JP4938314B2 - Photoelectric conversion device and method of manufacturing semiconductor junction element - Google Patents

Description

  The present invention relates to a photoelectric conversion device and a method for manufacturing a semiconductor junction element.

  Since iron sulfide has a high light absorption coefficient, it is expected to be applied to light receiving and emitting elements. Here, when considering application, at least conductivity type control (pn control) technology is indispensable, and for that purpose, energetic research and development has been carried out.

As iron sulfide, compositions of FeS, FeS ₂ and Fe ₂ S ₃ are known. FeS and FeS ₂ have a bivalent iron valence, whereas Fe ₂ S ₃ has a trivalent iron valence. Here, since Fe ₂ S ₃ is unstable and decomposes into FeS and FeS ₂ when ignited, and easily decomposes into iron oxide hydrate and sulfur in humid air, Not suitable for application.

  Iron sulfide, when not doped with impurities, exhibits p-type conductivity when sulfur is excessive compared to the stoichiometric ratio, while it exhibits n-type conductivity when sulfur is insufficient. Are known. However, most of the artificially produced iron sulfides have been reported to exhibit p-type conductivity, and making n-type iron sulfides with high reproducibility is a major issue for application. For this reason, vigorous research has been conducted on the control of the n conductivity type by impurity doping.

For example, JP-A-61-106499 (Patent Document 1) discloses that the stoichiometric deviation of pyrite material is in accordance with the formula: FeS _{2 ± X} [0 <x ≦ 0.05] and the concentration of impurities. Is <10 ²⁰ per cm ³ , and manganese (Mn), arsenic (As), cobalt (Co), or chlorine (Cl) is used as the doping material, and the doping concentration of the doping material is 1 cm. It is disclosed that when a photoactive pyrite layer of about 10 ¹⁶ to 10 ¹⁹ per ³ is applied to a solar cell, the solar cell exhibits good characteristics. In addition, n-type conductivity can be obtained by doping pyrite FeS ₂ with Ni or Co, while p-type conductivity can be obtained by doping Cu or As with pyrite FeS _2. Is disclosed.

In addition, in Japanese Translation of PCT International Publication No. 2002-516651A (Patent Document 2), a semiconductor substrate made of pyrite having a chemical composition FeS ₂ is at least partially selected from at least one of boron (B) and phosphorus (P). It has been disclosed that bonded semiconductor components or semiconductor components doped with these are optimal and extremely efficient, especially for applications for solar cells.

  However, the techniques disclosed in Patent Documents 1 and 2 have a problem that the conductivity type control (pn control) is insufficient. For example, taking Patent Document 2 as an example, the technology described therein is about what matters necessary for practical use, such as which conductivity type boron (B) or phosphorus (P) is a dopant of? There is also a problem that it is far from practical use.

As a result of the above-mentioned prior art being insufficient, for example, an all solid-state solar cell using pyrite FeS ₂ as a photoactive layer is exemplified. P. Altermatt, et. Al. Solar Energy MateriaAls & Solar Cells 71 (2002) p. As described in H.181 (Non-patent Document 1), all solid-state solar cells such as a Schottky diode structure have a problem that the photoelectric conversion efficiency is a low value of 1% or less.
JP 61-106499 A JP 2002-516651A P. P. Altermatt, et. Al. Solar Energy MateriaAls & Solar Cells 71 (2002) p. 181

  Therefore, an object of the present invention is to provide a photoelectric conversion device containing iron sulfide and a method for manufacturing a semiconductor junction element that can perform conductivity type control (pn control) without problems and can be used as a practical product.

In order to solve the above problems, the photoelectric conversion device of the present invention is
And FeS ₂ having a crystal structure of the pyrite type, and an A l, the Al is an n-type semiconductor contained ^{4 × 10 1 8 cm -3 ~5} × 10 21 cm -3,
A p-type semiconductor mainly composed of iron sulfide;
Including an all-solid-state semiconductor junction element including
The p-type semiconductor has a smaller band gap than the n-type semiconductor,
The band gap of the n-type semiconductor is 0.98 eV to 1.20 eV,
The n-type semiconductor is arranged on the light incident side.

  The iron sulfide may have a crystal structure, or may have a structure with a slight deviation from the stoichiometric ratio.

When making an n-type semiconductor by mixing a dopant with iron sulfide, the dopants studied so far include the characteristics as described in Patent Document 1, that is, belong to the same transition metal as iron, naturally It was Mn, Ni, Co, etc. that are often contained as impurities in the produced pyrite (FeS ₂ ). However, when any of them is used, characteristics that can be practically used as a semiconductor junction element have not been obtained. This is an n-conductivity type when divalent iron is replaced with a trivalent element, but the transition metal elements used so far can be trivalent but are basically easily divalent. In addition, since a plurality of other valences can be taken, it is surmised that the activation rate of the dopant is greatly influenced by the manufacturing method and the like, and it is difficult to obtain the intended conductivity. The present inventor tried to produce iron sulfide having n conductivity type by using a group IIIb element that has not been assumed as a dopant, and as a result, produced iron sulfide having n conductivity type having good reproducibility. I found it possible.

  Since the semiconductor junction element of the present invention contains iron sulfide and a group IIIb element, the conductivity type can be well controlled to n-type and the reproducibility can be remarkably improved, so that it can be used as a practical product. Can do.

The present inventor has discovered that the use of at least one of Al, Ga, and In as the group IIIb element can suppress the generation of an impurity phase. Furthermore, it has been found that the band gap can be increased when the group IIIb element contains Al. This is presumed to be because Al, Ga, and In have a relatively small difference in ionic radius from Fe ²⁺ among Group IIIb elements, and the inclusion of these elements can suppress the formation of impurity phases. Is done. Further, it is presumed that Al has a smaller ionic radius and electronegativity than Fe ²⁺ .

  Further, according to the present invention, a high-quality semiconductor junction element having good n-type conductivity can be realized.

  Further, according to the present invention, semiconductor characteristics suitable for application can be obtained.

  In addition, according to the present invention, characteristics of an n-type semiconductor such as electron conductivity can be improved, and element characteristics can be improved.

In one embodiment,
A p-type semiconductor composed mainly of iron sulfide;
The n-type semiconductor and the p-type semiconductor constitute a pn junction.

  According to the above embodiment, since the pn junction composed of the n-type semiconductor and the p-type semiconductor is provided, the rectification characteristics of the pn junction can be improved.

In one embodiment, FeS ₂ having a pyrite-type crystal structure and a IIIb group element including at least one of Al, Ga, and In, and the IIIb group element is 5 × 10 ¹⁵ cm. ^{-3 to} 5 × 10 ²¹ cm ^-3 includes an n-type semiconductor and includes a p-type semiconductor mainly composed of iron sulfide, and the n-type semiconductor and the p-type semiconductor constitute a pn junction. A semiconductor junction element.

According to the one embodiment, since the pn junction including the n-type semiconductor and the p-type semiconductor is provided, the photoelectric conversion efficiency can be significantly improved.
In addition, the method for manufacturing a semiconductor junction element of the present invention includes:
FeS ₂ having a pyrite type crystal structure and a group IIIb element including at least one of Al, Ga and In, and the group IIIb element is 5 × 10 ¹⁵ cm ^{−3 to} 5 × 10 ^21. an n-type semiconductor contained in cm ⁻³ ;
A p-type semiconductor mainly composed of iron sulfide;
A semiconductor junction element manufacturing method for manufacturing an all-solid-state semiconductor junction element including:
Each of the n-type semiconductor layer and the p-type semiconductor layer is baked after wet coating,
The n-type semiconductor layer is formed at a coating temperature of 80 ° C. or lower after the p-type semiconductor layer is formed at a coating temperature of 300 ° C. or higher .
In one embodiment,
After the wet application of the first layer, baking is performed at a temperature higher than 300 ° C.
In one embodiment,
After the wet application of the second layer, baking is performed at a temperature higher than 80 ° C.
In one embodiment,
The firing is performed in a sulfur-containing steam atmosphere.

  According to the present invention, since iron sulfide and a group IIIb element are contained, the conductivity type can be well controlled to n-type, reproducibility can be remarkably improved, and it can be used as a practical product.

  Hereinafter, the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a cross-sectional view of a photoelectric conversion device according to an embodiment of the present invention.

  This photoelectric conversion device includes a substrate 1, a first electrode layer 2 formed on at least a part of a surface region of the substrate 1, a photoelectric conversion layer 3 formed on the first electrode layer 2, and a photoelectric conversion layer. 2 and a second electrode layer 4 formed on the substrate 3.

  When the substrate 1 is located on the side opposite to the light incident, it does not matter whether the substrate 1 is translucent, but when the substrate 1 is located on the light incident side, the substrate 1 is at least partially It preferably has translucency. As a material for the light-transmitting substrate, glass, polyimide, polyvinyl, or polysulfide-based heat-transmitting resin, or a laminate of them can be used. As the material of the non-translucent substrate, stainless steel, non-translucent resin, or the like can be used. Concavities and convexities may be formed on the surface of the substrate 1, and in this case, various effects such as light confinement and antireflection can be obtained by refraction or scattering of light on the concave and convex surfaces. Further, the surface of the substrate 1 may be coated with a metal film, a semiconductor film, an insulating film, or a composite film thereof. The thickness of the substrate 1 is not particularly limited, but needs to have an appropriate strength and weight capable of supporting the structure. For example, the thickness of the substrate 1 can be 0.1 mm to 40 mm.

The form of the first electrode layer 2 is not particularly limited as long as the first electrode layer 2 is formed so as to be substantially in ohmic contact with the photoelectric conversion layer 3, but is preferably formed in a film shape on the substrate 1. The material used for the first electrode layer 2 is not particularly limited as long as it has conductivity, but preferably, an opaque material such as Mo, Al, Pt, C, Ti, Fe, Pd, Using such alloys, fluorine-doped tin oxide (SnO ₂ : F), antimony-doped tin oxide (SnO ₂ : Sb), tin-doped indium oxide (In ₂ O ₃ : Sn), Al-doped zinc oxide (ZnO: A transparent conductive oxide electrode material typified by Al), Ga-doped zinc oxide (ZnO: Ga), B-doped zinc oxide (ZnO: B), or the like can be used. In addition, the first electrode layer 2 may be a single layer film made of the above-described material or the like, or may be any one of a laminated film in which a plurality of the above-described materials are stacked.

  When the first electrode layer 2 is located on the light incident side, the first electrode layer 2 preferably has high translucency in the wavelength range of light contributing to photoelectric conversion. The first electrode layer 2 is made of a material component such as a vacuum deposition method, a sputtering method, a CVD method, a PVD method, a gas phase method such as a sol-gel method, a CBD (chemical bath deposition) method, a spray method, or screen printing. It is formed on the substrate 1 by a method or the like.

  As described above, when the substrate 1 is located on the light incident side, the first electrode layer 2 is required to have a high light transmittance. Therefore, in that case, the first electrode layer 2 is a grid-shaped metal electrode that does not cover the surface uniformly, such as a comb, or a transparent conductive layer with high light transmittance, or a combination of these requirements. It is preferable to be formed.

  The first electrode layer 2 preferably has irregularities on the surface thereof. The unevenness present on the surface of the first electrode layer 2 refracts and scatters light that has entered the photoelectric conversion device at the interface between the first electrode layer 2 and the photoelectric conversion layer 3 formed thereon. . As a result, the optical path length of incident light is increased, the light confinement effect is improved, and the amount of light that can be used in the photoelectric conversion layer 3 is increased. As a method for forming the unevenness, a dry etching method, a wet etching method, a mechanical process such as sand blasting, or the like on the surface of the first electrode layer 2 can be used.

As a dry etching method, in addition to physical etching using an inert gas such as Ar, fluorine-based gas such as CF ₄ and SF ₆ , chlorine-based gas such as CCl ₄ and SiCl ₄ , or methane gas is used. Chemical etching that has been used can be used. As the wet etching method, a method of immersing the first electrode layer 2 in an acid or alkali solution can be used. Here, examples of the acid solution that can be used include one or a mixture of two or more of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, acetic acid, formic acid, perchloric acid, and the alkaline solution includes sodium hydroxide, ammonia. , Potassium hydroxide, calcium hydroxide, aluminum hydroxide, or a mixture of two or more thereof. As a method other than the etching method described above, a method using surface irregularities formed by crystal growth of the material of the first electrode layer 2 by CVD or the like, or a surface depending on the crystal grain shape by sol-gel method or spray method There is a method using unevenness.

  The photoelectric conversion layer 3 is formed on the first electrode layer 2 so as to be substantially in ohmic contact. The photoelectric conversion layer 3 is formed by adding a group IIIb element to iron sulfide. The photoelectric conversion layer 3 has a structure including a semiconductor layer whose conductivity type is controlled to be n-type. The photoelectric conversion layer 3 has a structure having a pn junction having a p-type semiconductor layer and an n-type semiconductor layer, a pin having a p-type semiconductor layer, an intrinsic (i-type) semiconductor layer, and an n-type semiconductor layer. There are a structure having a junction, a Schottky junction having only an n-type semiconductor layer, a structure having a semiconductor junction such as a MIS structure, and the like. The i-type semiconductor layer may have a weak p-type or weak n-type conductivity type as long as the photoelectric conversion function is not impaired. Further, the photoelectric conversion device may have a structure in which two or more photoelectric conversion layers are stacked, and the photoelectric conversion device may be a so-called stacked photoelectric conversion device.

  When a group IIIb element is added to iron sulfide, a high-quality n-type conductive semiconductor layer having excellent reproducibility can be obtained. The reason for this is that, from the result of X-ray diffraction measurement, no impurity crystal phase other than the iron sulfide diffraction pattern was observed, and a peak shift was observed in the iron sulfide diffraction pattern. This is presumably because it exists in the crystal lattice.

For example, when a trivalent group IIIb element is substituted with a divalent iron site, the group IIIb element becomes a donor and an n-type conductive semiconductor layer is formed. Here, it is preferable that a group IIIb element is contained in the iron sulfide in a range of 5 × 10 ¹⁵ cm ^{−3 to} 5 × 10 ²¹ cm ⁻³ . Whether it can be made n-type depends on the carrier concentration of iron sulfide before doping. Most of the iron sulfide before doping was p-type, and the hole carrier concentration was 3 × 10 ¹⁵ cm ^{−3 to} 3 × 10 ²¹ cm ⁻³ . Here, in order to make it n-type, it is indispensable to include an effective donor whose concentration is higher than the hole carrier concentration of iron sulfide before doping. Actually, since not all of the doped group IIIb atoms become donors, it is necessary to do so slightly, and according to experiments, it is particularly good when the group IIIb element is 5 × 10 ¹⁵ cm ⁻³ or more. It was possible to obtain a high-quality iron sulfide semiconductor having n-type conductivity.

On the other hand, as described later, when the group IIIb element concentration in the iron sulfide was increased, the electron carrier concentration gradually increased and then showed a saturation tendency. When the group IIIb element concentration exceeds a certain value, the electrical characteristics do not change significantly even if the concentration is further increased. As a result, it was possible to obtain a particularly good iron sulfide semiconductor having n-type conductivity when the number of iron atoms and group IIIb atoms was 5 × 10 ²¹ cm ⁻³ or less. The type and concentration of group IIIb elements in iron sulfide can be evaluated by elemental analysis methods such as secondary ion mass spectrometry (SIMS) and Auger electron spectroscopy.

In addition, as shown below, when an element selected from Al, Ga, and In having a relatively small difference in ionic radius from Fe ²⁺ among group IIIb elements is included, generation of impurity crystal phases can be suppressed. Therefore, it is preferable. In particular, when Al is included as the IIIb group element, the band gap can be increased because both the ion radius and the electronegativity are smaller than those of Fe ²⁺ .

It was also found that when iron sulfide contains FeS ₂ having a pyrite type crystal structure, semiconductor characteristics suitable for application can be obtained. Since pyrite-type FeS ₂ has a high light absorption coefficient (−10 ⁵ cm ⁻¹ ) for visible light, it has a wavelength of ˜1.55 μm (˜0.85 eV), which is the lowest loss of an optical fiber as a solar cell material. Therefore, it is useful for materials for light receiving and emitting elements for optical communication. Therefore, it is preferable to include FeS ₂ having a pyrite-type crystal structure because the characteristics of iron sulfide can be brought close to characteristics useful for the above-mentioned use.

In addition, when iron sulfide contains a large amount of FeS ₂ having a pyrite-type crystal structure, relatively high carrier mobility (˜100 cm ² / Vs) can be realized even in a polycrystalline body. When used as a material, the semiconductor characteristics can be greatly improved.

Production methods for the photoelectric conversion layer 3 include MBE, CVD, vapor deposition, proximity sublimation, sputtering, sol-gel, spray, CBD (chemical bath deposition), and screen printing. Can be used. Examples of the CVD method include atmospheric pressure CVD, low pressure CVD, plasma CVD, thermal CVD, hot wire CVD, and MOCVD. In addition, in formation of the photoelectric converting layer 3, the sulfuration process in sulfur vapor | steam or hydrogen sulfide atmosphere can be performed as needed. The sulfiding treatment temperature is preferably 200 to 600 ° C. When sulfidation is performed, crystallization of an amorphous component can be promoted, the sulfur content in iron sulfide can be increased, or the proportion of FeS ₂ having a pyrite-type crystal structure can be increased. Here, the ratio of the amorphous component can be estimated by performing XRD measurement and comparing the peak intensity with the peak intensity when the film thickness is the same and the film is sufficiently crystallized. The proportion of FeS ₂ having a pyrite type crystal structure can be estimated by comparing the XRD peak intensity of the pyrite structure with the XRD peak intensity of other structures.

  The second electrode layer 4 is formed on the photoelectric conversion layer 3 so as to substantially make ohmic contact. The material and manufacturing method used for the second electrode layer 4 are the same as when the first electrode layer 2 was formed. In this way, a photoelectric conversion device with high photoelectric conversion efficiency is formed.

  FIG. 2 is a schematic cross-sectional view of the sulfide semiconductor of Examples 1 to 7 and the sulfide semiconductor of Comparative Example 1 that can be used in the present invention. FIG. 3 shows the compounds of Examples 1 to 7 and Comparative Example 1 It is a figure showing a kind and density | concentration. Hereinafter, based on FIG. 2 and FIG. 3, the n-type semiconductor layer of Examples 1-7 is demonstrated. The iron sulfide semiconductors of Examples 1 to 7 are manufactured by forming the iron sulfide layer 22 on the glass substrate 21 having a thickness of 1.1 mm by using both the spray pyrolysis method and the sulfidation method. .

Specifically, for example, 500 ml of pure water is mixed with iron chloride (FeCl ₂ ) and thiourea (NH ₂ CSNH ₂ ), so that iron chloride (FeCl ₂ ) is 0.05 mol / l and thio A solution is prepared in which urea (NH ₂ CSNH ₂ ) is 0.1 mol / l.

Next, a compound containing a doping element indicating the type and concentration of the compound shown in FIG. 3 is further dissolved in the prepared solution to prepare a spray solution. Here, if the solute is difficult to dissolve, hydrochloric acid is added. In this way, the solute can be easily dissolved. In Examples 1 to 5 and 7 and Comparative Example 1, hydrochloric acid was not added. In the case of Example 6, gallium hydroxide (Ga ₂ O ₃ .nH ₂ O was added by adding 3 ml of 35% hydrochloric acid. ) Was dissolved.

  Next, after the glass substrate 21 is heated to about 300 ° C. on a hot plate and in the atmosphere, the above-mentioned solution described in detail in FIG. 3 is spray-coated on the hot plate to form a thin film. As a result of XRD measurement of the thin film formed by spray coating, no peak of iron oxide or hydroxide was observed. From this, it was confirmed that the main component of the thin film was FeS.

Next, baking is performed at 500 ° C. for 1 hour in a sulfur vapor atmosphere. At this time, sulfur vapor is generated by heating sulfur at a temperature lower than 200 ° C. using a heater different from the heater for heating the sample, and nitrogen gas is supplied as a carrier gas at a flow rate of 5 l / min. When XRD measurement was performed after the sulfurization treatment, it was confirmed that a single phase of FeS ₂ pyrite was formed. Moreover, it was 700 nm when the thickness of the iron sulfide layer 22 was measured using the level | step difference film thickness meter. Thus, the iron sulfide semiconductor shown in FIG. 2 was produced.

  In FIG. 3, the conductivity type and carrier concentration are the results of hole measurement. In FIG. 3, the group IIIb element concentration is the result of SIMS measurement in Examples 1 and 2, and the result of Auger electron spectroscopy measurement in Examples 3-7. In FIG. 3, Eg (eV) is a result of optical band gap (Eg) measurement. Here, Eg plots the square of the light absorption coefficient against the energy of the incident light, and obtains the transition band gap directly from the X intercept.

  As shown in FIG. 3, in Comparative Example 1 in which doping was not performed, the conductivity type was p-type, while in Examples 1 to 7 in which doping was performed, the conductivity type was n-type. For this reason, an n-type iron sulfide semiconductor can be formed by adding a group IIIb element concentration to iron sulfide.

  In Examples 3, 6, and 7, the concentration of the group IIIb element is the same, but the type of the group IIIb element is different. When Examples 3, 6, and 7 are compared, an approximately equivalent value is obtained as the electron carrier concentration, while Eg is larger only in Example 3 than in Comparative Example 1. From this, when the dopant contains an Al element, a wide band gap can be formed simultaneously with the n-type conversion.

In Examples 1 to 5, the type of group IIIb element is the same, but the concentration of group IIIb element is different. When Examples 1 to 5 are compared, when the Al concentration increases to 2 × 10 ²¹ cm ⁻³ , the electron carrier concentration increases as the Al concentration increases, whereas when the Al concentration exceeds 2 × 10 ²¹ cm ^−3. Even if the Al concentration increases, the electron carrier concentration does not increase and shows a constant value, and the electron carrier concentration is saturated.

On the other hand, as described above, it is indispensable that the minimum doping amount as to whether or not n-type can be achieved is equal to or higher than the hole carrier concentration of iron sulfide before doping. Therefore, when the concentration of the group IIIb element contained in the iron sulfide is set in the range of 5 × 10 ¹⁵ cm ^{−3 to} 5 × 10 ²¹ cm ⁻³ , the conductivity type of the iron sulfide semiconductor can be made n-type. At the same time, excess electrons can be efficiently generated by doping the group IIIb element, and a carrier concentration corresponding to the doping amount of the group IIIb element can be realized. When a semiconductor junction element such as a diode, a transistor, or a semiconductor laser element is formed using the n-type semiconductor described above, characteristics such as electronic conductivity of the n-type semiconductor of the semiconductor junction element can be improved. Therefore, the element characteristics of the semiconductor junction element can be remarkably improved.

  FIG. 4 is a cross-sectional view of the photoelectric conversion devices according to Examples 8 to 14 of the present invention.

The photoelectric conversion devices of Examples 8 to 14 are formed as follows. First, for example, a 500 nm Pt film is formed on a glass substrate 41 having a thickness of 1.1 mm by a vacuum deposition method, thereby forming the electrode layer 42. Next, a photoelectric conversion layer 43 having a pn junction of FeS ₂ pyrite is formed on the electrode layer 42 by using a spray pyrolysis method and a sulfurization method in combination. Then, after forming the transparent conductive film 44 on the photoelectric converting layer 43, the grid electrode 45 is formed on the transparent conductive film 44, and a photoelectric conversion apparatus is formed.

Specifically, when preparing p-type FeS ₂ pyrite, the same p-type spray solution as in Comparative Example 1 in FIG. 3 is used, and the glass substrate 41 on which the first electrode layer 42 is laminated is placed on a hot plate. And it heats to about 300 degreeC under air | atmosphere, The said solution is spray-coated on it, and a thin film is formed. As a result of XRD measurement of the spray-coated thin film, no peak of iron oxide or hydroxide was observed, and it was confirmed to be FeS.

Next, baking is performed at 500 ° C. for 1 hour in a sulfur vapor atmosphere. At this time, sulfur vapor is generated by heating sulfur at a temperature lower than 200 ° C. using a heater different from the heater for heating the sample, and nitrogen gas is allowed to flow as a carrier gas at a flow rate of 5 l / min. When XRD measurement was performed after the sulfurization treatment, it was confirmed that a single phase of FeS ₂ pyrite was formed. The film thickness was 2 μm.

Subsequently, in order to produce n-type FeS ₂ pyrite on p-type FeS ₂ pyrite, it performed again spray coating. Figure 5 is a diagram showing a p-type spray solution, the n-type spray solution used in making the n-type FeS ₂ pyrite on p-type FeS ₂ pyrite. In Examples 8 to 14, the spray solution shown in FIG. 5 was used after being diluted 20 times with pure water.

A substrate formed up to p-type FeS ₂ pyrite is heated to about 80 ° C. in the air on a hot plate, and the above solution is sprayed thereon to form a thin film. At this time, after adjusting the number of sprays so that the film thickness becomes 50 nm, the baking is performed at 500 ° C. in the sulfur vapor atmosphere as in the case of the p-type. Here, the firing time was 10 minutes. In this way, the photoelectric conversion layer 43 including the p-type semiconductor layer 47 formed on the electrode layer 42 and the n-type semiconductor layer 48 formed on the p-type semiconductor layer 47 is formed.

  Thereafter, 700 nm of n-type gallium-doped zinc oxide (ZnO: Ga) is deposited on the photoelectric conversion layer 43 by magnetron sputtering to form a transparent conductive film 44, and then the comb-shaped silver is formed on the transparent conductive film 44. The grid electrode 45 is formed by forming (Ag) by magnetron sputtering. In this way, the photoelectric conversion device shown in FIG. 4 is formed.

This inventor investigated the photoelectric conversion efficiency of the photoelectric conversion apparatus produced in this way. Specifically, the photoelectric conversion device thus manufactured was irradiated with AM 1.5 (100 mW / cm ² ) light, and the photoelectric conversion efficiency was measured under the conditions of a cell temperature of 25 ° C. and a cell area of 1 cm ² . . The photoelectric conversion efficiency in FIG. 5 is this measurement result.

  As shown in FIG. 5, all the photoelectric conversion devices of Examples 8 to 14 exhibited rectifying properties, and the conversion efficiency of each photoelectric conversion device was a high value exceeding 2%. Therefore, when the above-described iron sulfide semiconductor is used as the n-type semiconductor, a good pn junction can be configured. Further, the photoelectric conversion efficiencies of 13, 14 that do not contain Al element as the n-type semiconductor dopant are smaller than the photoelectric conversion efficiency of Example 10 that contains Al element as the n-type semiconductor dopant. When a substance containing an Al element is employed as the n-type semiconductor dopant, the photoelectric conversion efficiency can be improved.

  It is surmised that the reason why the highest conversion efficiency can be obtained when Al is contained is as follows. That is, in this embodiment, since the n-type layer exists on the light incident side, light loss occurs in the n-type layer. Here, when the band gap of the n-type layer is large, light having energy less than or equal to the band gap is transmitted, so that the light loss reduction effect can be improved in the n-type layer. The increase in short-circuit current density due to this is considered to be the reason why the conversion efficiency is high when Al is included.

  In Examples 8 to 14, the photoelectric conversion element was manufactured using a pn junction including an n-type semiconductor and a p-type semiconductor containing iron sulfide. However, the n-type semiconductor and the p-type semiconductor containing iron sulfide were used. Of course, a pn junction element such as a diode, a transistor (pnp transistor, npn transistor, pnip transistor), or a switch having a pn junction (pnpm switch, pnpn switch) may be manufactured using a pn junction consisting of It is. When a pn junction element is manufactured using a pn junction composed of an n-type semiconductor and a p-type semiconductor containing iron sulfide, the rectifying characteristics of the pn junction element can be significantly improved. Can be significantly improved.

It is sectional drawing of the photoelectric conversion apparatus of one Embodiment of this invention. It is a schematic sectional drawing of the sulfide semiconductor of Examples 1-7 which can be used by this invention, and the sulfide semiconductor of the comparative example 1. FIG. 2 is a diagram showing the types and concentrations of the compounds of Examples 1 to 7 and Comparative Example 1. It is sectional drawing of the photoelectric conversion apparatus of Examples 8-14 of this invention. It is a figure showing the spray solution for p type and the spray solution for n type which were used when forming the photoelectric conversion apparatus shown in FIG.

DESCRIPTION OF SYMBOLS 1 Substrate 2 1st electrode layer 3 Photoelectric conversion layer 4 2nd electrode layer 21,41 Glass substrate 22 Iron sulfide layer 42 Electrode layer 43 Photoelectric conversion layer 44 Transparent conductive film 45 Grid electrode

Claims (5)

And FeS ₂ having a crystal structure of the pyrite type, and an A l, the Al is an n-type semiconductor contained ^{4 × 10 1 8 cm -3 ~5} × 10 21 cm -3,
A p-type semiconductor mainly composed of iron sulfide;
Including an all-solid-state semiconductor junction element including
The p-type semiconductor has a smaller band gap than the n-type semiconductor,
The band gap of the n-type semiconductor is 0.98 eV to 1.20 eV,
The n-type semiconductor is disposed on a light incident side, and is a photoelectric conversion device. FeS ₂ having a pyrite type crystal structure and a group IIIb element including at least one of Al, Ga and In, and the group IIIb element is 5 × 10 ¹⁵ cm ^{−3 to} 5 × 10 ^21. an n-type semiconductor contained in cm ⁻³ ;
A p-type semiconductor mainly composed of iron sulfide;
A semiconductor junction element manufacturing method for manufacturing an all-solid-state semiconductor junction element including:
Each of the n-type semiconductor layer and the p-type semiconductor layer is baked after wet coating,
A method for manufacturing a semiconductor junction element, wherein the p-type semiconductor layer is formed at a coating temperature of 300 ° C. or higher, and then the n-type semiconductor layer is formed at a coating temperature of 80 ° C. or lower . In the manufacturing method of the semiconductor junction element according to claim 2,
A method for producing a semiconductor junction element, comprising firing at a temperature higher than 300 ° C. after the wet coating of the first layer. In the manufacturing method of the semiconductor junction element according to claim 2,
A method for producing a semiconductor junction element, comprising firing at a temperature higher than 80 ° C. after wet coating of the second layer. In the manufacturing method of the semiconductor junction element according to claim 3 or 4,
The said baking is performed in sulfur-containing vapor | steam atmosphere, The manufacturing method of the semiconductor junction element characterized by the above-mentioned.

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