JPH05275331A - Manufacture of chalocopyrite thin film and solar cell - Google Patents

Abstract

PURPOSE:To provide a manufacture of chalcopyrite thin film which has stoichiometric rate composition, pn conductive form having little lattice defects and excess impurities, and can control conductivity. CONSTITUTION:When crucibles containing Cu, In, and Se are heated and vapor deposited on a glass substrate 30 where Mo metal film is formed on part of the surface in vacuum of 10<-7> Torr, nitrogen ions excited with an ion gun are simultaneously injected by being accelerated with the accelerating voltage of 150V, and form a CuInSe2:N thin film 2. This thin film having a chalcopyrite structure is put in a silica tube, and heated with the use of a heater 4 while making flow in nitrogen gas 3, and then heat treatment is conducted for one hour at the temperature of 500 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a chalcopyrite thin film and a thin film solar cell using the chalcopyrite thin film obtained by the method.

[0002]

2. Description of the Related Art Group I, Group III, Group VI elements or Group II
A chalcopyrite structure semiconductor, which is a compound of group IV and group V elements, is, for example, I-III-VI ₂ or II-IV-V ₂ (where
The group I element is Cu, Ag, etc., the group III element is Al, Ga, In, etc., and the group VI element is S, Se,
Compounds such as Te, Zn, Cd, etc. as group II elements, Si, Ge, Sn, etc. as group IV elements, and P, As, Sb, etc. as group V elements are known.
Materials having different band gaps can be obtained in a wide range depending on the constituent elements, and materials having a large light absorption coefficient can be obtained. Therefore, they are expected to be applied to solar cells and light emitting devices.

Since it is important to form a pn junction for application to such an element, it is necessary to control the conductivity type and carrier density. Conventionally, when controlling the pn conduction type of a chalcopyrite thin film, a group I element and a group III element, which are constituent elements of a chalcopyrite compound, or II.
Methods have been used in which the compositional ratio of group IV elements to group IV elements is varied.

For example, in the case of CuInSe ₂ thin film,
The composition ratio is Cu which is a group I element rather than In which is a group III element.
When there are more, the type is p-type, and when it is the opposite, the type is n-type. In this case, since the composition ratio is shifted, many lattice defects are generated, problems such as precipitation of excess components or appearance of heterophasic compounds other than chalcopyrite structure occur, and these cause electrical characteristics such as mobility and light absorption. The optical characteristics such as the coefficient deteriorate. In addition, it has been reported that it is difficult to control the carrier concentration and conductivity by changing the composition ratio (for example, Knowfi et al., Applied Physics Letter, R. Noufi et al., Appl. Phys. Lett). ., 45 (1984)
p.668).

On the other hand, when the method of manufacturing a chalcopyrite thin film in which vacuum evaporation is performed while irradiating an ion beam is used, irradiation is performed regardless of the composition ratio deviation, that is, at a composition ratio satisfying the stoichiometric ratio. It is possible to control the carrier concentration and the conductivity depending on the p- and n-type conductivity types and the irradiation ion density depending on the ions. However, disorder of the chalcopyrite structure due to ion irradiation has been observed, and a thin film having excellent crystallinity has not been obtained.

[0006]

When a chalcopyrite thin film is used to manufacture, for example, a solar cell, pn
It is necessary to make a bond. When a pn junction of a chalcopyrite thin film is produced by the composition ratio shift as described above, carrier recombination is increased due to precipitation of lattice defects and excess components, appearance of a heterophase compound other than the chalcopyrite structure, and the open circuit voltage of the solar cell. Also, there are problems such as a decrease in short-circuit current.

On the other hand, in a film produced by vapor deposition while irradiating with an ion beam, a p- or n-type is obtained by the irradiation ions with a stoichiometric composition, so that a hetero-phase compound other than chalcopyrite structure or excess Although the precipitation of the components can be prevented, lattice defects and the like due to the disorder of the chalcopyrite structure caused by ion irradiation become the center of carrier recombination, which causes a reduction in the open circuit voltage and short circuit current when applied to, for example, solar cells. There are problems such as.

The present invention has improved the drawbacks that many lattice defects occur, problems such as precipitation of excess components and appearance of heterophasic compounds other than chalcopyrite structure are solved, and therefore electrical properties such as mobility and light absorption. There is little risk of deterioration of optical properties such as the coefficient, the carrier concentration and conductivity can be easily controlled, the disorder of the chalcopyrite structure is small, and the crystallinity of the composition ratio satisfying the stoichiometric ratio It is an object of the present invention to provide an excellent method for producing a chalcopyrite thin film, and a solar cell with less reduction in open circuit voltage and short circuit current.

[0009]

In order to achieve the above object, the method for producing a chalcopyrite thin film according to the present invention comprises vacuum deposition or sputtering while irradiating an amorphous or crystalline or metal substrate with an ion beam. It is characterized in that the chalcopyrite thin film produced by vapor deposition or low pressure vapor phase chemical reaction vapor deposition is heat-treated in a gas atmosphere.

In the method for producing the chalcopyrite thin film, the heat treatment in a gas atmosphere is a method in which the heat treatment is performed in a gas atmosphere while vaporizing the powder of the group V or VI element which is a constituent element of the chalcopyrite thin film. Preferably.

In the method for producing a chalcopyrite thin film, it is preferable that the atmosphere gas for the heat treatment in a gas atmosphere is at least one kind of gas selected from hydrogen, helium, nitrogen and argon.

Further, the method for producing a chalcopyrite thin film according to the present invention comprises:
The chalcopyrite thin film produced by vacuum deposition, sputter deposition, or reduced pressure vapor phase chemical reaction deposition while irradiating with an ion beam is used in vacuum to remove the group V or VI elements that are the constituent elements of the chalcopyrite thin film. It is characterized in that the thin film is heat-treated while being evaporated near the thin film.

The thin-film solar cell of the present invention is a thin-film solar cell using a chalcopyrite thin film obtained by any one of the above-mentioned manufacturing methods as a light absorption layer.

[0014]

The function of the chalcopyrite thin film of the present invention is as follows:
The crystallinity is recovered by heat-treating the chalcopyrite thin film produced while irradiating with an ion beam in a gas atmosphere. Therefore, factors that hinder electrical characteristics such as lattice defects are reduced, and the characteristics are improved.

Further, in the method for producing a chalcopyrite thin film of the present invention, the heat treatment is performed while evaporating the powder of the group V or group VI element constituting the chalcopyrite thin film, whereby the group V or VI element in the thin film is treated. It is preferable because evaporation can be prevented, the composition ratio deviation can be further reduced, and the crystallinity can be recovered.

In the method for producing a chalcopyrite thin film according to the present invention, hydrogen, nitrogen, helium,
It is preferable to use at least one kind of gas selected from argon because the reaction between the gas and the chalcopyrite thin film can be prevented. Furthermore, a chalcopyrite thin film produced by irradiating hydrogen ions or nitrogen ions,
Heat treatment in a hydrogen atmosphere or a nitrogen atmosphere is preferable because it is possible to prevent desorption of hydrogen or nitrogen from the chalcopyrite thin film.

Further, in the method for producing a chalcopyrite thin film of the present invention, by adopting a method of heat treatment in a vacuum, the chalcopyrite thin film whose crystallinity has been restored is exposed to the atmosphere without any other material or conductive material. form,
It is possible to deposit chalcopyrite thin films with different conductivity. Therefore, it is possible to prevent the generation of foreign matters and the accumulation of impurities in the atmosphere due to the oxidation of the thin film surface and the like, which are caused by the exposure to the atmosphere, and it is possible to reduce the carrier recombination centers at the interface with the laminated film.

By the above manufacturing method, a chalcopyrite thin film having excellent crystallinity, whose conduction type and carrier density are controlled by irradiation ions, can be obtained. In addition, since the solar cell of the present invention uses the chalcopyrite thin film obtained by any one of the above-described manufacturing methods as the light absorption layer, carrier recombination centers generated by lattice defects, foreign substances at the pn junction interface, or the like. Therefore, a solar cell having high conversion efficiency can be provided.

[0019]

EXAMPLE In the present invention, as the substrate, an amorphous, crystalline or metal substrate is usually used as described above.

Examples of the amorphous substrate include glass and quartz substrates. Further, as the crystal substrate, for example, ZnSe, ZnS, ZnTe, CdS, C
Examples thereof include dSe, CdTe, GaAs, GaP, InP, etc., which can be appropriately selected and used according to the constituent elements of the chalcopyrite thin film, and in particular ZnSe, ZnS, C.
dS, GaAs, GaP, etc. are preferably used. In addition, various metals can be used as the metal substrate, and although not particularly limited, when applied to a solar cell, in addition to Mo, Al, Au, Pt and the like and alloys containing these metals are used. When used as an alloy, an Au-Ti alloy or the like is preferably used.

Examples of chalcopyrite include I-III-
VI₂Or II-IV-V₂(Here, the group I element is C
Group III elements such as u and Ag include Al, Ga and In.
However, as the group VI element, a group II element such as S, Se, Te, etc.
Is Zn, Cd, etc., and Group IV elements are Si, G
e, Sn, etc., and P, As, Sb as V group elements
, Etc.) are known, and they are appropriate depending on the purpose.
It can be selected and used. Give a few representative examples
Then, CuInSe₂, CuInS₂, CuAlS ₂Na
However, it is also a typical mixed crystal of a combination of multiple components.
What is Cu (Ga_1-xIn_x) Se₂(However, 0
<X <1), etc., but especially limited to these
is not.

The formation of these chalcopyrite thin films by the vacuum vapor deposition method cannot be unconditionally specified because the conditions vary depending on the composition of chalcopyrite, the substrate, etc., but a vacuum of 10 ^-3 Torr or less is usually used. Be done. Also in the case of the sputter deposition method, the conditions differ depending on the composition of chalcopyrite, the substrate, etc., and therefore cannot be specified unconditionally, but usually 10 ^-4 to 10 ^-2 Tor
A vacuum of about r is used. Further, in the case of the reduced pressure vapor phase chemical reaction vapor deposition method, the conditions differ depending on the composition of chalcopyrite, the substrate, etc., and therefore cannot be specified unconditionally, but it is a method of reacting under a vacuum condition of usually 10 ^-2 Torr or less. Etc. are common.

The ion beam is not particularly limited, but a normal ion gun may be used to irradiate an appropriate ion beam such as nitrogen ion, hydrogen ion, chlorine ion, argon ion, or helium ion, if necessary.
The irradiation conditions of the ion beam for irradiation differ depending on the ion generator used, the type of chalcopyrite thin film to be produced, the type and amount of impurities added, or the distance between the ion generator and the substrate, so it is not possible to specify. Although not possible, a preferable condition can be appropriately selected according to the condition from the range of 50 V to 2 KV in the normal accelerating voltage.

As the atmosphere gas for the heat treatment in the gas atmosphere, it is preferable to use at least one gas selected from hydrogen, nitrogen, helium, and argon.
These gases are preferably used because it is difficult for the gas and the chalcopyrite thin film to react with each other. Further, it is particularly preferable that the chalcopyrite thin film produced by irradiation with hydrogen ions or nitrogen ions is heat-treated in a hydrogen atmosphere or a nitrogen atmosphere because hydrogen or nitrogen in the chalcopyrite thin film can be prevented from being released.

The heat treatment in a vacuum is not particularly limited, but it is preferable to use a vacuum of 1 Torr or less. Also, the heat treatment conditions are different depending on the elements constituting the chalcopyrite structure, the types of added impurities, the types of substrates used, etc., and therefore cannot be clearly specified, but usually in the range of 200 ° C to 1000 ° C. It is possible to select and use the optimum heat treatment conditions that can recover the crystallinity and improve the electrical characteristics.

V which constitutes the chalcopyrite thin film
When heat treatment is performed while evaporating the powder of group VI or VI element, the vaporized group V or VI element is
It is preferable to use the same V group or VI group element as the V group or VI group element that constitutes the chalcopyrite thin film, since it is possible to prevent the vaporization of the V group or VI group element in the thin film and to reduce the composition ratio deviation. Can be reduced.

In order to make the present invention easier to understand, the present invention will be described below by using more specific examples. FIG. 1 is a conceptual diagram of an apparatus used when heat-treating a chalcopyrite thin film according to an embodiment of the present invention in a gas atmosphere.

Each of the crucibles containing Cu, In, and Se was heated at 1140 ° C., 860 ° C., and 200 ° C. to obtain 10 ^−7.
In the vacuum of Torr, at the time of vapor deposition on the glass substrate 30 having a Mo metal film formed on a part of the surface, nitrogen ions excited by an ion gun (ECR ion gun) using electron cyclotron resonance were simultaneously accelerated to an acceleration voltage of 150 V. The CuInSe ₂ : N thin film 2 having a chalcopyrite structure manufactured by accelerating and irradiating with is put into a quartz tube 1 and heated with a heater 4 while flowing a nitrogen gas 3 to 300 ° C. and 400 ° C., respectively. Heat treatment was performed at a temperature of 500 ° C. for 1 hour. To investigate the recovery of crystallinity, a wavelength of 51
Raman scattering spectra were measured using a 4.5 nm argon laser. The results are shown in Figure 2. FIG. 2 is a graph showing changes in Raman scattering spectrum with respect to heat treatment temperature.

Solid line 5 in FIG. 2 represents the Raman scattering spectrum of the film which was not heat-treated, solid line 6 represents the film which was heat-treated at 300 ° C., solid line 7 represents the film which was heat-treated at 400 ° C. and solid line 8 represents the film which was heat-treated at 500 ° C. .. A peak is observed around 170 cm ^{-1 in} all films. This proves that Se exists in the arrangement of chalcopyrite structure in CuInSe ₂ . However, the unheated film 5, the film 6 heat-treated at 300 ° C., and the film 7 heat-treated at 400 ° C.
The peak of the Raman scattering spectrum around 170 cm ^{−1 of 1} shows a distorted shape, and the peak half width is wide. That is,
It can be seen that the chalcopyrite structure is disordered. On the other hand, 170 cm for the film heat treated at 500 ° C
The peak near ^-1 is sharpened and the half-width of the peak is narrow. Therefore, it is considered that the disorder of the chalcopyrite structure caused by the ion irradiation was reduced and the crystallinity was recovered.

FIG. 3 is a graph showing the change in conductivity with respect to the heat treatment temperature, and the solid line 9 shows the difference in conductivity with respect to the heat treatment temperature. Non-heat treated film 11 and 300 ° C and 4
The conductivity of the films heat-treated at 00 ° C is almost equal,
The value is as low as 0 ⁻² / Ωcm, whereas the value of the film heat-treated at 500 ° C. is as high as 0.7 / Ωcm. It is considered that this is because the factors that hindered the electric conduction were removed due to the reduction of lattice defects and extra nitrogen that entered the interstitial spaces. From this, it is considered that the crystallinity was recovered by the heat treatment at 500 ° C.

Next, a chalcopyrite thin film CuInSe
An example of a method of heat-treating while vaporizing Se powder, which is the constituent element of No. ₂ , will be described. CuInSe formed in the quartz tube 1 of FIG. 1 by the same manufacturing method as that of the above-mentioned embodiment.
₂ : N thin film 2 and Se powder were put in and heated with a heater 4 while introducing nitrogen gas 3 to 300 ° C.,
Heat treatment was performed at a temperature of 400 ° C. and 500 ° C. for 1 hour. The result of the Raman scattering spectrum was almost the same as the result of FIG. The difference from the above example is the difference in conductivity. A broken line 10 in FIG. 3 shows a change in conductivity when heat treatment is performed using Se powder. Similar to the above-mentioned examples, the conductivity of the film heat-treated at 500 ° C. shows a high value. Further, it is 8 / Ωcm, which is an order of magnitude higher than the conductivity of the film heat-treated at 500 ° C. in the above example. It is considered that this is because the heat treatment while vaporizing the Se powder can prevent the vaporization of the Se element from the CuInSe ₂ film, which is considered to have occurred in the above-mentioned embodiment.

In the same manner as in the above two embodiments,
Even when hydrogen, helium, argon, or a mixed gas thereof was used as the atmosphere gas instead of nitrogen, the changes in the Raman scattering spectrum and the conductivity with respect to the heat treatment temperature were similar to the results shown in FIGS. 2 and 3.

Next, a method of heat-treating the chalcopyrite thin film in vacuum will be described. When heat-treated in vacuum,
Among the constituent elements of chalcopyrite thin film, V with high vapor pressure
Group VI or VI elements evaporate from the film. Therefore, the composition ratio of the constituent elements of the chalcopyrite thin film is shifted, and the lattice defects are increased. Therefore, a method of performing heat treatment while vaporizing the group V or VI element near the chalcopyrite thin film is used. In this case, above a certain heat treatment temperature, the evaporated group V or VI element does not deposit or react in the chalcopyrite thin film and the group V or VI element fills the vicinity of the thin film, so V
Evaporation of Group VI or VI elements can be prevented.

FIG. 4 is a conceptual diagram of an apparatus of one embodiment used for heat treatment while evaporating Se element in vacuum.
In the vacuum container 12, a CuI film was formed on the glass substrate 30 having a Mo metal film formed on a part of its surface in the same manner as in the above embodiment.
Immediately after forming the nSe ₂ : N thin film 2, heat treatment was performed using the substrate heater 14 while evaporating the Se element from the Se vapor deposition source 13. Reference numeral 15 is a power source for the substrate heater 14, and 16 is an exhaust port connected to a vacuum pump (not shown).

When the heat treatment temperature is 150 ° C. or lower, CuInS
A Se deposited film was formed on the e ₂ thin film, but at a temperature higher than that, the Se deposited film was not formed. Temperature 300 ℃, 400
The Raman scattering spectrum after heat treatment at 500 ° C. and 500 ° C. for 1 hour was almost the same as the result shown in FIG. 2, and a sharp peak was observed near 170 cm ⁻¹ at the heat treatment temperature of 500 ° C.
Therefore, it is considered that the crystallinity is recovered by heat treatment at 500 ° C. for 1 hour. Next, the change of the conductivity with respect to the heat treatment temperature is almost the same as the result shown by the broken line 10 in FIG.
Since the deficiency of the element e did not occur, the conductivity showed a high value.

Although the heater is used as the heating means in the above embodiments, the same effect can be obtained by using an infrared lamp or laser light. Next, the effectiveness of the present invention will be described for chalcopyrite thin films other than CuInSe ₂ . When a target of Cu and In was irradiated with an ion beam accelerated at 1 KV in a mixed gas atmosphere of 90% Ar and 10% H ₂ S with a vacuum degree of 10 ^-3 Torr to perform sputtering,
A CuInS ₂ : N thin film was manufactured by a method of accelerating nitrogen ions at 300 V and simultaneously irradiating the substrate. A glass substrate having a Mo metal film formed on a part of its surface is used as the substrate, and the substrate temperature during film formation is 300 ° C. or higher (350 ° C., 40 ° C.).
0 ° C. and 450 ° C.). The thin film is placed in a quartz tube for 10
% H ₂ S and 90% Ar mixed gas,
It heat-processed at the temperature of 0 degreeC or more for 1 hour. In the film heat-treated at a temperature of 450 ° C. or higher, recovery of crystallinity was confirmed by Raman scattering spectrum. In addition, the electric conductivity of the film before heat treatment was 10 ⁻⁴ / Ωcm or less, whereas that of the film heat-treated at 450 ° C. was about 1 / Ωcm, and the resistance was lowered.

In addition, C_FiveH_FiveCu ・ P (C₂H_Five)₃When
(C₂H_Five)₃Al organic metal and H ₂S for 10^-3Torr
When performing a low pressure vapor phase chemical reaction vapor deposition method of reacting in vacuum
And 15 chlorine ions excited by the ECR ion gun
GaA at a substrate temperature of 600 ° C. while accelerating and irradiating with 0 V
n-type CuA crystal grown on s substrate and ZnSe substrate
ls₂: Cl thin film in argon atmosphere and S in vacuum
Heat treatment was performed while evaporating.

From the Raman scattering spectrum, it was confirmed that the crystallinity of the CuAlS ₂ : Cl thin film heat-treated at a temperature of 400 ° C. for 1 hour was recovered by both methods. As a result of examining the distribution of chlorine element in the film thickness direction of the thin film and the substrate after the heat treatment, it was found that chlorine was sufficiently contained in the film and that chlorine did not penetrate into GaAs or ZnSe which was the substrate.

From the above, it can be seen that the heat treatment method of the present invention is useful for recovering the crystallinity of the chalcopyrite thin film produced by ion irradiation. FIG. 5 is a schematic sectional view of an example of a solar cell manufactured using the chalcopyrite thin film obtained by the method of the present invention. A p-type CuInSe ₂ : N thin film 2 which is a chalcopyrite thin film manufactured by irradiating nitrogen ions during a three-source deposition of Cu, In, and Se is formed in a predetermined region on the Mo thin film 17. Then, heat treatment is performed at 500 ° C. for 1 hour while evaporating the Se element from the Se source in the vicinity of the CuInSe ₂ : N thin film in a vacuum. CuInSe ₂ having a stoichiometric composition without ion irradiation
The thin film 18 is deposited. An n-type CdS thin film 19 is manufactured by a vacuum evaporation method to form a hetero pn junction thereon.
The upper transparent electrode 20 is formed in a predetermined area on the CdS film 19. Reference numerals 21 and 22 denote electrode lead wires connected to the Mo thin film 17 or the transparent electrode 20, respectively.

In such a manufacturing process, since the elements can be formed in vacuum without exposing each film to the atmosphere, generation of oxides at the film interface or adhesion of foreign matter in the atmosphere can be prevented,
In addition, a CuInSe ₂ film with few lattice defects and excess impurities can be manufactured. Therefore, since there are few foreign substances at the interface that becomes the carrier recombination center, lattice defects and excess impurities in the CuInSe ₂ film, a thin film solar cell having high conversion efficiency can be formed.

[0041]

According to the method for producing a chalcopyrite thin film of the present invention, it is possible to recover the disorder of the chalcopyrite structure caused by the irradiation of the ion beam. Therefore, pn with few lattice defects and excess impurities
A method for producing a chalcopyrite thin film having a controlled conductivity type and conductivity can be provided.

Further, in the method for producing a chalcopyrite thin film of the present invention, according to a preferred embodiment in which the heat treatment is carried out while vaporizing the V group or VI group element powder constituting the chalcopyrite thin film, the composition ratio deviation is further reduced. be able to.

In the method for producing a chalcopyrite thin film of the present invention, the atmosphere gas is hydrogen, nitrogen, helium,
According to a preferred embodiment using at least one kind of gas selected from argon, it is possible to prevent the reaction between the gas and the chalcopyrite thin film, and the chalcopyrite thin film produced by irradiation with hydrogen ions or nitrogen ions is hydrogen. Heat treatment in an atmosphere or a nitrogen atmosphere can prevent the release of hydrogen or nitrogen from the chalcopyrite thin film.

Further, in the method for producing a chalcopyrite thin film of the present invention, according to a preferred embodiment of heat treatment in vacuum, it is possible to prevent generation of foreign matter and accumulation of impurities in the atmosphere due to oxidation of the thin film surface, etc. Carrier recombination centers at the interface with the film can be reduced.

Further, the solar cell of the present invention can provide a solar cell having high conversion efficiency.

[Brief description of drawings]

FIG. 1 is a conceptual diagram of an apparatus used for heat treating a chalcopyrite thin film according to an embodiment of the present invention in a gas atmosphere.

FIG. 2 is a graph showing changes in Raman scattering spectrum with respect to heat treatment temperature.

FIG. 3 is a graph showing changes in conductivity with respect to heat treatment temperature.

FIG. 4 is a conceptual diagram of an apparatus used for heat treatment of a chalcopyrite thin film according to an embodiment of the present invention in a vacuum while vaporizing Se element.

FIG. 5 is a cross-sectional structural view of a solar cell according to an embodiment of the present invention.

[Explanation of symbols]

1 Quartz tube 2 CuInSe ₂ : N film 3 Nitrogen gas 4 Heater 5 Raman scattering spectrum of CuInSe ₂ : N film not heat treated 6 Raman scattering spectrum of CuInSe ₂ : N film heat treated at 300 ° C. for 1 hour 7 1 at 400 ° C. Raman scattering spectrum of CuInSe ₂ : N film heat-treated for 8 hours Raman scattering spectrum of CuInSe ₂ : N film heat-treated at 500 ° C. for 1 hour 9 CuInSe ₂ : N film 10 heat-treated CuInSe ₂ : N film 11 Se powder CuInS heat-treated while evaporating
e ₂ : N film 12 vacuum container 13 Se vapor deposition source 14 substrate heater 15 power supply 16 exhaust port 17 Mo thin film 18 CuInSe ₂ film 19 CdS film 20 upper transparent electrode 21 electrode lead satisfying the stoichiometric ratio composition without ion irradiation Wire 22 Electrode lead wire 30 Substrate

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Hirao 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.

Claims (5)

[Claims] 1. A chalcopyrite thin film produced by vacuum vapor deposition, sputter vapor deposition, or reduced pressure vapor phase chemical reaction vapor deposition while irradiating an ion beam on an amorphous, crystalline, or metal substrate in a gas atmosphere. A method for producing a chalcopyrite thin film, characterized by heat treatment. 2. The chalcopyrite according to claim 1, wherein the heat treatment in a gas atmosphere is a heat treatment in a gas atmosphere while vaporizing the powder of a V group or VI group element which is a constituent element of the chalcopyrite thin film. Thin film manufacturing method. 3. The chalcopyrite thin film according to claim 1, wherein the atmospheric gas used in the heat treatment in a gas atmosphere is at least one kind of gas selected from hydrogen, helium, nitrogen and argon. Production method. 4. A chalcopyrite thin film produced by vacuum vapor deposition, sputter vapor deposition or reduced pressure vapor phase chemical reaction vapor deposition while irradiating an ion beam on an amorphous, crystalline or metal substrate, in a vacuum, A method for producing a chalcopyrite thin film, which comprises heat-treating while vaporizing a V group or VI group element, which is a constituent element of the chalcopyrite thin film, in the vicinity of the thin film. 5. A thin-film solar cell comprising a chalcopyrite thin film obtained by the method according to claim 1 as a light absorption layer.