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EP1114470A1 - Method of producing solar cells - Google Patents

Method of producing solar cells

Info

Publication number
EP1114470A1
EP1114470A1 EP99938291A EP99938291A EP1114470A1 EP 1114470 A1 EP1114470 A1 EP 1114470A1 EP 99938291 A EP99938291 A EP 99938291A EP 99938291 A EP99938291 A EP 99938291A EP 1114470 A1 EP1114470 A1 EP 1114470A1
Authority
EP
European Patent Office
Prior art keywords
transition temperature
coating
cdte
glass transition
support
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.)
Withdrawn
Application number
EP99938291A
Other languages
German (de)
French (fr)
Inventor
Klaus-Peter Crone
Günter LÖFFELMANN
Karl Modemann
Eberhard Koch
Wolfgang Sauerteig
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.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Agfa Gevaert AG
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 NV, Agfa Gevaert AG filed Critical Agfa Gevaert NV
Publication of EP1114470A1 publication Critical patent/EP1114470A1/en
Withdrawn legal-status Critical Current

Links

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
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/169—Thin semiconductor films on metallic or insulating substrates
    • 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
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/128—Annealing
    • 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
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/169—Thin semiconductor films on metallic or insulating substrates
    • H10F77/1696—Thin semiconductor films on metallic or insulating substrates the films including Group II-VI materials, e.g. CdTe or CdS
    • 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.

Landscapes

  • 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.
EP99938291A 1998-07-30 1999-07-20 Method of producing solar cells Withdrawn EP1114470A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19834358 1998-07-30
DE19834358 1998-07-30
PCT/EP1999/005147 WO2000007250A1 (en) 1998-07-30 1999-07-20 Method of producing solar cells

Publications (1)

Publication Number Publication Date
EP1114470A1 true EP1114470A1 (en) 2001-07-11

Family

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EP99938291A Withdrawn EP1114470A1 (en) 1998-07-30 1999-07-20 Method of producing solar cells

Country Status (4)

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

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19904082A1 (en) * 1999-02-02 2000-08-03 Agfa Gevaert Ag Process for the production of solar cells
WO2002041363A2 (en) * 2000-11-16 2002-05-23 Solarflex Technologies, Inc. System and methods for laser assisted deposition
US7005669B1 (en) 2001-08-02 2006-02-28 Ultradots, Inc. Quantum dots, nanocomposite materials with quantum dots, devices with quantum dots, and related fabrication methods
US20030066998A1 (en) 2001-08-02 2003-04-10 Lee Howard Wing Hoon Quantum dots of Group IV semiconductor materials
US6819845B2 (en) 2001-08-02 2004-11-16 Ultradots, Inc. Optical devices with engineered nonlinear nanocomposite materials

Family Cites Families (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
JPH0671091B2 (en) * 1985-10-08 1994-09-07 帝人株式会社 Thin film solar cell
JPH0590624A (en) * 1991-09-28 1993-04-09 Nissha Printing Co Ltd Adhesive material for solar battery
DE4132882C2 (en) * 1991-10-03 1996-05-09 Antec Angewandte Neue Technolo Process for the production of pn CdTe / CdS thin-film solar cells

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
B.M. BASOL ET AL.: "Flexible and light weight copper indium diselenide solar cells on polyimide substrates", SOLAR ENERGY MATERIALS AND SOLAR CELLS, vol. 43, no. 1, 15 August 1996 (1996-08-15), Amsterdam, NL, pages 93 - 98 *

Also Published As

Publication number Publication date
WO2000007250A1 (en) 2000-02-10
AU5285199A (en) 2000-02-21
JP2002521848A (en) 2002-07-16

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