe (1-x) is used as 1, the second
As the III-VI group element compound layer 20, InxSe (1
It is desirable to use -x).

[0220] Depending on this, the group III-VI group elements highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process compound layer 11 and the second
Since the group III-VI element compound layer 20 can be arranged in the order of high reactivity near the Na metal supply layer 26 containing an alkali metal, the alkali metal is supplied locally at a predetermined position and precisely by a predetermined amount. The layer 26 can be doped by a heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

Further, by providing the Na metal supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be reduced with respect to a heat treatment requiring a process temperature of about 600 degrees. The substrate 13 can be expanded and has a high softening point, the crystal substrate 13 has a lattice constant and a plane orientation capable of increasing the crystal grain size , and the coefficient of linear expansion is M
There is an effect that various substrates 13 such as the substrate 13 similar to the o-layer 12 can be used.

As a result, the CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

For the same purpose, the I-III-VI group compound semiconductor 14 is composed of a Mo layer 12 formed on a substrate 13 such as silicon or quartz glass and a Mo layer 12 containing Na metal.
The first II having the Na metal supply layer 26 formed on the o-layer 12 and the Se compound formed on the Na metal supply layer 26
I-VI group element compound layer (InxSe (1-x) or Ga
xSe (1-x)) 11 and the second metal layer 16 containing a copper element formed on the first III-VI element compound layer 11
May be formed by executing the above-described selenization process.

[0227] Depending on this, Na metal supply layer 26 containing an alkali metal first group III-VI group element compound layer 11 highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process , The doping treatment of the alkali metal from the Na metal supply layer 26 by a heat treatment can be performed locally and precisely at a predetermined position by a predetermined amount.

Further, there is an effect that the structure of the precursor 24 can be realized so that other processes are not adversely affected as impurities unless heat treatment is applied.

Further, by providing the Na metal supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be reduced with respect to a heat treatment requiring a process temperature of about 600 ° C. The substrate 13 can be expanded and has a high softening point, the crystal substrate 13 has a lattice constant and a plane orientation capable of increasing the crystal grain size , and the coefficient of linear expansion is M
There is an effect that various substrates 13 such as the substrate 13 similar to the o-layer 12 can be used.

As a result, CIS based semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

Next, a fourth embodiment will be described.

FIG. 3 (b) shows the Na metal supply layer 26, Mo
Layer 12, first III-VI element compound layer 11, 2I
FIG. 4 is a cross-sectional view for explaining a basic configuration of a precursor 24 stacked in the order of a II-VI group element compound layer 20.
In the first to third embodiments, the same parts as those already described in the first to third embodiments (specifically, film forming conditions, final film thickness, and the like) will not be described repeatedly.

I-III-VI Group Compound Semiconductor 14
Is the Na metal supply layer 26 formed on the substrate 13 and Na
Metal supply layer 26 and M formed on Na metal supply layer 26
a first III-VI element compound layer (InxSe (1-x) having an Se compound formed on the o layer 12 and the Mo layer 12;
x) and GaxSe (1-x)) 11 and the first III-VI
The precursor 24 having the second III-VI group element compound layer 20 having the Se compound formed on the group element compound layer 11 is formed by performing the above-described selenization treatment.

At this time, InxSe (1-x), which is a selenium compound, is used as the first III-VI group element compound layer 11.
In the case where (0 ≦ x ≦ 1) is used, GaxSe which is a selenium compound is used as the second III-VI group element compound layer 20.
It is desirable to use (1-x).

In addition, the first III-VI group element compound layer 1
When GaxSe (1-x) is used as 1, the second
As the III-VI group element compound layer 20, InxSe (1
It is desirable to use -x).

[0238] Depending on this, the group III-VI group elements highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process compound layer 11 and the second
Since the group III-VI element compound layer 20 can be arranged in the order of high reactivity near the Na metal supply layer 26 containing an alkali metal, the alkali metal is supplied locally at a predetermined position and precisely by a predetermined amount. The layer 26 can be doped by a heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the Na metal supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be reduced with respect to a heat treatment requiring a process temperature of about 600 ° C. The substrate 13 can be expanded and has a high softening point, the crystal substrate 13 has a lattice constant and a plane orientation capable of increasing the crystal grain size , and the coefficient of linear expansion is M
There is an effect that various substrates 13 such as the substrate 13 similar to the o-layer 12 can be used.

As a result, CuIn as a CIS-based semiconductor
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

[0242] Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

To the same effect, the I-III-VI group compound semiconductor 14 is composed of the Na metal supply layer 26 formed on the substrate 13 and the Mo layer 12 formed on the Na metal supply layer 26.
And the first I having the Se compound formed on the Mo layer 12
II-VI group element compound layer (InxSe (1-x) or G
axSe (1-x)) 11 and the second metal layer 1 containing a copper element formed on the first III-VI element compound layer 11
6 may be formed by performing the selenization process described above.

[0245] Depending on this, Na metal supply layer 26 containing an alkali metal first group III-VI group element compound layer 11 highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process , The doping treatment of the alkali metal from the Na metal supply layer 26 by a heat treatment can be performed locally and precisely at a predetermined position by a predetermined amount.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the Na metal supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be reduced with respect to a heat treatment requiring a process temperature of about 600 degrees. The substrate 13 can be expanded and has a high softening point, the crystal substrate 13 has a lattice constant and a plane orientation capable of increasing the crystal grain size , and the coefficient of linear expansion is M
There is an effect that various substrates 13 such as the substrate 13 similar to the o-layer 12 can be used.

As a result, the CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

Next, a fifth embodiment will be described.

FIG. 3C is a cross-sectional view for explaining the basic structure of the precursor 24 in which the Mo layer 12, the Na metal supply layer 26, and the group VI element simple layer 15 are laminated in this order.
In the first to fourth embodiments, the same parts as those already described in the first to fourth embodiments (specifically, film formation conditions, final film thickness, and the like) are not described repeatedly.

I-III-VI Group Compound Semiconductor 14
Are formed on a Mo layer 12 formed on a substrate 13 such as silicon or quartz glass, a Na metal supply layer 26 formed on the Mo layer 12 in a state containing Na metal, and formed on the Na metal supply layer 26. Group III element single layer 15 and first III-V having Se compound formed on group VI element single layer 15
Group I element compound layer (InxSe (1-x) or GaxSe
(1-x)) is formed by executing the above-described selenization processing on the precursor 24 having (11).

[0254] Depending on this, the group VI element alone layer 15 and alkali metal first group III-VI elements compound layer 11 highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Since it can be arranged in the order of high reactivity near the containing Na metal supply layer 26,
The alkali metal can be locally doped at a predetermined position by a predetermined amount and accurately from the Na metal supply layer 26 by a heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the Na metal supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be reduced with respect to a heat treatment requiring a process temperature of about 600 degrees. The substrate 13 can be expanded and has a high softening point, the crystal substrate 13 has a lattice constant and a plane orientation capable of increasing the crystal grain size , and the coefficient of linear expansion is M
There is an effect that various substrates 13 such as the substrate 13 similar to the o-layer 12 can be used.

As a result, the CIS based semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

With the same principle, as shown in FIG.
The I-III-VI group compound semiconductor 14 includes a Na metal supply layer 26 formed on a substrate 13 such as silicon or quartz glass, a Mo layer 12 formed on the Na metal supply layer 26, and a Mo layer 12 formed on the Na metal supply layer 26. Formed Group VI Element Simple Layer 15 and VI
The precursor 24 having the second metal layer 16 having a copper element and formed on the group-group element simple layer 15 may be formed by performing the above-described selenization treatment.

[0261] Depending on this, the vicinity of Na metal supply layer 26 a VI group element alone layer 15 rich in most reactive to alkali metals such as sodium to be eliminated as not neat in a semiconductor process containing an alkali metal Can be placed in
The alkali metal can be locally doped at a predetermined position by a predetermined amount and accurately from the Na metal supply layer 26 by a heat treatment.

Further, there is an effect that the structure of the precursor 24 can be realized so as not to adversely affect other processes as impurities unless heat treatment is applied.

Further, by providing the Na metal supply layer 26 which can be made more alkali-rich than the substrate 13 separately from the substrate 13, the selectivity of the substrate 13 can be reduced with respect to a heat treatment requiring a process temperature of about 600 degrees. The substrate 13 can be expanded and has a high softening point, the crystal substrate 13 has a lattice constant and a plane orientation capable of increasing the crystal grain size , and the coefficient of linear expansion is M
There is an effect that various substrates 13 such as the substrate 13 similar to the o-layer 12 can be used.

As a result, the CIS semiconductor CuIn
Either the Se 2 -based or Cu (In, Ga) Se 2 -based precursor 24 has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

Next, an embodiment of a manufacturing process of the I-III-VI group compound semiconductor 14 will be described with reference to the drawings.

FIG. 4A shows the first metal layer 1 on the substrate 13.
FIG. 4 is a cross-sectional view for explaining a state where
(2) has a first III layer on the first metal layer 12 of FIG.
FIG. 4C is a cross-sectional view for explaining a state in which the group-VI element compound layers 11 are stacked. FIG.
FIG. 4D is a cross-sectional view illustrating a state where the second III-VI element compound layer 20 is stacked on the II-VI element compound layer 11, and FIG. 4D is a cross-sectional view of the second III-VI element compound layer 20 in FIG.
FIG. 4 (5) is a cross-sectional view for explaining a precursor 24 configured by laminating the second metal layer 16 on the group I element compound layer 20, and FIG. 4 (5) shows the precursor 24 of FIG. FIG. 5 is a cross-sectional view for explaining an I-III-VI group compound semiconductor 14 manufactured by processing.

First, as shown in FIG.
Substrate 1 containing Na metal under vacuum of [Torr]
3 (alkaline glass substrate such as soda glass substrate) 20
The substrate was heated to 0 degree, and the Mo layer 12 was
Sputter deposition is performed to a thickness of [μm].

Subsequently, as shown in FIG.
Mo heated to 200 degrees under a vacuum of 5 [Torr]
On the layer 12, GaxSe (1-x) (InxSe (1-x)
x)) deposit 11;

Subsequently, as shown in FIG.
Ga heated to 200 ° C. in a vacuum of 5 [Torr]
xSe (1-x) (InxSe (1-x)) 11
nxSe (1-x) (GaxSe (1-x)) 20 is deposited. Here, GaxSe (1-x) (InxSe
(1-x)) 11 and InxSe (1-x) (Ga
xSe (1-x)) 20 and the total thickness is 10,000
It is desirable to be about [angstrom].

Subsequently, as shown in FIG.
In heated to 200 degrees under a vacuum of 5 [Torr]
xSe (1-x) (GaxSe (1-x)) 20
The u layer 16 is deposited to a thickness of 2000 [angstrom]. By the above process, the precursor 24 can be formed.

Finally, as shown in FIG. 4 (5), the precursor 24 is subjected to the above-described selenization processing to perform II
The II-VI group compound semiconductor 14 can be formed. At this time, it is desirable that the film thickness of the I-III-VI group compound semiconductor 14 after the selenization treatment is approximately 20,000 [angstrom].

Next, the crystal grain size and the sodium content of the conventional I-III-VI group compound semiconductor and the I-III-VI group compound semiconductor manufactured in this embodiment will be compared.

FIG. 5 (a) is a chart for explaining the relationship between the crystal grain size and the sodium content in the I-III-VI group compound semiconductors 14 manufactured using various precursors 24 of CuInSe2 type. , Chart 5
(B) is a chart for explaining the relationship between the crystal grain size and the sodium content in the I-III-VI group compound semiconductor 14 manufactured using various precursors 24 of Cu (In, Ga) Se2 system. is there.

As shown in FIG. 5 (a), CuInSe
Any I prepared using various precursors 24 of type 2
In the III-VI group compound semiconductor 14, also, 1.
It can be seen that a crystal grain size of 3 to 2.0 μm was obtained, and a larger crystal grain size was obtained compared to the crystal grain size shown in FIG. 8 (a). At the same time, the sodium content is 1.
It can also be seen that it has increased from 0 to 1.8.

The measurement of the crystal grain size was derived from observation using a scanning electron microscope, and the sodium content was determined by SIMS (S
secondary Ionization Mass
(Spectroscopy).

Similarly, as shown in FIG.
Any of the I-III-VI group compound semiconductors 1 manufactured using various (In, Ga) Se2 based precursors 24
4 also shows that a crystal grain size of 1.3 to 1.7 μm was obtained. At the same time, it can be seen that the sodium content is as large as 1.0 to 1.9.

From the above results, it is considered that the sodium content in the precursor 24 contributes to increasing the crystal grain size of the I-III-VI group compound semiconductor. In other words, it is considered that the precursor rich in sodium 24 shows higher crystallinity.

As described above, the I-III-VI group compound semiconductor 14 described in the first to sixth embodiments is used as the p-type semiconductor layer 32 as a photocarrier generation layer, and the photocarriers are extracted as photocurrents. First for
By using the metal layer 12 as the electrode 34, the thin-film solar cell 30 can be configured.

According to this, CIS based semiconductor CuI
The crystal grain size can be increased in any of the precursors 24 of the nSe2 system or the Cu (In, Ga) Se2 system.
% As well as higher photovoltaic conversion efficiency, and a longer life of the photocarriers. As a result, a higher photocurrent output in the thin-film solar cell 30 is achieved. The effect that it becomes possible to do it is produced.

[0282]

According to the invention of claim 1 according to the present invention, the group III-VI group element compound layer and the high reactivity of the alkali metals such as sodium to be eliminated as not neat in a semiconductor process Since the 2III-VI group element compound layer can be arranged in the order of high reactivity in the vicinity of the substrate containing the alkali metal, the alkali metal can be locally and precisely doped at a predetermined position from the substrate by a predetermined amount at a predetermined position. Become like Further, there is an effect that a precursor structure can be realized that can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

[0284] Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

[0286] According to the invention of claim 2, the alkali metal first group III-VI group element compound layer rich in reactivity to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Since it can be arranged in the vicinity of the containing substrate, it becomes possible to dope the alkali metal from the substrate by a heat treatment locally and precisely by a predetermined amount at a predetermined position. Further, there is an effect that a precursor structure can be realized that can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

[0288] Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

[0290] according According to the invention described in claim 3, VI group element alone layer or the first high reactivity with respect to an alkali metal such as sodium to be eliminated as not neat in a semiconductor process
Since the group III-VI element compound layer can be arranged in the order of high reactivity near the substrate containing the alkali metal, the alkali metal can be locally doped at a predetermined position and precisely by a predetermined amount from the substrate by heat treatment. Become like
Further, there is an effect that a precursor structure can be realized that can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

[0294] According to the invention of claim 4, the group VI element alone layer rich in most reactive to alkali metals such as sodium to be eliminated as not neat in a semiconductor process containing an alkali metal Because it can be placed near the substrate,
Alkali metal can be locally doped at a predetermined position and precisely by a predetermined amount from a substrate by heat treatment. Further, there is an effect that a precursor structure can be realized that can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Also, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

[0298] According to the invention of claim 5, or the group III-VI group element compound layer rich in reactivity to alkali metals such as sodium to be eliminated as not neat in a semiconductor process first 2III- Since the group VI element compound layer can be arranged in the order of high reactivity near the alkali supply layer containing the alkali metal, doping of the alkali metal from the alkali supply layer by a heat treatment locally and precisely by a predetermined amount at a predetermined position. Be able to process.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer, which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, CuIn as a CIS-based semiconductor
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, a high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

[0304] According to the invention of claim 6, the alkali metal first group III-VI group element compound layer rich in reactivity to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Since it can be arranged in the vicinity of the contained alkali supply layer, it becomes possible to dope the alkali metal from the alkali supply layer with high accuracy and locally by a predetermined amount at a predetermined position.

Furthermore, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Also, by providing an alkali supply layer which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, the CuIn semiconductor CuIn
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

[0310] according According to the invention described in claim 7, VI group element alone layer or the first high reactivity with respect to an alkali metal such as sodium to be eliminated as not neat in a semiconductor process
Since the group III-VI element compound layer can be arranged in the order of high reactivity in the vicinity of the alkali supply layer containing the alkali metal, the alkali metal can be locally and precisely heat-treated from the alkali supply layer at a predetermined position by a predetermined amount. Therefore, the doping process can be performed.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Also, by providing an alkali supply layer which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, the CIS semiconductor CuIn
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

[0316] According to the invention of claim 8, the group VI element alone layer rich in most reactive to alkali metals such as sodium to be eliminated as not neat in a semiconductor process containing an alkali metal Since it can be arranged in the vicinity of the alkali supply layer, the alkali metal can be locally doped at a predetermined position and precisely by a predetermined amount from the alkali supply layer by heat treatment.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer, which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, CuIn as a CIS-based semiconductor
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

[0322] According to the invention of claim 9, or a group III-VI group element compound layer rich in reactivity to alkali metals such as sodium to be eliminated as not neat in a semiconductor process first 2III- Since the group VI element compound layer can be arranged in the order of high reactivity near the alkali supply layer containing the alkali metal, doping of the alkali metal from the alkali supply layer by a heat treatment locally and precisely by a predetermined amount at a predetermined position. Be able to process.

Further, there is an effect that it is possible to realize a precursor structure that can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer, which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, CuIn as a CIS based semiconductor
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

[0328] According to the invention of claim 10, the alkali metal first group III-VI group element compound layer rich in reactivity to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Since it can be arranged in the vicinity of the contained alkali supply layer, it becomes possible to dope the alkali metal from the alkali supply layer with high accuracy and locally by a predetermined amount at a predetermined position.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Also, by providing an alkali supply layer, which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, CuIn as a CIS based semiconductor
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

[0334] According to the invention of claim 11, VI group element alone layer and the group III-VI group elements highly reactive with respect to alkali metals such as sodium to be eliminated as not neat in a semiconductor process Since the compound layer can be arranged in the order of high reactivity in the vicinity of the alkali supply layer containing the alkali metal, the alkali metal can be locally doped at a predetermined position and precisely by a predetermined amount from the alkali supply layer by heat treatment. become.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

In addition, by providing an alkali supply layer which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, CuIn as a CIS-based semiconductor
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

[0340] According to the invention of claim 12, the Group VI element alone layer rich in most reactive to alkali metals such as sodium to be eliminated as not neat in a semiconductor process containing an alkali metal Since it can be arranged in the vicinity of the alkali supply layer, the alkali metal can be locally doped at a predetermined position and precisely by a predetermined amount from the alkali supply layer by heat treatment.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

Further, by providing an alkali supply layer, which can be made more alkali-rich than the substrate, separately from the substrate,
For heat treatment requiring a process temperature of about 600 degrees,
A substrate having a high softening point, a substrate having a lattice constant or plane orientation capable of increasing the crystal grain size , a substrate having a linear expansion coefficient close to that of the first metal layer, etc. There is an effect that various substrates can be used.

As a result, the CIS semiconductor CuIn
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

[0346] According to the invention of claim 13, in addition to the effects according to any one of claims 1 to 12, most reactions to sodium to be eliminated as not neat in a semiconductor process Since the group VI elemental element layer rich in properties can be arranged in the vicinity of the alkali-containing layer containing sodium, it becomes possible to dope the sodium from the alkali-supplying layer locally at a predetermined position with high accuracy by a predetermined amount by heat treatment. .

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS based semiconductor CuIn
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to the fourteenth aspect of the present invention, in addition to the effects of any one of the first to thirteenth aspects, the use of a Group VI element such as selenium, sulfur, or tellurium provides This has the effect of achieving high photocarrier generation efficiency. In particular, selenium and its compounds have the effect that a highly crystalline I-III-VI group compound semiconductor thin film (sodium-containing CIS thin film) can be easily formed.

According to the fifteenth aspect of the present invention, in addition to the effects described in any one of the first to thirteenth aspects, the use of a group III element such as gallium or indium allows a high photocarrier to be obtained. There is an effect that the generation efficiency can be realized.

Further, gallium or indium or a compound thereof has an effect that a thin film of a group I-III-VI compound semiconductor having a high crystallinity (a CIS thin film containing sodium) can be easily formed.

According to the invention of claim 16, claims 1, 2, 5, 6, 7, 9, 10, 11, 12, 13, 1
In addition to the effects described in the item 4 or 15, a semiconductor
In InxSe highly reactive with respect to alkali metals such as sodium to be eliminated as not neat (1-x) and GaxS
Since e (1-x) can be arranged in the order of high reactivity near the alkali metal-containing alkali supply layer or the substrate, the alkali metal is heat-treated from the alkali supply layer by a predetermined amount locally at a predetermined position. Allows doping treatment.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, a high photoelectric conversion efficiency of more than 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

In addition, InxSe (1-x) and GaxSe
By using a group III compound such as (1-x), high photocarrier generation efficiency can be realized, and further, a highly crystalline I-III-VI group compound semiconductor thin film (sodium-containing CIS thin film) Can be easily formed.

According to the seventeenth aspect, an effect similar to that of the sixteenth aspect is obtained.

[0361] According to the invention of claim 18, in addition to the effects described in any one of claims 3,4,7,8,11, or 12, as not neat in a semiconductor process A single element of selenium, which is most reactive with alkali metals such as sodium that is excluded, can be arranged near an alkali supply layer or a substrate containing alkali metals, so that only a predetermined amount of alkali can be locally localized at a predetermined position. The metal can be doped from the alkali supply layer by heat treatment.

Further, there is an effect that a precursor structure can be realized which can prevent other processes from being adversely affected as impurities unless heat treatment is applied.

As a result, the CIS semiconductor CuIn
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of photocarriers can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to the nineteenth aspect of the present invention, in addition to the effect of any one of the first to eighteenth aspects, it is possible to add 600
Metal that has a high melting point,
A metal having a lattice constant or a plane orientation capable of increasing the crystal grain size ;
-It is possible to use a metal or the like similar to the group VI element compound layer.

As a result, CuIn which is a CIS-based semiconductor
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

[0368] Also, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, there is an effect that the output of the photocurrent can be increased.

Further, the first metal layer (that is, the molybdenum metal layer) 12 containing a high melting point metal such as molybdenum, tungsten, and chromium comprises a substrate, a first III-VI group element compound layer (selenium compound layer) 11, Forming an I-III-VI group compound semiconductor without excellent adhesion between the group element element layer and the film and without peeling or cracking of the film even when the precursor is exposed to a high temperature process. This has the effect of being able to perform.

Aluminum, which has the second highest conductivity next to the noble metal, is a suitable amount of wiring material for a low-temperature process using CVD or the like.

[0372] Polysilicon or metal silicide commonly used in the LSI process is an amount of wiring material suitable for a low-temperature process using CVD or the like. By using such polysilicon or metal silicide for the first metal layer, the Si and GaAs semiconductor devices are
-III-VI compound semiconductors (sodium-containing CI
(S layer) 14 can be connected using a conventional semiconductor process. In other words, a process for fabricating an I-III-VI group compound semiconductor (sodium-containing CIS) 14 can be included in a process for fabricating an integrated circuit using Si or GaAs, and as a result, I-III-
It is possible to achieve an OEIC that is realized as an LSI by using the group VI compound semiconductor (sodium-containing CIS) 14 as a photoelectric conversion unit.

[0373] According to the invention of claim 20, in addition to the effects according to any one of claims 1 to 19, an alkali metal such as sodium to be eliminated as not neat in a semiconductor process On the other hand, since the group VI elemental element layer having the highest reactivity can be disposed near the alkali supply layer containing the alkali metal, the alkali metal is locally and precisely removed from the alkali supply layer at a predetermined position by a predetermined amount. Through the heat treatment, the doping process can be performed efficiently and with good controllability.

Further, by providing a molybdenum layer having a thickness of about 1 to 2 μm, it is possible to realize a precursor structure which can prevent other processes from being adversely affected as impurities unless heat treatment is applied. It works.

In addition, there is an effect that sufficient strength can be maintained for heat treatment requiring a process temperature of about 600 degrees.

As a result, CuIn as a CIS based semiconductor
Either the Se2-based or Cu (In, Ga) Se2-based precursor has the effect of increasing the crystal grain size.

Further, by obtaining a large crystal grain size, high photoelectric conversion efficiency exceeding 10% can be achieved, and further, the life of the photocarrier can be extended. It has the effect of becoming

As a result, it is possible to increase the output of the photocurrent.

According to the twenty-first aspect of the present invention, in addition to the effects of any one of the sixteenth to twentieth aspects, selenium having a sufficient doping amount can be implanted into the precursor as a dopant, and selenium-rich It is possible to obtain an effective I-III-VI group compound semiconductor.

According to the twenty-second aspect of the present invention, in addition to the effect of the twenty-first aspect, by controlling the acceleration voltage, a sufficiently doped amount of selenium can be used as a dopant at a predetermined position in the precursor. Selenium-rich high-quality I-III-
An effect is obtained that a group VI compound semiconductor can be obtained.

According to the twenty-third aspect of the present invention, in addition to the effects of the first aspect, the CIS
CuInSe2 or Cu (In, G)
a) It is possible to increase the crystal grain size in any of the precursors of the Se2 series, and further to achieve high photoelectric conversion efficiency exceeding 10% by obtaining a large crystal grain size. As a result, the life of the photocarrier can be prolonged, and as a result, the output of the photocurrent in the thin-film solar cell can be increased.

[Brief description of the drawings]

FIG. 1A is a cross-sectional view for explaining a basic configuration of a precursor having a group III-VI element compound layer and a group III-VI element compound layer, and FIG.
FIG. 2B is a cross-sectional view illustrating a basic configuration of the I-III-VI group compound semiconductor manufactured using the precursor of FIG.

FIG. 2A is a cross-sectional view for explaining a basic configuration of a precursor having a group III-VI element compound layer and a group VI element simple substance layer, and FIG.
I-III-V prepared using the precursor of (a)
FIG. 1 is a cross-sectional view for explaining a basic configuration of a group I compound semiconductor.

FIG. 3A shows a first metal layer, an alkali supply layer,
FIG. 3B is a cross-sectional view for explaining a basic configuration of a precursor laminated in the order of the III-VI group element compound layers, and FIG. 3B is an alkali supply layer, a first metal layer, and a first III layer.
FIG. 3C is a cross-sectional view for explaining a basic configuration of a precursor in which a -VI group element compound layer and a second III-VI group compound layer are stacked in this order, and FIG. 3C illustrates a first metal layer, an alkali supply layer, FIG. 3 is a cross-sectional view for explaining a basic configuration of a precursor laminated in the order of a group VI element single layer, and FIG.
(D) is a cross-sectional view for explaining a basic configuration of a precursor in which an alkali supply layer, a first metal layer, and a group VI element single layer are stacked in this order.

FIG. 4A is a cross-sectional view for explaining a state in which a first metal layer is stacked on a substrate, and FIG. 4B is a cross-sectional view of FIG. FIG. 4 (3) is a cross-sectional view for explaining a state in which a first III-VI group element compound layer is laminated on FIG. 4 (b). FIG. 4 (4) is a cross-sectional view for explaining a state in which the group III element compound layers are stacked, and FIG.
FIG. 4 (5) is a cross-sectional view for explaining a precursor formed by laminating a second metal layer on the second III-VI group element compound layer of (3), and FIG. 4 (5) is a precursor of FIG. FIG. 4 is a cross-sectional view for explaining a group I-III-VI-based compound semiconductor manufactured by performing a selenization treatment on.

FIG. 5A is a table for explaining a relationship between a crystal grain size and a sodium content in an I-III-VI group compound semiconductor manufactured using various CuInSe 2 -based precursors, FIG. 5B shows Cu (I
3 is a table for explaining the relationship between the crystal grain size and the sodium content in an I-III-VI group compound semiconductor manufactured using various precursors of (n, Ga) Se2 series.

FIG. 6 is a diagram for explaining the first conventional example, and is a cross-section for explaining a precursor using solid-phase selenization technology and an I-III-VI group compound semiconductor manufactured using the precursor. FIG.

FIG. 7 is a diagram for explaining a second conventional example, and is a cross-section for explaining a precursor using a vapor-phase selenization technique and an I-III-VI group compound semiconductor manufactured using the precursor. FIG.

FIG. 8 (a) shows CuInS using the solid-state selenization technology of the first conventional example or the gas-phase selenization technology of the second conventional example.
I-III prepared using various precursors of e2 series
FIG. 8 is a chart for explaining the relationship between the crystal grain size and the sodium content in the group-VI compound semiconductor.
(B) shows Cu (In, Ga) Se using the solid-phase selenization technology of the first conventional example or the gas-phase selenization technology of the second conventional example.
3 is a table for explaining the relationship between the crystal grain size and the sodium content in Group 2 precursor precursors and I-III-VI group compound semiconductors manufactured using the precursors.

[Description of Signs] 11 First III-VI group element compound layer (selenium compound layer) 12 First metal layer (molybdenum metal layer) 13 Substrate (alkali glass substrate) 14 I-III-VI group compound semiconductor (sodium-containing CIS) Layer) 15 Group VI element simple layer (Selenium simple layer) 16 Second metal layer (Cu) 20 Second III-VI group element compound layer (Selenium compound layer) 24 Precursor 26 Alkali supply layer 30 Thin film solar cell 32 P-type semiconductor layer (I-III-VI group compound semiconductor) 34 electrode

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tsuyoshi Ikeya 1500 Onjuku Yasushi Sogyo Co., Ltd., Susono City, Shizuoka Prefecture (72) Inventor Shinichi Nakagawa 1500 Yashiro Sogyo Co., Ltd. 1500 Yazaki Sogyo Co., Ltd., Susono-shi, Shizuoka Prefecture (72) Inventor Kazuhiro Toyota 1500 sharks, Onozu, Shizuoka Prefecture, Yazaki Sogyo Co., Ltd. Inventor Masaharu Ishida 1500 Onjuku, Susono City, Shizuoka Prefecture Inside Yazaki Corporation

Claims (23)

[Claims] 1. A group I-III-VI compound semiconductor, comprising: a first metal layer formed on a substrate containing an alkali metal; and a group III-VI element compound formed on the first metal layer. A precursor having a first III-VI element compound layer having the formula III and a second III-VI element compound layer having a III-VI element compound formed on the first III-VI element compound layer in a predetermined atmosphere. A group I-III-VI compound semiconductor formed by performing a heat treatment of heating at a predetermined temperature. 2. A group I-III-VI compound semiconductor, comprising: a first metal layer formed on a substrate containing an alkali metal; and a group III-VI element compound formed on the first metal layer. Heat treatment is performed to heat a precursor having a first III-VI element compound layer having the above and a second metal layer having a copper element formed on the first III-VI element compound layer at a predetermined temperature in a predetermined atmosphere. A group I-III-VI compound semiconductor formed by the following steps. 3. A group I-III-VI compound semiconductor, comprising: a first metal layer formed on a substrate containing an alkali metal; and a group VI element simple substance layer formed on the first metal layer. The
It is formed by performing a heat treatment of heating a precursor having a first III-VI element compound layer having a III-VI element compound formed on a group VI element single layer at a predetermined temperature in a predetermined atmosphere. A group I-III-VI group compound semiconductor, which is characterized in that: 4. A group I-III-VI compound semiconductor, comprising: a first metal layer formed on a substrate containing an alkali metal; and a group VI element simple substance layer formed on the first metal layer. The
Formed by performing a heat treatment of heating a precursor having a second metal layer having a copper element formed on a group VI element simple substance layer at a predetermined temperature in a predetermined atmosphere. III-VI compound semiconductors. 5. An I-III-VI group compound semiconductor, comprising: an alkali supply layer formed on a substrate; a first metal layer formed on the alkali supply layer; and an alkali supply layer formed on the first metal layer. A first group III-VI element compound layer having a group III-VI element compound formed thereon and a layer formed on the first group III-VI element compound layer
I-III- formed by performing a heat treatment of heating a precursor having a second III-VI element compound layer having a III-VI element compound at a predetermined temperature in a predetermined atmosphere. Group VI compound semiconductor. 6. An I-III-VI group compound semiconductor, comprising: an alkali supply layer formed on a substrate, a first metal layer formed on the alkali supply layer, and a first metal layer formed on the first metal layer. A precursor having a first III-VI element compound layer having a III-VI element compound and a second metal layer having a copper element formed on the first III-VI element compound layer in a predetermined atmosphere in a predetermined atmosphere. A group I-III-VI compound semiconductor formed by performing a heat treatment of heating at a temperature. 7. An I-III-VI group compound semiconductor, comprising: an alkali supply layer formed on a substrate, a first metal layer formed on the alkali supply layer, and a first metal layer formed on the first metal layer. Formed on the group VI element simple substance layer and the group VI element simple substance layer
Formed by performing a heat treatment of heating a precursor having a first III-VI element compound layer having a III-VI element compound at a predetermined temperature in a predetermined atmosphere. I-III- Group VI compound semiconductor. 8. An I-III-VI group compound semiconductor, comprising: an alkali supply layer formed on a substrate, a first metal layer formed on the alkali supply layer, and a first metal layer formed on the first metal layer. Formed by performing a heat treatment of heating a precursor having a single group VI element layer and a second metal layer having a copper element formed on the single group VI element layer at a predetermined temperature in a predetermined atmosphere. A group I-III-VI group compound semiconductor, which is characterized in that: 9. A group I-III-VI compound semiconductor, comprising: a first metal layer formed on a substrate; and an alkali supply layer formed on the first metal layer while containing an alkali metal. A first III-VI element compound layer having a III-VI element compound formed on the alkali supply layer and the first III-VI element compound layer;
Formed by performing a heat treatment of heating a precursor having a second III-VI element compound layer having a III-VI group compound formed on the group III element compound layer at a predetermined temperature in a predetermined atmosphere, I-III-VI group compound semiconductors, characterized in that: 10. A group I-III-VI compound semiconductor, comprising: a first metal layer formed on a substrate; and an alkali supply layer formed on the first metal layer while containing an alkali metal. A first III-VI element compound layer having a III-VI element compound formed on the alkali supply layer and the first III-VI element compound layer;
I-III formed by performing a heat treatment of heating a precursor having a second metal layer having a copper element formed on a group III element compound layer at a predetermined temperature in a predetermined atmosphere. -Group VI compound semiconductor. 11. A group I-III-VI compound semiconductor, comprising: a first metal layer formed on a substrate; and an alkali supply layer formed on the first metal layer while containing an alkali metal. A precursor having a group VI element single layer formed on the alkali supply layer and a first III-VI group compound layer containing a III-VI element compound formed on the group VI element single layer is placed in a predetermined atmosphere. A group I-III-VI group compound semiconductor formed by performing a heat treatment of heating at a predetermined temperature in the above. 12. A group I-III-VI compound semiconductor, comprising: a first metal layer formed on a substrate; and an alkali supply layer formed on the first metal layer while containing an alkali metal. A group VI element single layer formed on the alkali supply layer and a second group containing a copper element formed on the group VI element single layer;
A group I-III-VI compound semiconductor formed by performing a heat treatment of heating a precursor having a metal layer at a predetermined temperature in a predetermined atmosphere. 13. The group I-III-VI compound semiconductor according to claim 1, wherein the alkali metal is sodium. 14. The group I-III-VI compound semiconductor according to claim 1, wherein the group VI element is any one of selenium, sulfur and tellurium. 15. The group I-III-VI compound semiconductor according to claim 1, wherein the group III element is gallium or indium. 16. The method according to claim 16, wherein the first III-VI element compound layer is In.
The second III-VI element compound layer has xSe (1-x), and the second III-VI group element compound layer has GaxSe (1-x).
I-III- described in 0, 11, 12, 13, 14, or 15
Group VI compound semiconductor. 17. The method according to claim 17, wherein the first group III-VI element compound layer is Ga
The second III-VI element compound layer has xSe (1-x), and the second III-VI group element compound layer has InxSe (1-x).
I-III- described in 0, 11, 12, 13, 14, or 15
Group VI compound semiconductor. 18. The method according to claim 3, wherein the group VI element simple substance layer is a layer formed using selenium element simple substance.
I-II according to any one of 4, 7, 8, 11, or 12
I-VI group compound semiconductor. 19. The method according to claim 19, wherein the first metal layer is made of molybdenum, tungsten, chromium, polysilicon, metal silicide,
19. I-III-VI according to any one of claims 1 to 18, wherein the layer is formed using aluminum or aluminum.
Group compound semiconductor. 20. The group I-III-VI compound according to claim 1, wherein the first metal layer is a molybdenum layer having a thickness of 1 to 2 μm. semiconductor. 21. The heat treatment according to claim 16, wherein the heat treatment is a selenization treatment in which the precursor is heated in a selenium vapor atmosphere to inject selenium into the precursor. The I-III-VI group compound semiconductor according to [1]. 22. Instead of the selenization treatment, selenium is ionized, and a predetermined acceleration voltage is applied between the ionized selenium and the precursor to inject the accelerated selenium ions into the precursor. 22. The I-III-VI group compound semiconductor according to claim 21, wherein an ion implantation process is performed. 23. A photocarrier generation layer comprising the I-
23. A semiconductor device comprising: a p-type semiconductor layer using a III-VI group compound semiconductor; and at least an electrode using the first metal layer for extracting the photocarriers as a photocurrent. A thin-film solar cell using the I-III-VI group compound semiconductor according to any one of the above.