WO2011108033A1 - Photopile en couches minces composite et son procédé de fabrication - Google Patents

Photopile en couches minces composite et son procédé de fabrication Download PDF

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WO2011108033A1
WO2011108033A1 PCT/JP2010/001581 JP2010001581W WO2011108033A1 WO 2011108033 A1 WO2011108033 A1 WO 2011108033A1 JP 2010001581 W JP2010001581 W JP 2010001581W WO 2011108033 A1 WO2011108033 A1 WO 2011108033A1
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light absorption
thin film
absorption layer
layer
solar cell
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PCT/JP2010/001581
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English (en)
Japanese (ja)
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中川直之
桜田新哉
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株式会社 東芝
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Priority to PCT/JP2010/001581 priority Critical patent/WO2011108033A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a compound thin film solar cell.
  • II-VI group II-VI CdTe or I, III, VI group I-III-VI 2- type CuInSe 2 having a chalcopyrite structure is used as the light absorption layer.
  • Cu (In, Ga) Se 2 (CIGS) is widely used.
  • the band gap (Eg) can be greatly modulated.
  • Patent Document 1 in order to obtain a large crystal grain size of 500 nm or more, when a chalcopyrite type compound thin film is deposited by vacuum evaporation or sputtering, a chalcogenide element and a rare gas element are irradiated with an ion beam. A method of manufacturing a pyrite-type compound thin film is disclosed.
  • carriers of chalcopyrite type compound thin-film solar cells represented by CIGS are insensitive to crystal grain boundaries, and it is known that crystal grain boundaries are less likely to become recombination centers of carriers. Yes.
  • the present invention aims to solve such problems, and by controlling the crystal grain size of the light absorption layer, a highly efficient compound thin film solar cell including a light absorption layer adjusted to a band gap optimal for light absorption, and its An object is to provide a manufacturing method.
  • the compound thin film solar cell 10 includes a substrate 11, a back electrode 12 provided on the substrate 11, a first extraction electrode 13 provided on the back electrode 12, and a Cu provided on the back electrode 12.
  • a highly efficient compound thin film solar cell is provided by controlling the particle size of the light absorption layer.
  • the compound thin film solar cell 10 shown in the conceptual diagram of FIG. 1 includes a substrate 11, a back electrode 12 provided on the substrate, a first extraction electrode 13 provided on the back electrode 12, and the back electrode. 12, a light absorption layer 14 provided on the buffer layer 15, a buffer layer 15 (15 a, 15 b) provided on the light absorption layer 14, a transparent electrode layer 16 provided on the buffer layer 15, and the transparent electrode And a second extraction electrode 17 provided on the layer 16.
  • the following method is mentioned as an example.
  • a back electrode 12 is formed on the substrate 11.
  • Examples of the film forming method include a sputtering method.
  • Step of forming light absorption layer on back electrode After the back electrode 12 is deposited, a compound semiconductor thin film that becomes the light absorption layer 14 is deposited. Since the light absorption layer 14 and the first extraction electrode 13 are deposited on the back electrode 12, the light absorption layer 14 is deposited on a part of the back electrode 12 excluding at least the portion where the first extraction electrode 13 is deposited. To do.
  • the film forming method include vacuum processes such as sputtering and vacuum deposition. In the sputtering method, all the constituent elements of the light absorption layer are supplied from the sputtering target. There may be one source target or a plurality of targets. It is desirable to adjust the preparation composition of the target constituent elements so that the formed thin film has a stoichiometric composition and, in some cases, the Group III element is slightly excessive, and the insufficient elements are supplied from other targets. May be.
  • Step of heat-treating light absorption layer After film formation, the film formation chamber is evacuated and annealed in an ultra-high vacuum atmosphere.
  • the compound semiconductor thin film immediately after sputtering is amorphous and has a very small particle size. Therefore, the compound semiconductor thin film can be crystallized by performing annealing at a high temperature. The average crystal grain size varies depending on the annealing temperature.
  • the crystallization of the compound semiconductor thin film may be annealed during the film formation of the compound semiconductor thin film in addition to the annealing after the film formation.
  • the heating means is not particularly limited, such as annealing or infrared laser.
  • Buffer layers 15 a and 15 b are deposited on the obtained light absorption layer 14.
  • Examples of the method for forming the buffer layer 15a include a sputtering method in a vacuum process, a vacuum deposition method or metal organic chemical vapor deposition (MOCVD), and a chemical deposition (CBD) method in a liquid phase process.
  • Examples of the method for forming the buffer layer 15b include sputtering in a vacuum process, vacuum deposition, or metal organic chemical vapor deposition (MOCVD).
  • the transparent electrode 16 is deposited on the buffer layer 15b.
  • the film forming method include sputtering in a vacuum process, vacuum vapor deposition, or metal organic chemical vapor deposition (MOCVD).
  • the first extraction electrode 13 is deposited on a portion excluding at least the portion where the light absorption layer is formed on the back electrode 12.
  • the second extraction electrode 17 is deposited on a portion excluding at least a portion where the antireflection film is formed on the transparent electrode 16.
  • Examples of the film forming method include a sputtering method and a vacuum deposition method. The film formation of the first and second extraction electrodes may be performed in one step, or may be performed after any step as a separate step.
  • Step of forming an antireflection film on a transparent electrode Finally, an antireflection film 18 is deposited on the transparent electrode 16 except at least the portion where the second extraction electrode 17 is formed.
  • the film forming method include a sputtering method and a vacuum deposition method.
  • the compound thin film solar cell shown in the conceptual diagram of FIG. 1 is produced through the above steps.
  • the step of dividing the back electrode with a laser after the step of forming the buffer layer on the light absorption layer, and the buffer layer
  • the step of dividing the sample by mechanical scribing is sandwiched between the layers, thereby enabling integration.
  • a preferred band gap for converting sunlight into energy is 1.0 eV to 1.5 eV.
  • the band gap for the optimal sunlight spectrum is often 1.4 eV to 1.5 eV.
  • the conversion efficiency becomes maximum in the vicinity of 1.2 eV.
  • it can use for the light absorption layer 14 for converting the light of the short wavelength side of sunlight.
  • the conversion efficiency of the compound thin-film solar cell using the light absorption layer 14 for converting light on the short wavelength side alone is not high. However, it is possible to improve the conversion efficiency of the solar cell by combining the light absorption layer 14 in the above preferable range and the light absorption layer 14 that converts light on the short wavelength side.
  • the light absorption layer 14 includes a chalcopyrite type compound semiconductor thin film that can be represented by ABC 2 (the alphabet of ABC 2 is not an element symbol).
  • A is Cu.
  • B is one or more elements selected from the group consisting of Al, In and Ga.
  • C is one or more elements selected from the group consisting of S, Se and Te.
  • the conditions of the light absorption layer 14 can be summarized as follows.
  • the light absorption layer 14 is Cu (Al 1-xy Ga x In y ) (Te 1-ab Se a S b ) 2 (where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ x + y ⁇ 1, and 0 ⁇ a + b ⁇ 1).
  • the light absorption layer 14 is preferably formed on the back electrode by sputtering.
  • the thickness of the light absorption layer 14 is preferably 0.5 to 3.0 ⁇ m.
  • the thickness of the light absorbing layer 14 is thinner than 0.5 ⁇ m, it is too thin to function as the light absorbing layer, and if it is thicker than 3.0 ⁇ m, it is not preferable that the manufacturing cost of the light absorbing layer 14 increases. .
  • the crystal grain size of the compound thin film semiconductor of the light absorption layer 14 is adjusted by heat treatment during or after the film formation.
  • the higher the heating temperature the larger the crystal grain size of the compound thin film semiconductor.
  • the band gap is suitable for absorption of sunlight.
  • a compound semiconductor having a wide gap is used in advance, it can be controlled to a band gap suitable for absorption of sunlight by heat treatment at a relatively low temperature.
  • the crystal grain size is controlled by heat treatment after film formation, in the range where the average crystal grain size is 10 nm or less, the crystallinity is low and an appropriate band gap may not be formed.
  • the crystal grain size is preferably 10 nm or more and 100 nm or less.
  • the light absorption layer 14 includes a compound semiconductor thin film having an average crystal grain size of 1 nm to 50 nm.
  • a compound semiconductor thin film having an average crystal grain size of 1 nm to 50 nm and a compound semiconductor thin film having an average crystal grain size of more than 50 nm and not more than 100 nm are laminated as the light absorption layer 14. It is preferable.
  • the number of stacked compound thin film semiconductors is 2 or more because a wide range of wavelengths can be absorbed and converted in sunlight.
  • a compound semiconductor thin film having an average crystal grain size of 50 nm or more and 100 nm or less capable of capturing light with a short wavelength may be disposed on the side irradiated with sunlight. preferable.
  • the annealing temperature is preferably 200 ° C. or more and 500 ° C. or less at the substrate temperature.
  • the band gap has a crystal grain size that is suitable for the light absorption layer 14 of the solar cell.
  • the annealing time is preferably 10 minutes or more and 120 minutes or less.
  • a method using an infrared laser is also preferable.
  • the infrared laser include CW Nd: YAG or a semiconductor laser.
  • the heating temperature is preferably 200 ° C. or higher and 500 ° C. or lower from the viewpoint of conversion efficiency of sunlight.
  • the preferred range of the average crystal grain size of the compound semiconductor thin film is the same as that of annealing.
  • the light absorption layer 14 in which the average crystal grain size is changed in the film thickness direction as shown in the conceptual diagram of the correlation between the film thickness direction and the particle size in FIG. It is also possible.
  • the grain size stepwise the band structure of the conduction band changes in synchronization with it.
  • the light absorption layer 14 in which the average crystal grain size is changed stepwise in the film thickness direction is preferable because it can improve carrier collection efficiency by forming an internal electric field and increase open circuit voltage by reducing carrier recombination at the pn junction interface. .
  • the change in the grain size in the film thickness direction is preferably the shape shown in the correlation conceptual diagram of FIG. 4, but may be a shape that monotonously increases from the pn junction interface.
  • a crystal growth inhibitor may be added to the chalcopyrite type semiconductor.
  • the growth of the crystal grain size can be adjusted (suppressed).
  • the heat treatment is performed at the same temperature, if a crystal growth inhibitor is added, crystal growth can be suppressed as compared with a case where a crystal growth inhibitor is not added.
  • the crystal growth inhibitor include elements such as B, Ti, Fe, Ni, and Nb.
  • the amount of the crystal growth inhibitor added is preferably 5 at% or more and 30 at% or less with respect to the atomic weight of the light absorption layer 14, for example. As described above, when a crystal growth inhibitor is added, the band gap can be easily adjusted, and light in a wide range of wavelengths suitable for absorption of sunlight can be absorbed and converted.
  • the light absorption layer 14 to which the crystal growth inhibitor is added so that the concentration of the crystal growth inhibitor has a gradient distribution in the film thickness direction of the light absorption layer 14 is formed, and the band graded film shown in FIG.
  • the light absorption layer 14 may be used.
  • the light absorption layer 14 whose average crystal grain size is changed stepwise in the film thickness direction by the addition of the crystal growth inhibitor improves carrier collection efficiency by forming an internal electric field and carriers at the pn junction interface. It is preferable because the open circuit voltage can be improved by reducing recombination.
  • the change in the grain size in the film thickness direction is preferably the shape shown in the correlation conceptual diagram of FIG. 4, but may be a shape that monotonously increases from the pn junction interface.
  • a light absorption layer 14 having a multilayer structure may be formed by laminating compound semiconductor thin films to which different concentrations of crystal growth inhibitors are added.
  • a narrow gap and wide gap compound semiconductor as the light absorption layer 14 and heat-treating it, a light absorption layer capable of converting light in a wider wavelength range into energy in sunlight is obtained. More preferably.
  • the substrate 11 it is desirable to use blue plate glass, and it is also possible to use a metal plate such as stainless steel, Ti or Cr, or a resin such as polyimide.
  • a metal film such as Mo or W can be used as the back electrode 12.
  • Mo molybdenum
  • W molybdenum
  • the extraction electrodes 13 and 17 for example, Al, Ag, or Au can be used. Furthermore, in order to improve the adhesion with the transparent electrode 15, after depositing Ni or Cr, Al, Ag or Au may be deposited.
  • the buffer layer 15 CdS, Zn (O, S, OH), or ZnO added with Mg can be used.
  • the chalcopyrite compound semiconductor of the light absorption layer 14 functions as a p-type semiconductor
  • the buffer layer 15a typified by CdS or ZnO: Mg functions as an n-type semiconductor
  • the buffer layer 15b typified by ZnO functions as an n + -type layer. Conceivable.
  • the transparent electrode layer 16 is required to transmit sunlight and have conductivity, for example, ZnO containing 2 wt% of alumina (Al 2 O 3 ): ZnO containing Al or B from diborane as a dopant. : B can be used.
  • MgF 2 is desirably used as the antireflection film 18.
  • the present invention will be described in detail by way of examples.
  • Example 1 A blue glass substrate was used as the substrate 11, and a Mo thin film serving as the back electrode 12 was deposited by about 700 nm by sputtering. Sputtering was performed by applying RF 200 W in an Ar gas atmosphere using Mo as a target. After the Mo thin film serving as the back electrode 12 was deposited, a CuAlTe 2 thin film serving as the light absorption layer 14 was similarly deposited by about 2 ⁇ m by RF sputtering. Film formation was performed by applying RF 200 W in an Ar gas atmosphere.
  • the film formation chamber was evacuated and annealed in an ultra-high vacuum atmosphere at 200 ° C.
  • the CuAlTe 2 thin film immediately after sputtering is amorphous and has a very small particle size. Therefore, by performing annealing at a high temperature, the CuAlTe 2 thin film crystallized and the particle size became about 10 nm. As a result, the CuAlTe 2 thin film had a band gap value suitable for the light absorption layer 14.
  • a ZnO thin film to which Mg was added as a buffer layer 15a was deposited on the obtained light absorption layer 14 to a thickness of about 50 nm.
  • RF sputter was used for film formation, but it was performed at an output of 50 W in consideration of plasma damage at the interface.
  • a ZnO thin film was deposited as a buffer layer 15b on the buffer layer 15a, and then ZnO: Al containing 2 wt% of alumina (Al 2 O 3 ) to be the transparent electrode 16 was deposited to a thickness of about 1 ⁇ m.
  • MgF 2 was deposited by sputtering as the antireflection film 18 to produce the compound thin film solar cell shown in FIG.
  • the optical property evaluation result (a) and cross-sectional SEM image (b) of the light absorption layer of the manufactured compound thin film solar cell are shown in FIG. From the optical property evaluation results, the band gap of the light absorption layer 14 of Example 1 was estimated to be 1.05 eV. Moreover, the thin film which consists of a compound semiconductor with a very small particle size was confirmed from the SEM image.
  • Example 2 A compound thin-film solar cell was manufactured in the same manner as in Example 1 except that Cu (Al 1-x In x ) Te 2 to be the light absorption layer 14 was formed by RF sputtering.
  • x is a numerical value larger than 0 and smaller than 1. Even when Cu (Al 1-x In x ) Te 2 is used as the light absorption layer 14, it was amorphous before high-temperature heat treatment, but by annealing at 200 ° C., Cu (Al 1-x In x ) Te 2 is crystallized, and a compound thin film solar cell having a band gap value suitable as the light absorption layer 14 is obtained.
  • Example 3 A compound thin-film solar cell is manufactured in the same manner as in Example 1 except that Cu (Al 1-x Ga x ) Te 2 to be the light absorption layer 14 is formed by RF sputtering.
  • x is a numerical value larger than 0 and smaller than 1. Even when Cu (Al 1-x Ga x ) Te 2 is used as the light absorption layer 14, it was amorphous before high-temperature heat treatment, but by annealing at 200 ° C., Cu (Al 1-x Ga x) x ) Te 2 crystallizes, and a compound thin film solar cell having a band gap value suitable as the light absorption layer 14 is obtained.
  • Example 4 A compound thin-film solar cell is manufactured by the same method as in Example 1 except that Cu (Al 1-xy In x Ga y ) Te 2 to be the light absorption layer 14 is formed by RF sputtering.
  • x and y are numerical values larger than 0 and smaller than 1. Even when Cu (Al 1-xy In x Ga y ) Te 2 is used as the light absorption layer 14, it was amorphous before high-temperature heat treatment, but by annealing at 200 ° C., Cu (Al 1-xy In x Ga y ) Te 2 is crystallized, and a compound thin film solar cell having a band gap value suitable as the light absorption layer 14 is obtained.
  • Example 5 A compound thin film solar cell is manufactured by the same method as in Example 1 except that CuAlSe 2 to be the light absorption layer 14 is formed by RF sputtering. Even when CuAlSe 2 is used as the light absorption layer 14, it was amorphous before the high-temperature heat treatment, but by annealing at 200 ° C., CuAlSe 2 crystallized, and a band gap value suitable for the light absorption layer 14. The compound thin film solar cell is obtained.
  • Example 6 A compound thin film solar cell is manufactured by the same method as in Example 1 except that CuGaSe 2 to be the light absorption layer 14 is formed by RF sputtering. Even when CuGaSe 2 is used as the light absorption layer 14, it was amorphous before the high-temperature heat treatment, but by annealing at 200 ° C., CuGaSe 2 crystallizes, and a band gap value suitable for the light absorption layer 14. The compound thin film solar cell is obtained.
  • Examples 5 and 6 are not examples in which any one of Al, In, and Ga is combined, but Al, In, and Ga may be used in combination.
  • Example 7 A compound thin film solar cell is manufactured by the same method as in Example 1 except that CuAlS 2 to be the light absorption layer 14 is formed by RF sputtering. Even when CuAlS 2 is used as the light absorption layer 14, it was amorphous before high-temperature heat treatment, but by annealing at 200 ° C., CuAlS 2 crystallized, and a band gap value suitable for the light absorption layer 14. The compound thin film solar cell is obtained.
  • Example 8 A compound thin film solar cell is manufactured by the same method as in Example 1 except that CuInS 2 to be the light absorption layer 14 is formed by RF sputtering. Even when CuInS 2 is used as the light absorption layer 14, it was amorphous before high-temperature heat treatment, but by annealing at 200 ° C., CuInS 2 crystallized, and a band gap value suitable for the light absorption layer 14. The compound thin film solar cell is obtained.
  • Example 9 A compound thin film solar cell is manufactured by the same method as in Example 1 except that CuGaS 2 to be the light absorption layer 14 is formed by RF sputtering. Even when CuGaS 2 is used as the light absorption layer 14, it was amorphous before the high-temperature heat treatment, but CuGaS 2 was crystallized by annealing at 200 ° C., which is suitable for the light absorption layer 14. Value compound thin film solar cells are obtained.
  • Example 7-9 is not an example in which any of Al, In, and Ga is combined, but Al, In, and Ga may be used in combination.
  • FIG. 3 shows an optical property evaluation result (a) and a cross-sectional SEM image (b) of the light absorption layer 14 when CuAlTe 2 is used for the light absorption layer in this example.
  • the band gap of the light absorption layer 14 was estimated to be 2.25 eV.
  • the thin film which consists of a compound semiconductor whose average crystal grain diameter is about 100 nm was confirmed from the SEM image. Since the band gap increases as the average crystal grain size increases, it is suitable as the light absorption layer 14 for converting light on the short wavelength side.
  • Comparative Example 1-9 The same as in Examples 1 to 9, except that the annealing temperature is 100 ° C. In this embodiment, the processing is performed at a lower temperature than in the first embodiment. By processing at a lower temperature than in Example 1, the crystal of the light absorption layer 14 hardly grows. In the case of this comparative example, CuAlTe 2 is generally amorphous, and the crystal grain size and the band gap of the compound of the light absorption layer 14 cannot be suitably controlled.
  • Example 10 A compound thin-film solar cell is manufactured by the same method as in Example 1 except that CuInTe 2 serving as the light absorption layer 14 is formed by RF sputtering.
  • CuInTe 2 serving as the light absorption layer 14
  • the bulk value of the band gap is originally 1.0 eV or less, and the band gap cannot be suitably controlled by controlling the crystal grain size of the light absorption layer.
  • Example 11 A compound thin film solar cell is manufactured by the same method as in Example 1 except that CuGaTe 2 serving as the light absorption layer 14 is formed by RF sputtering. Even when CuGaTe 2 is used as the light absorption layer 14, it was amorphous before the high-temperature heat treatment, but can be crystallized by annealing at 200 ° C. However, since the bulk value of the band gap is originally 1.5 eV or less, when the annealing temperature is 200 ° C., the band gap cannot be suitably controlled by controlling the crystal grain size of the light absorption layer.
  • Example 12 A compound thin-film solar cell is manufactured by the same method as in Example 1 except that Cu (In 1-x Ga x ) Te 2 to be the light absorption layer 14 is formed by RF sputtering.
  • x is a numerical value larger than 0 and smaller than 1.
  • the bulk value of the band gap is originally 1.5 eV or less, the band gap cannot be suitably controlled by controlling the crystal grain size of the light absorption layer at an annealing temperature of 200 ° C.
  • Example 13 A compound thin film solar cell is manufactured by the same method as in Example 1 except that CuInSe 2 to be the light absorption layer 14 is formed by RF sputtering. Even when CuInSe 2 is used as the light absorption layer 14, it was amorphous before high-temperature heat treatment, but can be crystallized by annealing at 200 ° C. However, since the bulk value of the band gap is originally 1.5 eV or less, when the annealing temperature is 200 ° C., the band gap cannot be suitably controlled by controlling the crystal grain size of the light absorption layer.
  • Example 1 is the same as Example 1 except that the light absorption layer 14 is heat-treated at 200 ° C. during film formation. Even when heat treatment is performed during the formation of the light absorption layer, CuAlTe 2 grows to a crystal grain size suitable for the light absorption layer 14.
  • Example 20 The same as Example 1 except that B is added to the material of the light absorption layer 14 to form a light absorption layer and anneal at 500 ° C.
  • the addition of B is 20 at% on the front side and 5 at% on the back side with respect to the atomic weight of the light absorption layer 14.
  • the addition amount of B is controlled so that the addition amount of B has a gradient distribution from the front side to the back side. By changing the band gap in the film thickness direction of the light absorption layer 14, a band-graded light absorption layer 14 is obtained.
  • Example 21 It is the same as that of Example 1 except performing heat processing from the both sides of the light absorption layer 14 with a CW Nd: YAG laser instead of annealing.
  • heat treatment is performed with an infrared laser, to control the average crystal grain size of CuAlTe 2 in a suitable range can be adjusted to a suitable band gap value CuAlTe 2 thin film as a light absorbing layer 14 .
  • Example 21 is the same as Example 21 except that the intensity of the CW Nd: YAG laser is adjusted and heat treatment is performed only from the back surface of the light absorption layer 14.
  • heat treatment is performed only with the infrared laser from the back surface of the light absorption layer, and the average crystal grain size of CuAlTe 2 of the light absorption layer 14 is distributed in the film thickness direction.
  • the obtained light absorption layer 14 is band graded.
  • Example 12 is the same as Example 12 except that the back side of the light absorption layer 14 is irradiated with a strong laser with a CW Nd: YAG laser and a weak laser is irradiated from the front side.
  • the distribution of the average crystal grain size of CuAlTe 2 in the light absorption layer 14 is caused in the film thickness direction as in Example 22.
  • the obtained light absorption layer 14 is band graded.
  • Example 24 B is added to the material of the light absorption layer 14, and the addition of B is performed by laminating the light absorption layer 1 ⁇ m at a time so that the front side is 20 at% and the back side is 5 at% with respect to the atomic weight of the light absorption layer 14. Except for this, this is the same as Example 21.
  • the addition amount of B so that the addition amount of B is different between the front side and the back side, the light absorption layer after heating becomes a light absorption layer 14 in which layers having different average crystal grain sizes are laminated.
  • Example 25 After laminating 1 ⁇ m of CuAlTe 2 to which 20 at% of B is added as the light absorption layer 14 with respect to the atomic weight of the light absorption layer 14, 1 ⁇ m of CuAlTe 2 having no addition of B or the like is further laminated and annealed at 500 ° C. Other than the above, this embodiment is the same as the first embodiment.
  • the obtained light absorption layer 14 changed the short wavelength light 23 on the front side like the light absorption layer 14 of the multi-junction solar cell of FIG.
  • the wide gap CuAlTe 2 layer 21 that absorbs has a large crystal grain size
  • the narrow gap CuAlTe 2 layer 22 that absorbs the long wavelength light 24 on the back side has a small grain size. Accordingly, the light absorption layer 14 having layers having different band gaps can be obtained.
  • heat treatment is performed to obtain the light absorption layer 14 in which the front side absorbs the short wavelength and the back side absorbs the long wavelength.
  • Te, Se, and S are not limited to one, but may be a combination of two or more.
  • the above example is an example of an embodiment of the present invention. Therefore, the compound thin film solar cell provided with the element of the present invention and the manufacturing method thereof are included in the scope of the present invention.
  • SYMBOLS 10 Compound thin film solar cell, 11 ... Board

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  • Photovoltaic Devices (AREA)

Abstract

L'invention porte sur une photopile en couches minces composite qui est extrêmement efficace et dans laquelle une couche d'absorption de lumière (14) est ajustée afin d'obtenir la bande d'énergie interdite la plus appropriée pour l'absorption de lumière en régulant la taille de ses particules cristallines, ainsi que sur son procédé de fabrication. Plus précisément, l'invention porte sur une photopile en couches minces composite qui est caractérisée en ce qu'elle est pourvue d'au moins un substrat (11), d'une électrode de surface arrière (12) disposée sur le substrat (11), d'une première électrode d'extraction (13) disposée sur l'électrode de surface arrière (12), d'une couche d'absorption de lumière (14) disposée sur l'électrode de surface arrière (12) et comprenant une couche mince de semi-conducteur composite représentée par Cu(Al1-x-yGaxIny)(Te1-a-bSeaSb)2 (où 0 ≤ x ≤ 1, 0 ≤ y ≤1 , 0 ≤ a ≤ 1, 0 ≤ b ≤ 1, 0 ≤ x + y ≤ 1, 0 ≤ a + b ≤ 1), d'un tampon (15) disposé sur la couche d'absorption de lumière (14), d'une couche électrode transparente (16) disposée sur la couche tampon (15) et d'une seconde électrode d'extraction (17) disposée sur la couche électrode transparente (16) et en ce que la taille moyenne des particules cristallines de la couche mince de semi-conducteur composite est de 1 à 100 nm.
PCT/JP2010/001581 2010-03-05 2010-03-05 Photopile en couches minces composite et son procédé de fabrication WO2011108033A1 (fr)

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PCT/JP2010/001581 WO2011108033A1 (fr) 2010-03-05 2010-03-05 Photopile en couches minces composite et son procédé de fabrication

Applications Claiming Priority (1)

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PCT/JP2010/001581 WO2011108033A1 (fr) 2010-03-05 2010-03-05 Photopile en couches minces composite et son procédé de fabrication

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WO2011108033A1 true WO2011108033A1 (fr) 2011-09-09

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Publication number Priority date Publication date Assignee Title
JP2013522910A (ja) * 2010-03-17 2013-06-13 ダウ グローバル テクノロジーズ エルエルシー 接合層を含む光電子活性カルコゲン系薄膜構造体
WO2013129557A1 (fr) * 2012-03-02 2013-09-06 Tdk株式会社 Cellule solaire à semi-conducteurs composés, et procédé de fabrication de couche d'absorption de lumière pour celle-ci
CN103855249A (zh) * 2012-11-29 2014-06-11 台积太阳能股份有限公司 可用作太阳能电池吸收层的基于黄铜矿的材料的铟溅射方法和材料
JP2014123720A (ja) * 2012-11-20 2014-07-03 Toshiba Corp 光電変換素子、光電変換素子の製造方法及び太陽電池
US20140366944A1 (en) * 2012-01-27 2014-12-18 Kyocera Corporation Photoelectric conversion device
JP2018067590A (ja) * 2016-10-18 2018-04-26 国立研究開発法人物質・材料研究機構 銅ガリウムテルル系ｐ型熱電半導体、及びそれを用いた熱電発電素子

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JPH05263219A (ja) * 1991-03-27 1993-10-12 Japan Energy Corp セレン化銅インジウム薄膜の製造方法
JP2000144377A (ja) * 1998-11-11 2000-05-26 Fujikura Ltd 化合物薄膜の製造方法
JP2008192542A (ja) * 2007-02-07 2008-08-21 Nippon Oil Corp カルコパイライトナノ粒子の製造方法及び光電変換素子
JP2008277422A (ja) * 2007-04-26 2008-11-13 Kyocera Corp 積層型光電変換装置

Patent Citations (4)

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JPH05263219A (ja) * 1991-03-27 1993-10-12 Japan Energy Corp セレン化銅インジウム薄膜の製造方法
JP2000144377A (ja) * 1998-11-11 2000-05-26 Fujikura Ltd 化合物薄膜の製造方法
JP2008192542A (ja) * 2007-02-07 2008-08-21 Nippon Oil Corp カルコパイライトナノ粒子の製造方法及び光電変換素子
JP2008277422A (ja) * 2007-04-26 2008-11-13 Kyocera Corp 積層型光電変換装置

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013522910A (ja) * 2010-03-17 2013-06-13 ダウ グローバル テクノロジーズ エルエルシー 接合層を含む光電子活性カルコゲン系薄膜構造体
US20140366944A1 (en) * 2012-01-27 2014-12-18 Kyocera Corporation Photoelectric conversion device
EP2808902A4 (fr) * 2012-01-27 2015-09-23 Kyocera Corp Dispositif de conversion photoélectrique
US9698288B2 (en) 2012-01-27 2017-07-04 Kyocera Corporation Photoelectric conversion device
WO2013129557A1 (fr) * 2012-03-02 2013-09-06 Tdk株式会社 Cellule solaire à semi-conducteurs composés, et procédé de fabrication de couche d'absorption de lumière pour celle-ci
JPWO2013129557A1 (ja) * 2012-03-02 2015-07-30 Tdk株式会社 化合物半導体太陽電池
JP2014123720A (ja) * 2012-11-20 2014-07-03 Toshiba Corp 光電変換素子、光電変換素子の製造方法及び太陽電池
US9705018B2 (en) 2012-11-20 2017-07-11 Kabushiki Kaisha Toshiba Photoelectric conversion element, method for manufacturing photoelectric conversion element, and solar cell
CN103855249A (zh) * 2012-11-29 2014-06-11 台积太阳能股份有限公司 可用作太阳能电池吸收层的基于黄铜矿的材料的铟溅射方法和材料
JP2018067590A (ja) * 2016-10-18 2018-04-26 国立研究開発法人物質・材料研究機構 銅ガリウムテルル系ｐ型熱電半導体、及びそれを用いた熱電発電素子

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