WO2013094941A1 - Cellule solaire et son procédé de fabrication - Google Patents

Cellule solaire et son procédé de fabrication Download PDF

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Publication number
WO2013094941A1
WO2013094941A1 PCT/KR2012/010969 KR2012010969W WO2013094941A1 WO 2013094941 A1 WO2013094941 A1 WO 2013094941A1 KR 2012010969 W KR2012010969 W KR 2012010969W WO 2013094941 A1 WO2013094941 A1 WO 2013094941A1
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WO
WIPO (PCT)
Prior art keywords
layer
crystal structure
solar cell
buffer layer
electrode layer
Prior art date
Application number
PCT/KR2012/010969
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English (en)
Inventor
Chul Hwan Choi
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Lg Innotek Co., Ltd.
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Filing date
Publication date
Application filed by Lg Innotek Co., Ltd. filed Critical Lg Innotek Co., Ltd.
Publication of WO2013094941A1 publication Critical patent/WO2013094941A1/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
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • 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
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/0749—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • 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
    • 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
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the embodiment relates to a solar cell and a method of fabricating the same.
  • Solar cells may be defined as devices to convert light energy into electric energy through a photovoltaic effect of generating electrons when light is incident onto a P-N junction diode.
  • the solar cell may be classified into a silicon solar cell, a compound semiconductor solar cell mainly including a group I-III-VI compound or a group III-V compound, a dye-sensitized solar cell, and an organic solar cell according to materials constituting the junction diode.
  • a solar cell made from CIGS (CuInGaSe), which is one of group I-III-VI Chalcopyrite-based compound semiconductors, represents superior light absorption, higher photoelectric conversion efficiency with a thin thickness, and superior electro-optic stability, so the CIGS solar cell is spotlighted as a substitute for a conventional silicon solar cell.
  • a CIGS thin film solar cell is fabricated by sequentially forming a substrate including sodium, a back electrode layer, a light absorbing layer, a buffer layer, and a front electrode layer.
  • the buffer layer is interposed between the light absorbing layer and the front electrode layer representing the lattice constant difference and the energy bandgap difference therebetween, so that the light absorbing layer and the front electrode layer represent superior adhesive strength therebetween.
  • CdS cadmium sulfide
  • Cd cadmium
  • Cd has toxicity, and is formed through a wet process called a chemical bath deposition (CBD) process.
  • the Cd-free solar cell employs ZnS having the bandgap energy greater than that of CdS for the buffer. Since the ZnS layer has wide bandgap energy Eg, the ZnS layer represents superior transmittance with respect to a short wavelength so that efficiency can be improved. However, since the bandgap energy Eg of the ZnS layer makes a great difference from the bandgap energy Eg of the light absorbing layer, the ZnS layer represents lower efficiency than that of a CdS layer, which is employed as the buffer layer, due to the alignment of the bandgap.
  • the embodiment provides a solar cell having the aligned bandgap energy (Eg) between the layers and a method of fabricating the same.
  • a solar cell includes a back electrode layer on a support substrate, a light absorbing layer on the back electrode layer, a buffer layer provided on the light absorbing layer and employing a cubic crystal structure as a main crystal structure, and a front electrode layer on the buffer layer.
  • a solar cell includes a front electrode layer provided on a support substrate and employing a cubic crystal structure as a main crystal structure, a buffer layer provided on the front electrode layer and employing a cubic crystal structure as a main crystal structure, a light absorbing layer on the buffer layer, and a back electrode layer on the light absorbing layer.
  • a method of fabricating a solar cell includes forming a back electrode layer on a support substrate, forming a light absorbing layer on the back electrode layer, forming a buffer layer, which employs a cubic crystal structure as a main crystal structure, on the light absorbing layer, and forming a front electrode layer on the buffer layer.
  • the solar cell of the embodiments includes the buffer layer employing the cubic crystal structure as the main crystal structure.
  • the buffer layer employing the cubic crystal structure as the main crystal structure can represent bandgap energy less than that of the conventional buffer layer employing the hexagonal crystal structure as a main crystal structure. Therefore, according to the solar cell of the embodiments, the bandgap of the buffer layer can match with the bandgap of the adjacent layers, thereby minimizing the recombination between electrons and holes and improving the photoelectric conversion efficiency.
  • FIGS. 1 to 5 are sectional views showing a method of fabricating a solar cell according to the embodiment.
  • FIGS. 1 to 5 are sectional views showing a method of fabricating the solar cell according to the first embodiment.
  • the solar cell and the method of fabricating the solar cell according to the first embodiment will be described with reference to FIGS. 1 to 5.
  • the back electrode layer 200 is formed on the support substrate 100.
  • the support substrate 100 has a plate shape and supports a back electrode layer 200, a light absorbing layer 300, a buffer layer 400, a high resistance buffer layer 500 and a front electrode layer 600.
  • the support substrate 100 may include an insulator.
  • the support substrate 100 may include a glass substrate, a plastic substrate, or a metallic substrate.
  • the support substrate 100 may include a soda lime glass substrate.
  • the support substrate 100 may be transparent.
  • the support substrate 100 may be rigid or flexible.
  • the back electrode layer 200 may be formed on the support substrate through a physical vapor deposition (PVD) scheme or a plating scheme.
  • PVD physical vapor deposition
  • the back electrode layer 200 is a conductive layer.
  • the back electrode layer 200 may include one selected from the group consisting of molybdenum (Mo), gold (Au), aluminum (Al), chrome (Cr), tungsten (W), and copper (Cu).
  • Mo represents a less thermal expansion coefficient difference from the support substrate 100 as compared with that of another element, so that Mo has a superior adhesive strength to prevent delamination from the support substrate 100.
  • Mo may satisfy the characteristics required for the back electrode layer 200.
  • the light absorbing layer 300 is provided on the back electrode layer 200.
  • the light absorbing layer 300 includes a group I-III-VI compound.
  • the light absorbing layer 300 may have a Cu (In,Ga) Se2 (CIGS) crystal structure, a Cu (In) Se2 crystal structure, or a Cu (Ga) Se2 crystal structure.
  • the light absorbing layer 300 has an energy bandgap in the range of about 1eV to about 1.8eV.
  • the light absorbing layer 300 may be formed through various schemes such as a scheme of forming a Cu(In,Ga)Se2 (CIGS) based light absorbing layer 300 by simultaneously or separately evaporating Cu, In, Ga, and Se and a scheme of performing a selenization process after a metallic precursor layer has been formed.
  • CIGS Cu(In,Ga)Se2
  • the metallic precursor layer is formed on the back electrode layer 200 through a sputtering process employing a Cu target, an In target, or a Ga target. Thereafter, the metallic precursor layer is subject to the selenization process so that the Cu (In, Ga) Se2 (CIGS) based light absorbing layer 300 is formed.
  • a sputtering process employing a Cu target, an In target, or a Ga target.
  • the sputtering process employing the Cu target, the In target, and the Ga target and the selenization process may be simultaneously performed.
  • a CIS or a CIG based light absorbing layer 300 may be formed through the sputtering process employing only Cu and In targets or only Cu and Ga targets and the selenization process.
  • the buffer layer 400 is provided on the light absorbing layer 300.
  • a P-N junction is formed between the light absorbing player 300 of a CIGS or CIGSS compound thin film, which serves as a P-type semiconductor, and the front electrode layer 600 which serves as an N-type semiconductor.
  • a buffer layer having the intermediate band-gap between the band-gaps of the two materials is required to form the superior junction between the two materials.
  • the buffer layer 400 may have a thickness in the range of about 10 nm to about 30 nm, but the embodiment is not limited thereto.
  • the buffer layer 400 may include cadmium sulfide (CdS), zinc sulfide (ZnS), InXSY, and InXSeYZn(O, OH).
  • the buffer layer 400 may be zinc sulfide (ZnS).
  • the main crystal structure of a ZnS layer according to the embodiment is a cubic crystal structure.
  • the cubic crystal structure preferably occupies 50% of the crystal structure of the ZnS layer. More preferably, the cubic crystal structure occupies about 80% or more of the crystal structure of the ZnS layer, but the embodiment is not limited thereto. In particular, actually, the whole crystal structure of the ZnS layer is preferably the cubic crystal structure.
  • the ZnS layer employing the cubic crystal structure as the main crystal structure may represent bandgap energy less than that of the ZnS layer employing the conventional hexagonal crystal structure as a main crystal structure.
  • the bandgap energy of the ZnS layer employing the cubic crystal structure according to the embodiment as a main structure may be reduced by about 0.1 eV to about 0.2 eV as compared with the bandgap energy of a ZnS layer employing the conventional hexagonal crystal structure as the main structure, but the embodiment is not limited thereto.
  • the difference between the bandgap energy of the ZnS layer according to the embodiment and the bandgap energy of the light absorbing layer 300 may be reduced. Therefore, according to the solar cell of the embodiment, the recombination between electrons and holes can be minimized and the photoelectric conversion efficiency can be improved by improving the alignment of the bandgap between the buffer layer 400 and the adjacent layers.
  • the bandgap energy of the ZnS layer employing the cubic crystal structure as the main crystal structure may be in the range of about 3.4 eV to about 3.5 eV, but the embodiment is not limited thereto.
  • the ZnS layer employing the cubic crystal structure as the main crystal structure may be formed through an atomic layer deposition (ALD), an MOCVD (Metal-Organic Chemical Vapor Deposition) scheme, or a chemical bath deposition (CBD) scheme. More preferably, the ZnS layer employing the cubic crystal structure as the main crystal structure may be formed the following CBD scheme.
  • ALD atomic layer deposition
  • MOCVD Metal-Organic Chemical Vapor Deposition
  • CBD chemical bath deposition
  • a metal complex compound is formed through the reaction between a zinc ion source and a complex compound.
  • the zinc ion source may include a zinc acetate solution
  • the complex compound may include ethylene diamine tetra acetic acid disodium salt (Na2EDTA).
  • Na2EDTA ethylene diamine tetra acetic acid disodium salt
  • reaction solution is formed by mixing the metal complex compound with a sulfur source to prepare a reaction solution.
  • the sulfur source may include thioacetamide or thiourea SC(NH2)2.
  • sodium hydroxide (NaOh) may be additionally used as a pH control agent.
  • CBD scheme used to form the ZnS layer according to the embodiment does not require ammonia or hydrazine.
  • the support substrate 100 having the light absorbing layer 300 is dipped into the reaction solution, so that the ZnS layer employing the cubic crystal structure as the main crystal structure is deposited on the light absorbing layer 300.
  • the CBD process may be performed at the temperature of about 65°C to about 80°C.
  • the crystal structure of the ZnS layer formed through the above scheme may be measured through typical X-ray diffraction. That is to say, regarding the X-ray diffraction peak, a hexagonal crystal system shows the peaks of a (100) plane and a (002) plane, and a cubic crystal system shows the peak of a (111) surface. Determining if the ZnS layer has a hexagonal crystal structure may be made based on the crystal orientation in which the peaks are shown. In detail, after preparing an amorphous glass sample case (plate shape) having an about 0.5 mm-concave part, the ZnS layer is filled in the concave part. Then, after the surface of the concave part has been formed to the uniform flat surface, the X ray is irradiated to the surface of the concave part. Accordingly, a small amount of specimens may be used for the measurement.
  • the high resistance buffer layer 500 is provided on the buffer layer 400.
  • the high resistance buffer layer 500 may include i-ZnO which is zinc oxide not doped with impurities.
  • the high resistance buffer layer 500 may be formed on the buffer layer 400 through a sputtering process.
  • the cubic crystal structure may be predominantly represented in even the high resistance buffer layer 500.
  • the high-temperature heat treatment process employing the temperature of about 700°C may be additionally performed, but the embodiment is not limited thereto.
  • the front electrode layer 600 is formed on the high resistance buffer layer 500.
  • the front electrode layer 600 is transparent conductive layer.
  • the front electrode layer 600 may include B doped zinc oxide (ZnO:B, BZO), Al doped zinc oxide (AZO), or Ga doped zinc oxide (GZO).
  • the front electrode layer 600 may use Al doped zinc oxide (AZO) or B doped zinc oxide (ZnO:B, BZO) by taking the bandgap and contact with the buffer layer 500 into consideration, but the embodiment is not limited thereto.
  • the front electrode layer 600 may be formed by depositing a transparent conductive material on the high resistance buffer layer 500.
  • the front electrode layer 600 may be deposited through a sputtering scheme or a Metal-Organic Chemical Vapor Deposition (MOCVD) scheme.
  • MOCVD Metal-Organic Chemical Vapor Deposition
  • the front electrode layer 600 may be deposited through a sputtering process.
  • the cubic crystal structure may be predominantly formed in even the front electrode layer 600.
  • a high-temperature and high-pressure process may be additionally performed.
  • the front electrode layer 600 having the cubic crystal structure may be formed by processing the front electrode layer 600 having the hexagonal crystal structure under the condition that the temperature is about 550K and the pressure is about 15 GPa.
  • the embodiment of the disclosure may include a superstrate-structure solar cell.
  • the solar cell according to the second embodiment may include the front electrode layer 600 provided on the support substrate 100 and employing the cubic crystal structure as the main crystal structure, the buffer layer 400 provided on the front electrode layer 600 and employing the cubic crystal structure as a main crystal structure, the light absorbing layer 300 provided on the buffer layer 400, and the back electrode layer 200 provided on the light absorbing layer 300.
  • the solar cell according to the second embodiment may include all components described regarding the solar cell according to the first embodiment, and the details of the components will be omitted in order to avoid redundancy for the convenience of explanation.
  • any reference in this specification to “one embodiment,” “an embodiment,” “example embodiment,” etc. means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention.
  • the appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment.

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  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Energy (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne une cellule solaire et son procédé de fabrication. La cellule solaire comprend une couche d'électrode arrière sur un substrat de support, un couche absorbant la lumière sur la couche d'électrode arrière, une couche tampon disposée sur la couche absorbant la lumière et employant une structure de cristal cubique comme structure de cristal principale, et couche d'électrode avant sur la couche tampon.
PCT/KR2012/010969 2011-12-19 2012-12-14 Cellule solaire et son procédé de fabrication WO2013094941A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020110137802A KR101338557B1 (ko) 2011-12-19 2011-12-19 태양전지 및 이의 제조방법
KR10-2011-0137802 2011-12-19

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WO2013094941A1 true WO2013094941A1 (fr) 2013-06-27

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KR101643236B1 (ko) * 2015-02-27 2016-07-29 주식회사 무한 박막형 태양전지를 이용한 구조물
KR102396820B1 (ko) * 2017-09-06 2022-05-16 한국전자통신연구원 태양 전지 모듈 및 그 제조 방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100122980A (ko) * 2009-05-14 2010-11-24 주식회사 신안에스엔피 솔라셀을 이용한 윈도우 제조방법 및 이에 이용되는 카세트
KR20110048731A (ko) * 2009-11-03 2011-05-12 엘지이노텍 주식회사 태양전지 및 이의 제조방법
JP2011146594A (ja) * 2010-01-15 2011-07-28 Toyota Central R&D Labs Inc 光電素子用バッファ層及びその製造方法、並びに、光電素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100122980A (ko) * 2009-05-14 2010-11-24 주식회사 신안에스엔피 솔라셀을 이용한 윈도우 제조방법 및 이에 이용되는 카세트
KR20110048731A (ko) * 2009-11-03 2011-05-12 엘지이노텍 주식회사 태양전지 및 이의 제조방법
JP2011146594A (ja) * 2010-01-15 2011-07-28 Toyota Central R&D Labs Inc 光電素子用バッファ層及びその製造方法、並びに、光電素子

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