[go: up one dir, main page]

WO2011118203A1 - Composition de particules de semi-conducteur composé, film semi-conducteur composé et son procédé, élément de conversion photoélectrique et cellule solaire - Google Patents

Composition de particules de semi-conducteur composé, film semi-conducteur composé et son procédé, élément de conversion photoélectrique et cellule solaire Download PDF

Info

Publication number
WO2011118203A1
WO2011118203A1 PCT/JP2011/001687 JP2011001687W WO2011118203A1 WO 2011118203 A1 WO2011118203 A1 WO 2011118203A1 JP 2011001687 W JP2011001687 W JP 2011001687W WO 2011118203 A1 WO2011118203 A1 WO 2011118203A1
Authority
WO
WIPO (PCT)
Prior art keywords
particle
compound semiconductor
group
semiconductor
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/001687
Other languages
English (en)
Japanese (ja)
Inventor
良太 小宮
貴理博 中野
寛政 澁谷
秀利 工藤
一彦 松浦
佐々木　繁
鶴田　仁志
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to JP2012506845A priority Critical patent/JPWO2011118203A1/ja
Publication of WO2011118203A1 publication Critical patent/WO2011118203A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02601—Nanoparticles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02623—Liquid deposition
    • H01L21/02628—Liquid deposition using solutions
    • 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 chalcopyrite compound semiconductor particle composition, a chalcopyrite compound semiconductor film using the same, a manufacturing method thereof, a photoelectric conversion element and a solar cell using the compound semiconductor film.
  • the chalcopyrite compound semiconductor is a compound represented by the general formula LMX 2 (wherein L represents at least one group IB element, M represents at least one group IIIB, and X represents at least one group VIB). is there.
  • L is at least one selected from the group consisting of Cu, Ag, and Au.
  • M is preferably at least one selected from the group consisting of Al, Ga, and In.
  • X is preferably at least one selected from the group consisting of S, Se, and Te.
  • CIS CuInSe 2
  • Cu In, Ga) Se 2
  • CIGS Cu (In, Ga) Se 2
  • CIS and CIGS are collectively referred to as a CI (G) S system.
  • CI (G) S-based chalcopyrite compound semiconductors can be made lighter than conventional solar cells using silicon, and can be manufactured at low cost because material costs can be reduced. It has the advantage that it can be used (Non-Patent Document 1, etc.).
  • a multi-source deposition method is known as a method for forming a CIGS film (Non-Patent Document 2 or the like).
  • the III-VI group compound is formed by simultaneously depositing a group III element and a VI group element in the first stage, and the group I element and the VI group element are simultaneously deposited in the second stage.
  • a three-stage vapor deposition method is known in which a group III element and a group VI element are deposited at the same time. It is known that a film showing high photoelectric conversion efficiency can be formed by this production method.
  • this method needs to form a film under a vacuum, the manufacturing facility is limited, so it is not suitable for mass production and is a manufacturing method with high manufacturing cost.
  • a selenization method As another film formation method for CIGS films, a selenization method is known (Patent Documents 1, 2, etc.).
  • the selenization method components other than selenium, such as copper, indium, and gallium, are previously formed into a thin film by vapor deposition or sputtering, and then solid selenium, selenium gas, hydrogen selenide, or alkyl selenium is used.
  • This is a manufacturing method for forming a CIGS film by selenization.
  • this method can improve the mass productivity as compared with the above-described multi-source vapor deposition method, it is a production process under vacuum and the production cost is high because a selenium compound is used.
  • Non-patent Document 3 As a film forming method capable of reducing the manufacturing cost by a non-vacuum process, a particle coating method using chalcopyrite compound semiconductor particles has been studied. For example, Wada et al. Of Ryukoku University obtained an ink for screen printing by adding an organic solvent to CIGS particles produced by a low-temperature, short-time MCP (Mechanochemical process), and applied this onto the substrate by screen printing, and selenium gas A CIGS film is formed by firing at 575 ° C. in an atmosphere (Non-patent Document 3). However, the CIGS film actually formed in Non-Patent Document 3 has a low photoelectric conversion efficiency of 2.7%.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a chalcopyrite compound semiconductor particle composition capable of improving the photoelectric conversion efficiency of a compound semiconductor film by a particle coating method. Is. Another object of the present invention is to provide a chalcopyrite compound semiconductor film that is manufactured using the above-described particle composition and can improve the photoelectric conversion efficiency, and a manufacturing method thereof.
  • the compound semiconductor particle composition of the present invention comprises: A group of particles each consisting of at least one semiconductor particle comprising a chalcopyrite compound semiconductor (i) represented by the following general formula and having a number average particle size calculated by a transmission electron microscope of 100 nm or more ( A) and A particle group (BX) composed of at least one kind of a plurality of semiconductor particles and having a number average particle size calculated by a transmission electron microscope smaller than the particle group (A) and / or a non-solid which becomes a solid semiconductor by heating It consists of a semiconductor precursor composition (BY) and contains a filler (B) that fills the gaps between the particle groups (A).
  • LMX 2 wherein L represents at least one group IB element, M represents at least one group IIIB, and X represents at least one group VIB.
  • the compound semiconductor film of the present invention is A compound semiconductor film comprising at least one chalcopyrite compound semiconductor represented by the general formula (i), A step (1) of preparing the compound semiconductor particle composition of the present invention, The film thickness is 0.5 ⁇ m or more and 10 ⁇ m or less manufactured by a manufacturing method that sequentially includes the step (2) of forming the coating film by applying the compound semiconductor particle composition on a substrate.
  • the method for producing the compound semiconductor film of the present invention comprises: A method for producing a compound semiconductor film comprising at least one chalcopyrite compound semiconductor represented by the general formula (i), A step (1) of preparing the compound semiconductor particle composition of the present invention, A step (2) of applying the compound semiconductor particle composition on a substrate to form a coating film.
  • the method for producing a compound semiconductor film of the present invention preferably includes a step (3) of baking the coating film after the step (2).
  • the photoelectric conversion element of the present invention comprises a light absorption layer comprising the compound semiconductor film of the present invention and a pair of electrodes.
  • the solar cell of the present invention comprises the above-described photoelectric conversion element of the present invention.
  • the chalcopyrite type compound semiconductor particle composition which can aim at the improvement of the photoelectric conversion efficiency of the compound semiconductor film by a particle-coating method can be provided.
  • a chalcopyrite-based compound semiconductor film that is manufactured by a particle coating method and can improve the photoelectric conversion efficiency and a method for manufacturing the same can be provided by using the particle composition. .
  • the compound semiconductor film of the present invention includes at least one chalcopyrite compound semiconductor represented by the following general formula (i) and is manufactured by a particle coating method.
  • L represents at least one group IB element, M represents at least one group IIIB, and X represents at least one group VIB.
  • L include Cu, Ag, and Au.
  • M include Al, Ga, and In.
  • X include O, S, Se, and Te.
  • the compound semiconductor film of the present invention preferably includes at least one compound semiconductor represented by the following general formula (ii), and is represented by the following general formula (iii). More preferably, it contains at least one compound semiconductor.
  • (L1) (M1) (X1) 2 (where L1 is at least one IB group element selected from the group consisting of Cu, Ag, and Au, and M1 is selected from the group consisting of Al, Ga, and In) At least one group IIIB, X1 represents at least one group VIB selected from the group consisting of S, Se, and Te.) (Ii), (L2) (M2) (X2) 2 (where L2 is at least one group IB element containing Cu, M2 is at least one group IIIB containing Ga and / or In, and X2 is at least one containing Se) Each represents a VIB family of species.) ... (iii)
  • Examples of the compound semiconductor represented by the formula (iii) include CuInSe 2 (CIS) and Cu (In, Ga) Se 2 (CIGS). These CI (G) S systems have a matching band gap, a high light absorption coefficient, and a high photoelectric conversion efficiency can be obtained with a thin film.
  • the method for producing the compound semiconductor film of the present invention comprises: A step (1) of preparing the compound semiconductor particle composition of the present invention, A step (2) of applying the compound semiconductor particle composition on a substrate to form a coating film.
  • the method for producing a compound semiconductor film of the present invention preferably includes a step (3) of baking the coating film after the step (2).
  • the compound semiconductor particle composition of the present invention is prepared.
  • the relationship between the semiconductor conductivity types of the particle group (A) and the filler (B) is not particularly limited (unless otherwise specified in the present specification, the semiconductor precursor composition (BY)). Is the semiconductor conductivity type after heating.), And these conductivity types are preferably the same.
  • a p-type is generally used as a light absorption layer of a photoelectric conversion element. Accordingly, the semiconductor conductivity type of the particle group (A) and the filler (B) is preferably p-type.
  • composition of the particle group (A) and the filler (B) may be any composition as long as the composition of the compound semiconductor film to be finally formed as a whole.
  • the composition of the particle group (A) may be the same as or different from the composition of the compound semiconductor film to be formed.
  • the amount of selenium in the particle group (A) is set to be smaller than the amount of selenium of the compound semiconductor film of the present invention to be finally produced. it can.
  • the composition of the particle group (BX) and the fired semiconductor precursor composition (BY) may be a chalcopyrite compound semiconductor or any other semiconductor.
  • the semiconductor band gap Eg of the particle group (A) and the filler (B) (unless otherwise specified in the present specification, the semiconductor precursor composition (BY) means a semiconductor band gap after heating). The difference is preferably within 15%.
  • the particle group (BX) is preferably a chalcopyrite compound semiconductor.
  • the compound semiconductor particle composition of the present invention when the compound semiconductor particle composition of the present invention includes a particle group (BX), the compound semiconductor particle composition of the present invention is a chalcopyrite compound represented by the above general formula as the particle group (BX). It is preferable to include a particle group composed of at least one kind of a plurality of semiconductor particles composed of the semiconductor (i).
  • the composition of the semiconductor precursor composition (BY) after firing is preferably a chalcopyrite compound semiconductor.
  • the compound semiconductor particle composition of the present invention includes a semiconductor precursor composition (BY)
  • the compound semiconductor particle composition of the present invention is heated as the semiconductor precursor composition (BY) by heating.
  • the semiconductor precursor composition (BY) comprises at least one elemental metal and / or metal compound containing at least one constituent metal element of the chalcopyrite compound semiconductor (i) represented by the general formula. It is set as the composition containing.
  • the metal compound include various metal salts such as metal halide salts.
  • the simple metal and / or metal compound may form a metal complex in the semiconductor precursor composition (BY).
  • the semiconductor precursor composition (BY) includes at least one organic solvent and / or inorganic solvent that solubilizes the at least one elemental metal and / or the metal compound.
  • the semiconductor precursor composition (BY) can contain any additive such as a pH adjuster or a dispersant.
  • a compound semiconductor particle composition comprising a semiconductor precursor composition (BY) and a filler (B) that fills the gaps of the particle group (A) is used.
  • the particle group (A) having a relatively large average particle diameter may increase the gap between the particles when the coating film is formed.
  • the particle interface distance is long, and the fusion of the particle interface is difficult to proceed during firing. For this reason, voids are not filled during firing, and the resulting compound semiconductor film has large voids.
  • an n-type semiconductor enters a void in a buffer layer formation process such as a chemical bath deposition method (CBD method) after the formation of the light absorption layer. .
  • CBD method chemical bath deposition method
  • a particle group (A) having a relatively large average particle diameter and a particle group (BX) having a relatively small average particle diameter are used in combination, as shown in FIG.
  • Into the voids of a plurality of particles (A) having a relatively large average particle diameter are filled with the particle group (BX) having a relatively small average particle diameter to obtain a film having a small void volume per unit volume. It is done.
  • the generated carrier group (A) having a relatively large average particle diameter functions as a conductive path, deactivation of the carrier can be suppressed.
  • a non-solid semiconductor precursor composition that becomes a solid semiconductor by heating, a particle group (A) having a relatively large average particle diameter, a particle group (BX) having a relatively small average particle diameter, and heating. Even if it uses together with a thing (BY), the effect similar to FIG. 2C and FIG. 2D is acquired.
  • the average particle diameter of the particle group (BX) is smaller because the void volume per unit volume can be reduced.
  • the number average particle diameter calculated from the transmission electron microscope of the particle group (BX) is 50% or less of the number average particle diameter calculated from the transmission electron microscope of the particle group (A). Is preferable, more preferably 20% or less, and still more preferably 10% or less.
  • the particle group (BX) is preferably a particle group (BX-1) having a number average particle diameter calculated by a transmission electron microscope of 100 nm or less.
  • the number average particle size of the particle group (BX) is more preferably 0.1 to 100 nm, further preferably 1 to 80 nm, and particularly preferably 5 to 50 nm.
  • particle diameter the average value of the lengths of the longest axis and the shortest axis.
  • the compound semiconductor particle composition includes a particle group (BX), a particle group (A-1) having a particle diameter mode value calculated by a laser diffraction scattering method of 250 nm or more as the particle group (A); It is preferable that the particle group (BX) includes a particle group (BX-1) having a number average particle diameter calculated by a transmission electron microscope of 100 nm or less.
  • the volume content of the particle group (A-1) in all particles is preferably 20 vol% or more, and the volume content of the particle group (BX-1) is preferably 30 vol% or more.
  • the proportion of the particle group (A) in the compound semiconductor particle composition increases, the deactivation of carriers can be suppressed, which is preferable.
  • the theoretical packing rate when the spherical particles are packed close-packed is 74 vol%.
  • the particle group (A) is combined at a mixing ratio of 74 vol% and the particle group (BX) is 26 vol%. It can be said that it is the most preferable aspect that it is a film.
  • the particle size (BX) is determined from the above volume ratio because the particle shape is not perfectly spherical, has a particle size distribution, does not have a close-packed structure in the film, and the like. It is preferable to increase the ratio of the film structure to reduce the voids.
  • the amount of the particle group (A) in all the particles is preferably 20 to 70 vol%, more preferably 30 to 65 vol%, and further preferably 40 to 60 vol%.
  • the amount of the particle group (BX) in all particles is preferably 30 to 80 vol%, preferably 35 to 70 vol%, and more preferably 40 to 60 vol%.
  • the particle size distribution of the particle group (A) and the particle group (BX) is not limited, but it is easy to design a film structure in which voids are reduced and carrier deactivation is suppressed, and such a film structure can be stably obtained and uniform. In order to obtain a simple film structure, it is preferable that the particle size distribution of each particle is narrow.
  • Examples of the method for producing a chalcopyrite compound semiconductor particle group include a method of applying a known pulverization technique to a bulk or film of a chalcopyrite compound semiconductor and a method for synthesizing fine particles in a liquid phase. Examples include a method of synthesizing fine particle groups in the process of crystal growth from the nucleus.
  • a method for producing a bulk body of a chalcopyrite compound semiconductor for pulverization A method for obtaining a uniform group I-III-VI chalcopyrite crystal by applying pressure while heating a group I element, a group III element, a group VI element, and / or a compound thereof in a solid phase; A solid phase synthesis method such as a method of obtaining a uniform group I-III-VI chalcopyrite crystal by melting a group I element, a group III element, a group VI element, and / or a compound thereof in a high-temperature furnace and air cooling. Can be mentioned.
  • a group I element and a group III element are mixed in a vapor deposition method, a sputtering method, or a molten state to prepare an alloy-like precursor composed of a group I element and a group III element in advance.
  • a method of obtaining a bulk body of chalcopyrite compound semiconductor by a solid phase synthesis method and pulverizing it is particularly preferable.
  • the pulverization method a known technique can be applied, and examples thereof include a dry pulverization method and a wet pulverization method.
  • the dry pulverization method is a method of pulverization in a gas phase such as air or an inert gas. Examples thereof include a method using a mortar and a method using a ball mill or a jet mill.
  • the wet pulverization method is a method of pulverizing in a liquid phase using a solvent, and examples thereof include a method of pulverizing using a mill such as a ball mill, a bead mill, and a jet mill. Since the particle size distribution of the powder obtained by the pulverization method is different, a suitable pulverization method is selected so as to obtain a desired particle size distribution. By classifying the obtained pulverized product using a sieve or the like, a powder having a desired particle size distribution can be obtained.
  • Non-patent Document 5 A method of obtaining CIGS fine particle groups (Non-patent Document 5), or reacting copper chloride, indium chloride, gallium chloride, and selenium element in oleylamine by raising the temperature from room temperature to 240 ° C., and then centrifuging the reaction solution
  • Non-Patent Document 6 A method for obtaining CIGS fine particle groups (Non-Patent Document 6) and the like are known.
  • composition used in the above method for synthesizing fine particle groups in the process of crystal growth from the nucleus can be used as a non-solid semiconductor precursor composition (BY) that becomes a solid semiconductor by heating.
  • the compound semiconductor particle composition of the present invention preferably contains a solvent from the viewpoint of ease of application on a substrate.
  • a solvent is not particularly limited, and an organic solvent, an inorganic solvent such as water, or an organic / inorganic mixed solvent can be used.
  • an organic solvent, an inorganic solvent such as water, or an organic / inorganic mixed solvent can be used.
  • the solvent concentration is too high, there is a high possibility that the film will crack due to bubbles generated in the process of volatilization of the solvent. In addition, if the solvent concentration is too low, it is difficult to obtain a uniform coating film.
  • halides and chalcogenides of Group I elements such as CuCl, CuCl 2 , CuBr, CuBr 2 , and CuSe
  • simple chalcogen elements such as S, Se, and Te
  • firing aids it is preferable to use a material composed of the same kind of element because different elements act as impurities, and CuSe, Se, or the like that melts at a firing temperature or lower is suitable.
  • the compound semiconductor particle composition of the present invention can be prepared by mixing a plurality of components constituting the composition.
  • the method for mixing a plurality of constituent components is not particularly limited, and all the constituent components may be mixed at once, or the plurality of constituent components may be separately mixed and finally mixed.
  • Step (2) is a step of forming a coating film on the substrate by applying the compound semiconductor particle composition prepared in step (1).
  • the compound semiconductor particle composition does not contain the semiconductor precursor composition (BY) or the amount thereof is small, a powdery compound semiconductor particle composition containing little or no solvent (dispersing a solid if necessary) Can also be applied directly dry.
  • an inert gas such as nitrogen or argon, or the same group VI group as the I-III-VI group chalcopyrite compound. It is preferable to use elemental gas.
  • the firing step (3) may be performed in multiple stages by changing the heating temperature.
  • the “multi-stage baking process” mentioned here includes a temporary baking process before the main baking and an annealing process after the main baking. As described above, the chalcopyrite compound semiconductor film of the present invention is manufactured.
  • the entire composition of the compound semiconductor film of the present invention may be uniform or may have a composition distribution in the thickness direction.
  • steps (1) and (2) are repeated by changing the composition of the coating film
  • steps (1) to (3) are repeated.
  • a compound semiconductor film having a composition distribution in the thickness direction can be produced by repeating the above composition. Moreover, even if there is only one coating film, composition distribution may occur naturally in the thickness direction in the step (3) and the like.
  • the thickness of the compound semiconductor film of the present invention is not too large compared to the particle size of the particle group (A), and is preferably 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the film thickness exceeds 10 ⁇ m, the influence of the grain boundary between the particle groups (A) becomes large, and it becomes difficult to sufficiently achieve the effects of the present invention.
  • a chalcopyrite compound semiconductor particle composition capable of improving the photoelectric conversion efficiency of a compound semiconductor film by a particle coating method.
  • a chalcopyrite-based compound semiconductor film that is manufactured by a particle coating method and can improve the photoelectric conversion efficiency and a method for manufacturing the same can be provided by using the particle composition.
  • a compound semiconductor film is manufactured by a particle coating method, unlike a conventional multi-source deposition method or a selenization method, a high-quality compound semiconductor film can be manufactured at a low cost without requiring a vacuum process. .
  • FIG. 1 is a cross-sectional view, and in order to facilitate visual recognition, the actual scales of the layers are appropriately changed.
  • the photoelectric conversion element 10 includes a back electrode layer 12, a light absorption layer (p-type semiconductor layer) 13, a buffer layer (n-type semiconductor layer) 14, a translucent high resistance layer 15, a translucent layer, on a substrate 11.
  • the photoelectrode layer 16 is sequentially laminated.
  • the translucent high resistance layer 15 is a layer provided as necessary, and is not essential.
  • extraction electrodes 17 and 18 are provided on the back electrode layer 12 and the translucent electrode layer 16 as necessary.
  • light and electricity are converted by generating electrons and holes when light is applied to the interface between the p-type semiconductor and the n-type semiconductor.
  • the type of the substrate 11 is not limited and a glass substrate is generally used.
  • a flexible film such as a resin film such as PET (polyethylene terephthalate) or polyimide, or a metal foil such as aluminum or stainless steel may be used.
  • a metal foil such as aluminum or stainless steel
  • an insulating film is necessary on the substrate surface.
  • an alkali metal such as Na and / or an alkaline earth metal such as Mg is supplied from the substrate side during the formation of the light absorption layer, the crystallinity of the film is improved and photoelectric conversion is performed. It is known to improve efficiency.
  • a substrate containing Na such as blue plate glass is used, or an alkali (earth) metal supply layer such as sodium halide is formed between the above-mentioned substrate not containing Na and the light absorption layer 13 by a known method. Also good.
  • a known material can be applied to the back electrode layer 12 as long as it can make ohmic contact with the light absorption layer 13.
  • a known material include gold, molybdenum, nickel, titanium, tantalum, and combinations thereof. Among them, molybdenum and the like are preferably applied because they are inexpensive and easily available.
  • a known method can be applied, and a sputtering method, a heat evaporation method, an electrolytic plating method, an electroless plating method, or the like can be applied.
  • the light absorption layer 13 is a p-type semiconductor layer made of the chalcopyrite compound semiconductor film of the present invention.
  • a thicker light absorption layer 13 is preferable because it can increase light absorption and generate more carriers.
  • the p-type semiconductor layer also functions as a resistance component, it is preferable that the film thickness is small from the viewpoint of efficient extraction of generated carriers. Considering both, the film thickness of the light absorption layer 13 is preferably 0.5 to 10 ⁇ m, more preferably 1 to 5 ⁇ m, and further preferably 1.5 to 3 ⁇ m.
  • the light absorption layer is adjusted at a temperature at which CdS is precipitated by adjusting an aqueous solution containing a cadmium salt (for example, cadmium iodide) and a sulfur-containing compound (for example, thiourea) to a pH at which sulfur is dissociated.
  • a cadmium salt for example, cadmium iodide
  • a sulfur-containing compound for example, thiourea
  • the thickness of the buffer layer 14 is preferably 1 to 300 nm, more preferably 10 to 200 nm, and still more preferably 20 to 150 nm.
  • the high resistance film 15 can be introduced on the buffer layer 14 as necessary.
  • the material of the high resistance film 15 include ZnO.
  • the film thickness of the high resistance film is preferably 300 nm or less, more preferably 100 nm or less.
  • the material of the translucent electrode layer 16 a material having high light transmittance and low resistance is applied.
  • Preferred examples of such materials include indium tin oxide (ITO), indium zinc oxide (IZO), fluorine-doped tin oxide (FTO), and zinc oxide ZnO doped with various metals.
  • the doping element of zinc oxide include gallium, aluminum, boron, silicon, tin, indium, germanium, antimony, iridium, rhenium, cerium, zirconium, scandium, yttrium, and lanthanoid. .05-15 mol% can be doped.
  • a known technique can be applied to the method for forming the translucent electrode layer 16, such as sputtering, electron beam vapor deposition, ion plating, molecular beam epitaxy, ionization vapor deposition, laser ablation, arc plasma vapor deposition, A thermal CVD method, a plasma CVD method, an MOCVD method, a spray pyrolysis method, a sol-gel method, an electroless plating method, an electrolytic plating method, a coating baking method, an aerosol deposition method, a fine particle coating method, and the like can be applied.
  • the photoelectric conversion element 10 of this embodiment can be provided with arbitrary layers other than the above as needed.
  • the photoelectric conversion element 10 of the present embodiment uses the compound semiconductor film of the present invention as the light absorption layer 13, it can be manufactured at a low cost and can improve the photoelectric conversion efficiency. is there.
  • the photoelectric conversion element 1 can be used as a solar cell with a cover glass and a protective film.
  • Average particle diameter / particle group (A-1) The particle group (A-1) having a particle size mode value calculated by the laser diffraction scattering method of 250 nm or more was measured using the following apparatus and solvent.
  • Solvent Chloroform and isopropanol particle group (A)
  • TEM Transmission electron microscope
  • the open circuit voltage (Voc), short circuit current (Jsc), fill factor (FF), and conversion efficiency were calculated as follows.
  • Open circuit voltage (Voc) Voltage at the intersection with the voltage axis
  • Short-circuit current (Jsc) Current at the intersection with the current axis
  • Fill factor (FF) Ratio of maximum output to the product of Voc and Jsc
  • Conversion efficiency ratio of maximum output per unit area to incident power (1000 W / m 2 ). The maximum output per unit area was calculated and taken as the conversion efficiency (%) by taking the ratio with the incident power (1000 W / m 2 ).
  • the CIGS particle group (P2) dispersion having an average particle diameter of 200 nm and the average particle diameter of 100 nm are obtained by changing the pulverization method, rotation speed, pulverization time, and the like of the CIGS bulk body 1 g produced above.
  • a CIGS particle group (P3) dispersion liquid and a CIGS particle group (P4) dispersion liquid having an average particle diameter of 800 nm were obtained.
  • the CIGS particle group (P2) was a wet jet mill
  • the CIGS particle group (P3) was a wet ball mill
  • the CIGS particle group (P4) was a dry jet mill.
  • the CIGS particle concentration in the dispersion was 2% by mass.
  • the CIGS particles after pulverization were used as they were.
  • a crude CIGS particle group was obtained.
  • chloroform, ethanol, and a small amount of oleylamine were added to this particle group and centrifuged, and the supernatant was removed.
  • a CIGS particle group was obtained (6.1 g, 18.5 mmol).
  • the yield was 37%.
  • chloroform By adding chloroform to this CIGS particle group and diluting it, a dispersion having a CIGS particle concentration of 1% by mass was obtained.
  • the number average particle diameter calculated from the transmission electron microscope of the obtained CIGS particle group was 15 nm.
  • the light absorption layer 13 was formed on the back electrode layer 12 by the following process. At least one of the CIGS particle groups (P1) to (P5) dispersions obtained above and the CIGS precursor composition (PC) and a solvent (toluene) are mixed at a predetermined mixing ratio to obtain a total CIGS. It diluted so that particle concentration might be 0.03 vol%, and the coating liquid (particle composition) was obtained. The blending ratio was changed according to Examples and Comparative Examples. 0.4 ml of the coating solution was dropped onto the back electrode 12 to obtain a coating film. After heating at 60 ° C. for 3 minutes, the solvent was removed by heating at 230 ° C. for 10 seconds.
  • the CIGS particle groups (P1) to (P5) dispersions obtained above and the CIGS precursor composition (PC) and a solvent (toluene) are mixed at a predetermined mixing ratio to obtain a total CIGS. It diluted so that particle concentration might be 0.03 vol%, and the coating liquid (particle composition)
  • the operation of coating and solvent removal was repeated 5 times. Thereafter, the obtained coating film was baked at 575 ° C. for 1 hour in a nitrogen atmosphere or a hydrogen / nitrogen atmosphere. This fired film was formed at a rate of 2 L / min. With diethyl selenium gas as nitrogen or hydrogen / nitrogen as a carrier gas.
  • the light absorption layer 13 was obtained by baking at 520 ° C. for 1 hour while flowing at a flow rate of 92 ml / min.
  • a high resistance film 15 was formed by depositing ZnO having a purity of 3N (manufactured by Toyoshima Seisakusho Co., Ltd.) at 100 nm by RF sputtering.
  • the i-ZnO transparent electrode layer 16 is deposited by RF sputtering in the range of 100 to 1000 nm using ZnO (manufactured by Toshima Seisakusho Co., Ltd.) with a purity of 3N and 2 mol% Ga doped.
  • ZnO manufactured by Toshima Seisakusho Co., Ltd.
  • Comparative Example 1-1 Using only the CIGS particle group (P1) dispersion liquid, a coating liquid used for film formation of the light absorption layer was prepared, and a comparative photoelectric conversion element was obtained according to the above process. Table 2 shows the main production conditions and evaluation results. The photoelectric conversion efficiency of the obtained device was 0.1%, and the short-circuit current was 1.6 mA / cm 2 .
  • Comparative Example 1-2 Using only the CIGS particle group (P5) dispersion liquid, a coating liquid used for film formation of the light absorption layer was prepared, and a comparative photoelectric conversion element was obtained according to the above process. Table 2 shows the main production conditions and evaluation results. The photoelectric conversion efficiency of the obtained device was 0.03%, and the short-circuit current was 1.3 mA / cm 2 .
  • Example 2 Using the CIGS particle group (P2) dispersion liquid (average particle diameter 200 nm) and the CIGS particle group (P5) dispersion liquid (average particle diameter 15 nm), a coating liquid used for film formation of the light absorption layer was prepared.
  • the volume ratio of the particle group (P2) and the particle group (P5) in the coating solution was 1: 1, and the photoelectric conversion element of the present invention was obtained according to the above process.
  • Table 3 shows the main production conditions and evaluation results.
  • the photoelectric conversion efficiency of the obtained device was 0.20%, and the short-circuit current was 3.7 mA / cm 2 . A short-circuit current was higher than that of Comparative Example 2 described later, and a highly efficient device was obtained.
  • the photoelectric conversion element using the compound semiconductor film of the present invention as a light absorption layer has high conversion efficiency between light and electricity and can be manufactured at low cost, it is used as a photoelectric conversion element such as a solar cell, an optical sensor, an image sensor, and a photodiode. Available.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Photovoltaic Devices (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)

Abstract

La présente invention a trait à une composition de particules de semi-conducteur composé de chalcopyrite qui permet d'augmenter l'efficacité de conversion photoélectrique d'un film semi-conducteur composé. La composition de particules de semi-conducteur composé selon la présente invention comprend : des particules (A) qui sont formées à partir d'une pluralité d'au moins un type de particules de semi-conducteur et qui ont un diamètre moyen des particules supérieur ou égal à 100 nm, tel que calculé au moyen d'un microscope électronique en transmission ; et un matériau de remplissage (B), qui est formé à partir d'une pluralité d'au moins un type de particules de semi-conducteur, est constitué de particules (BX) qui ont un diamètre moyen des particules inférieur à celui des particules (A) tel que calculé au moyen d'un microscope électronique en transmission, et/ou d'une composition de précurseur de semi-conducteur non solide (BY) qui forme un semi-conducteur solide lorsqu'elle est chauffée. (A) et (B) sont formés à partir de semi-conducteurs composés de chalcopyrite chacun étant représenté par la formule générale ci-dessous, et le matériau de remplissage (B) remplit les espaces entes les particules (A). (i) LMX2 (où, L représente au moins un type d'élément de groupe IB, M représente au moins un type de groupe IIIB, et X représente au moins un type de groupe VIB).
PCT/JP2011/001687 2010-03-23 2011-03-23 Composition de particules de semi-conducteur composé, film semi-conducteur composé et son procédé, élément de conversion photoélectrique et cellule solaire Ceased WO2011118203A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012506845A JPWO2011118203A1 (ja) 2010-03-23 2011-03-23 化合物半導体粒子組成物、化合物半導体膜とその製造方法、光電変換素子、及び太陽電池

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2010065467 2010-03-23
JP2010-065467 2010-03-23
JP2011-055789 2011-03-14
JP2011055789 2011-03-14

Publications (1)

Publication Number Publication Date
WO2011118203A1 true WO2011118203A1 (fr) 2011-09-29

Family

ID=44672781

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/001687 Ceased WO2011118203A1 (fr) 2010-03-23 2011-03-23 Composition de particules de semi-conducteur composé, film semi-conducteur composé et son procédé, élément de conversion photoélectrique et cellule solaire

Country Status (3)

Country Link
JP (1) JPWO2011118203A1 (fr)
TW (1) TW201201373A (fr)
WO (1) WO2011118203A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013129537A1 (fr) * 2012-02-28 2013-09-06 Tdk株式会社 Cellule solaire à semiconducteur composé
WO2013180137A1 (fr) * 2012-05-30 2013-12-05 凸版印刷株式会社 Procédé de fabrication pour une couche mince semi-conductrice composée, et pile solaire dotée de ladite couche mince semi-conductrice composée
JP2015107899A (ja) * 2013-12-05 2015-06-11 旭化成株式会社 結晶成長促進剤及びそれを用いたカルコゲナイド化合物の製造方法
JP2015193513A (ja) * 2014-03-31 2015-11-05 旭化成株式会社 結晶成長促進剤及びそれを用いた金属カルコゲナイド化合物の製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018016213A1 (fr) * 2016-07-20 2018-01-25 ソニー株式会社 Film semi-conducteur, procédé de fabrication associé, élément de conversion photoélectrique, élément d'imagerie à semi-conducteurs et dispositif électronique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06140646A (ja) * 1992-07-14 1994-05-20 Canon Inc 光起電力素子
JPH0730138A (ja) * 1993-06-25 1995-01-31 Matsushita Electric Ind Co Ltd ＣｄＳ焼結膜の製造方法
JP2009146578A (ja) * 2007-12-11 2009-07-02 Noritake Co Ltd 太陽電池および太陽電池用アルミニウムペースト
JP2010129642A (ja) * 2008-11-26 2010-06-10 Kyocera Corp 薄膜太陽電池の製法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04127483A (ja) * 1990-06-21 1992-04-28 Fuji Electric Co Ltd ＣｕＩｎＳｅ↓２太陽電池の製造方法
JP3244408B2 (ja) * 1995-09-13 2002-01-07 松下電器産業株式会社 薄膜太陽電池及びその製造方法
JP2005117012A (ja) * 2003-09-17 2005-04-28 Matsushita Electric Ind Co Ltd 半導体膜とその製造方法、およびそれを用いた太陽電池とその製造方法
US7736940B2 (en) * 2004-03-15 2010-06-15 Solopower, Inc. Technique and apparatus for depositing layers of semiconductors for solar cell and module fabrication
JP4131965B2 (ja) * 2004-12-28 2008-08-13 昭和シェル石油株式会社 Ｃｉｓ系薄膜太陽電池の光吸収層の作製方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06140646A (ja) * 1992-07-14 1994-05-20 Canon Inc 光起電力素子
JPH0730138A (ja) * 1993-06-25 1995-01-31 Matsushita Electric Ind Co Ltd ＣｄＳ焼結膜の製造方法
JP2009146578A (ja) * 2007-12-11 2009-07-02 Noritake Co Ltd 太陽電池および太陽電池用アルミニウムペースト
JP2010129642A (ja) * 2008-11-26 2010-06-10 Kyocera Corp 薄膜太陽電池の製法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
T.WADA ET AL.: "Fabrication of Cu(In,Ga)Se2 thin films by a combination of mechanochemical and screen-printing/sintering processes", PHYSICA STATUS SOLIDI(A), vol. 203, no. 11, 2006, pages 2593 - 2597, XP055154224, DOI: doi:10.1002/pssa.200669652 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013129537A1 (fr) * 2012-02-28 2013-09-06 Tdk株式会社 Cellule solaire à semiconducteur composé
JPWO2013129537A1 (ja) * 2012-02-28 2015-07-30 Tdk株式会社 化合物半導体太陽電池
WO2013180137A1 (fr) * 2012-05-30 2013-12-05 凸版印刷株式会社 Procédé de fabrication pour une couche mince semi-conductrice composée, et pile solaire dotée de ladite couche mince semi-conductrice composée
CN104350611A (zh) * 2012-05-30 2015-02-11 凸版印刷株式会社 化合物半导体薄膜的制作方法及具备该化合物半导体薄膜的太阳能电池
JPWO2013180137A1 (ja) * 2012-05-30 2016-01-21 凸版印刷株式会社 化合物半導体薄膜の作製方法およびその化合物半導体薄膜を備える太陽電池
JP2015107899A (ja) * 2013-12-05 2015-06-11 旭化成株式会社 結晶成長促進剤及びそれを用いたカルコゲナイド化合物の製造方法
JP2015193513A (ja) * 2014-03-31 2015-11-05 旭化成株式会社 結晶成長促進剤及びそれを用いた金属カルコゲナイド化合物の製造方法

Also Published As

Publication number Publication date
JPWO2011118203A1 (ja) 2013-07-04
TW201201373A (en) 2012-01-01

Similar Documents

Publication Publication Date Title
TWI687369B (zh) 用於光伏打吸收膜之核殼奈米顆粒
CN106233470B (zh) 薄膜太阳能电池的光吸收层的制备方法及利用其的薄膜太阳能电池
CN102458832A (zh) 用于光电电池的薄膜
TWI609840B (zh) 用於薄膜光伏打裝置之無機鹽－奈米粒子墨水及相關方法
US10170651B2 (en) Metal-doped cu(In,Ga) (S,Se)2 nanoparticles
US9893220B2 (en) CIGS nanoparticle ink formulation having a high crack-free limit
WO2011118203A1 (fr) Composition de particules de semi-conducteur composé, film semi-conducteur composé et son procédé, élément de conversion photoélectrique et cellule solaire
US20180248057A1 (en) Preparation of Copper-Rich Copper Indium (Gallium) Diselenide/Disulphide Nanoparticles
JP2012151221A (ja) カルコゲナイト系化合物半導体及びその製造方法
JP2012191147A (ja) 成膜用塗布剤とその製造方法、化合物半導体膜とその製造方法、光電変換素子、及び太陽電池
JP2013051224A (ja) 化合物半導体粒子とその製造方法、化合物半導体膜、光電変換素子、及び太陽電池
US20180355201A1 (en) CIGS Nanoparticle Ink Formulation with a High Crack-Free Limit
Watt et al. Copper-based Multinary Materials for Solar Cells
WATTª et al. Copper-based Multinary Materials for Solar
HK1222408B (en) Cigs nanoparticle ink formulation having a high crack-free limit
JP2014203864A (ja) 無機膜とその製造方法、無機膜の製造用基材、光電変換素子、及び太陽電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11759013

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012506845

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11759013

Country of ref document: EP

Kind code of ref document: A1