WO2000007250A1 - Method of producing solar cells - Google Patents

Method of producing solar cells Download PDF

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Publication number
WO2000007250A1
WO2000007250A1 PCT/EP1999/005147 EP9905147W WO0007250A1 WO 2000007250 A1 WO2000007250 A1 WO 2000007250A1 EP 9905147 W EP9905147 W EP 9905147W WO 0007250 A1 WO0007250 A1 WO 0007250A1
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WO
WIPO (PCT)
Prior art keywords
transition temperature
coating
cdte
glass transition
support
Prior art date
Application number
PCT/EP1999/005147
Other languages
French (fr)
Inventor
Klaus-Peter Crone
Günter LÖFFELMANN
Karl Modemann
Eberhard Koch
Wolfgang Sauerteig
Original Assignee
Agfa-Gevaert Naamloze Vennootschap
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 Agfa-Gevaert Naamloze Vennootschap filed Critical Agfa-Gevaert Naamloze Vennootschap
Priority to JP2000562962A priority Critical patent/JP2002521848A/en
Priority to AU52851/99A priority patent/AU5285199A/en
Priority to EP99938291A priority patent/EP1114470A1/en
Publication of WO2000007250A1 publication Critical patent/WO2000007250A1/en

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Classifications

    • 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
    • H01L31/036—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 their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • 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
    • H01L31/036—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 their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03925—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIIBVI compound materials, e.g. CdTe, CdS
    • 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
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1864—Annealing
    • 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
    • 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

  • CdTe cadmium telluride.
  • CdTe is used below merely as an example for all thin-layer solar cells.
  • CdTe and CdTe/CdS solar cells may be produced by various methods (US-5 304 499), common to all of which is heat treatment at at least 575°C, to achieve adequate efficiency. These temperatures allow the use only of expensive types of glass as supports.
  • the use of glass as a support has the disadvantage that glass panels may be coated with CdTe only in discontinuous manner, irrespective of the coating method selected.
  • the glass firstly to be provided with a transparent, electrically conductive layer, e.g. of doped tin oxide. This is followed by a thin cadmium sulfide layer (CdS), to which the light-sensitive CdTe layer is then applied by sublimation at 480 to 520°C.
  • a transparent, electrically conductive layer e.g. of doped tin oxide.
  • CdS thin cadmium sulfide layer
  • the apparatus required for application of the CdTe layer is complex and expensive: support material and CdTe source are held in such a way by opposing graphite blocks, which are heated to the necessary temperature, that the CdTe source is located only 2 to 3 mm from the support surface. Sublimation is then effected in a 0.1 mbar inert gas atmosphere, e.g. a nitrogen, helium, argon or hydrogen atmosphere. Large areas of CdTe-coated material for producing solar cells cannot be produced economically in this way.
  • a 0.1 mbar inert gas atmosphere e.g. a nitrogen, helium, argon or hydrogen atmosphere.
  • the object of the invention was the economic production of a support with a photovoltaically active layer, e.g. a CdTe layer.
  • a method was surprisingly found, which permits the use of flexible polymeric films for coating with CdTe and annealing, without the polymeric supporting material being damaged by the high temperatures. In this way, a starting material is obtained for high efficiency solar cells.
  • the invention therefore provides a method of coating organic polymeric supporting materials with CdTe and annealing the CdTe layer of the materials thus coated, characterised in that the supporting material consists of a polymeric material with a glass transition temperature of from 90°C to 200°C and coating of the CdTe layer is carried out at temperatures below the glass transition temperature and annealing at temperatures of at least 250°C, in particular 400 to 600°C, by means of a laser for 0.01 to 1 s with an energy of 2 to 5000 watt per mm 2 .
  • the supporting material is at least 60 ⁇ m, in particular 90 to 120 ⁇ m. thick and the CdTe layer is at most 30 ⁇ m, in particular 2 to 7 ⁇ m, thick.
  • Coating is carried out for example with an aqueous or solvent-containing CdTe suspension.
  • the material is then dried.
  • Suitable coating methods are, for example, flooding and* knife coating.
  • Annealing may be carried out several times; cooling phases are preferably provided between pairs of annealing steps.
  • Suitable polymers are PET and PEN.
  • the polymeric supporting material may be provided with a substrate layer, e.g. of indium-tin oxide, which improves the adhesion of the CdTe layer.
  • the substrate layer should be transparent and electrically conductive.
  • Suitable lasers are, for example, argon lasers and yag lasers with frequency duplication.
  • Organic polymeric supporting materials are flexible and thus permit continuous coating using a suitable coating method.
  • the CdTe particles are particularly fine, in particular in the form of so-called nano-particles, i.e. particles whose average diameter lies in the nanometric range and amounts, for example, to from 3 to 5 nm.
  • an agent e.g. tributyl- phosphane.
  • the invention also provides a solar cell comprising at least one CdTe layer at most
  • the support is a polymeric organic material at least 60 ⁇ m thick and having a glass transition temperature of at least 90°C.
  • the polymeric organic support permits continuous coating by means of a coater, for example a meniscus or curtain coater, as known from the coating of photographic films.
  • a coater for example a meniscus or curtain coater, as known from the coating of photographic films.
  • a film of PEN 100 ⁇ m thick and 100 cm wide is coated continuously with a suspension containing a dispersant and 31 g of cadmium telluride per litre. The coated film is then dried and the layer applied exhibits a dry layer thickness of 5 ⁇ m.
  • the film is annealed as follows:
  • the entire surface is irradiated with an Ar ion laser (wavelength 514 nm; power 7 W) with a focal point of 50 ⁇ m.
  • the temperature is adjusted at from 400 to 450°C.
  • the film After annealing, the film exhibits light-dependent electrical resistance and is thus suitable for the production of a photovoltaic cell.
  • the supporting material is not damaged by exposure to the laser.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Organic polymeric films may serve as supporting materials for at least one photovoltaically active layer, if the supporting material consists of a polymeric material with a glass transition temperature of from 90 °C to 200 °C. The coating of the photovoltaically active layer is carried out at temperatures below the glass transition temperature and annealing is carried out at temperatures of at least 250° by means of a laser.

Description

Method of producing solar cells
The invention relates to an economically improved method of producing thin-layer solar cells, e.g. CdTe solar cells (CdTe = cadmium telluride). CdTe is used below merely as an example for all thin-layer solar cells.
CdTe and CdTe/CdS solar cells may be produced by various methods (US-5 304 499), common to all of which is heat treatment at at least 575°C, to achieve adequate efficiency. These temperatures allow the use only of expensive types of glass as supports. The use of glass as a support has the disadvantage that glass panels may be coated with CdTe only in discontinuous manner, irrespective of the coating method selected.
US-5 304499 describes a method in which coating is carried out at temperatures of only 480 to 520°C, it thus being possible to use cheap types of glass ("window glass",).
To this end, it is necessary for the glass firstly to be provided with a transparent, electrically conductive layer, e.g. of doped tin oxide. This is followed by a thin cadmium sulfide layer (CdS), to which the light-sensitive CdTe layer is then applied by sublimation at 480 to 520°C.
The apparatus required for application of the CdTe layer is complex and expensive: support material and CdTe source are held in such a way by opposing graphite blocks, which are heated to the necessary temperature, that the CdTe source is located only 2 to 3 mm from the support surface. Sublimation is then effected in a 0.1 mbar inert gas atmosphere, e.g. a nitrogen, helium, argon or hydrogen atmosphere. Large areas of CdTe-coated material for producing solar cells cannot be produced economically in this way.
H. Nishiwaki et al, Solar Energy Materials and Solar Cells 37 (1995) 295 to 306 use a polyimide film as support because this material has sufficient heat resistance in comparison to polyethylene terephthalate (PET) and polyethylene naphthalate (PEN),, because of its glass transition temperature of more than 500°C. Polyimide has the disadvantage to be insoluble in usual solvents and to be unable to be molten. It is therefore extremely difficult to be processed.
The known methods do not permit the use of easily produceable films of polymeric organic materials as supports.
The object of the invention was the economic production of a support with a photovoltaically active layer, e.g. a CdTe layer.
A method was surprisingly found, which permits the use of flexible polymeric films for coating with CdTe and annealing, without the polymeric supporting material being damaged by the high temperatures. In this way, a starting material is obtained for high efficiency solar cells.
The invention therefore provides a method of coating organic polymeric supporting materials with CdTe and annealing the CdTe layer of the materials thus coated, characterised in that the supporting material consists of a polymeric material with a glass transition temperature of from 90°C to 200°C and coating of the CdTe layer is carried out at temperatures below the glass transition temperature and annealing at temperatures of at least 250°C, in particular 400 to 600°C, by means of a laser for 0.01 to 1 s with an energy of 2 to 5000 watt per mm2.
Preferably the supporting material is at least 60 μm, in particular 90 to 120 μm. thick and the CdTe layer is at most 30 μm, in particular 2 to 7 μm, thick.
Coating is carried out for example with an aqueous or solvent-containing CdTe suspension. The material is then dried. Suitable coating methods are, for example, flooding and* knife coating.
Annealing may be carried out several times; cooling phases are preferably provided between pairs of annealing steps.
Suitable polymers are PET and PEN. Prior to coating, the polymeric supporting material may be provided with a substrate layer, e.g. of indium-tin oxide, which improves the adhesion of the CdTe layer. The substrate layer should be transparent and electrically conductive.
Suitable lasers are, for example, argon lasers and yag lasers with frequency duplication.
Organic polymeric supporting materials are flexible and thus permit continuous coating using a suitable coating method.
It is especially advantageous for the CdTe particles to be particularly fine, in particular in the form of so-called nano-particles, i.e. particles whose average diameter lies in the nanometric range and amounts, for example, to from 3 to 5 nm.
In this case, it is expedient for an agent to be present during production of the nanoparticles which prevents agglomeration of the nanoparticles. e.g. tributyl- phosphane.
The invention also provides a solar cell comprising at least one CdTe layer at most
30 μm thick on a support, characterised in that the support is a polymeric organic material at least 60 μm thick and having a glass transition temperature of at least 90°C.
Owing to its flexibility, the polymeric organic support permits continuous coating by means of a coater, for example a meniscus or curtain coater, as known from the coating of photographic films. Example
A film of PEN 100 μm thick and 100 cm wide is coated continuously with a suspension containing a dispersant and 31 g of cadmium telluride per litre. The coated film is then dried and the layer applied exhibits a dry layer thickness of 5 μm.
The film is annealed as follows:
The entire surface is irradiated with an Ar ion laser (wavelength 514 nm; power 7 W) with a focal point of 50 μm. The temperature is adjusted at from 400 to 450°C.
After annealing, the film exhibits light-dependent electrical resistance and is thus suitable for the production of a photovoltaic cell.
The supporting material is not damaged by exposure to the laser.

Claims

Claims 4
1. A method of coating organic polymeric supporting materials with at least one photovoltaically active layer and annealing the materials thus coated, characterised in that the supporting material consists of a polymeric material with a glass transition temperature of from 90┬░Cto 200┬░C. Coating is carried out at temperatures below the glass transition temperature and annealing at temperatures of at least 250┬░, in particular 400 to 600┬░C, by means of a laser for 0.01 to 1 s with an energy to 2 to 5000 watt per mm2.
2. A method according to claim 1, wherein the supporting material is at least 60 ╬╝m thick and the photovoltaic layer is at most 30 ╬╝m thick.
3. A method according to claim 1, wherein the supporting material is of polyethylene terephthalate or polyethylene naphthalate.
4. A solar cell comprising at least one photovoltaically active layer on a support, characterised in that the support is a polymeric organic material having a glass transition temperature of from 90┬░C to 200┬░C.
5. A solar cell, according to claim 4, characterised in that the photovoltaically active layer comprises cadmium telluride.
6. A solar cell according to claim 4, characterised in that the support consists of polyethylene terephthalate or polyethylene naphthalate.
PCT/EP1999/005147 1998-07-30 1999-07-20 Method of producing solar cells WO2000007250A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2000562962A JP2002521848A (en) 1998-07-30 1999-07-20 Solar cell manufacturing method
AU52851/99A AU5285199A (en) 1998-07-30 1999-07-20 Method of producing solar cells
EP99938291A EP1114470A1 (en) 1998-07-30 1999-07-20 Method of producing solar cells

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19834358.2 1998-07-30
DE19834358 1998-07-30

Publications (1)

Publication Number Publication Date
WO2000007250A1 true WO2000007250A1 (en) 2000-02-10

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EP (1) EP1114470A1 (en)
JP (1) JP2002521848A (en)
AU (1) AU5285199A (en)
WO (1) WO2000007250A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000046861A1 (en) * 1999-02-02 2000-08-10 Agfa-Gevaert N.V. A method for the production of solar cells
WO2002041363A2 (en) * 2000-11-16 2002-05-23 Solarflex Technologies, Inc. System and methods for laser assisted deposition
US6819845B2 (en) 2001-08-02 2004-11-16 Ultradots, Inc. Optical devices with engineered nonlinear nanocomposite materials

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58194377A (en) * 1982-05-07 1983-11-12 Agency Of Ind Science & Technol Manufacture of thin film solar battery
JPS61168271A (en) * 1985-01-21 1986-07-29 Sumitomo Bakelite Co Ltd Amorphous silicon solar battery
JPS6284568A (en) * 1985-10-08 1987-04-18 Teijin Ltd Thin-film solar cell
JPH0590624A (en) * 1991-09-28 1993-04-09 Nissha Printing Co Ltd Adhesive material for solar battery
US5304499A (en) * 1991-10-03 1994-04-19 Battelle-Institut E.V. Methods of making pn CdTe/CdS thin film solar cells

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58194377A (en) * 1982-05-07 1983-11-12 Agency Of Ind Science & Technol Manufacture of thin film solar battery
JPS61168271A (en) * 1985-01-21 1986-07-29 Sumitomo Bakelite Co Ltd Amorphous silicon solar battery
JPS6284568A (en) * 1985-10-08 1987-04-18 Teijin Ltd Thin-film solar cell
JPH0590624A (en) * 1991-09-28 1993-04-09 Nissha Printing Co Ltd Adhesive material for solar battery
US5304499A (en) * 1991-10-03 1994-04-19 Battelle-Institut E.V. Methods of making pn CdTe/CdS thin film solar cells

Non-Patent Citations (6)

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Title
HAILIN HU ET AL: "CHEMICAL DEPOSITION OF PHOTOSENSITIVE CDS THIN FILMS ON POLYESTER FOILS", JOURNAL OF CRYSTAL GROWTH,NL,NORTH-HOLLAND PUBLISHING CO. AMSTERDAM, vol. 152, no. 3, pages 150-157, XP000626678, ISSN: 0022-0248 *
NISHIWAKI H ET AL: "DEVELOPMENT OF AN ULTRALIGHT, FLEXIBLE A-SI SOLAR CELL SUBMODULE", SOLAR ENERGY MATERIALS AND SOLAR CELLS,NL,ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, VOL. 37, NR. 3/04, PAGE(S) 295-306, ISSN: 0927-0248, XP000521870 *
PATENT ABSTRACTS OF JAPAN vol. 008, no. 036 (E - 227) 16 February 1984 (1984-02-16) *
PATENT ABSTRACTS OF JAPAN vol. 010, no. 376 (E - 464) 13 December 1986 (1986-12-13) *
PATENT ABSTRACTS OF JAPAN vol. 011, no. 286 (E - 541) 16 September 1987 (1987-09-16) *
PATENT ABSTRACTS OF JAPAN vol. 017, no. 434 (E - 1412) 11 August 1993 (1993-08-11) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000046861A1 (en) * 1999-02-02 2000-08-10 Agfa-Gevaert N.V. A method for the production of solar cells
WO2002041363A2 (en) * 2000-11-16 2002-05-23 Solarflex Technologies, Inc. System and methods for laser assisted deposition
WO2002041363A3 (en) * 2000-11-16 2003-05-15 Solarflex Technologies Inc System and methods for laser assisted deposition
US6819845B2 (en) 2001-08-02 2004-11-16 Ultradots, Inc. Optical devices with engineered nonlinear nanocomposite materials

Also Published As

Publication number Publication date
JP2002521848A (en) 2002-07-16
AU5285199A (en) 2000-02-21
EP1114470A1 (en) 2001-07-11

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