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WO2009030281A1 - Procédé de formation d'une pile solaire à couche mince - Google Patents

Procédé de formation d'une pile solaire à couche mince Download PDF

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Publication number
WO2009030281A1
WO2009030281A1 PCT/EP2007/059422 EP2007059422W WO2009030281A1 WO 2009030281 A1 WO2009030281 A1 WO 2009030281A1 EP 2007059422 W EP2007059422 W EP 2007059422W WO 2009030281 A1 WO2009030281 A1 WO 2009030281A1
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WO
WIPO (PCT)
Prior art keywords
layer
copper
chalcogenide
substrate
atoms
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/EP2007/059422
Other languages
English (en)
Inventor
Ayodhya Nath Tiwari
Kaia Ernits
Christopher John Hibberd
Marc Roland Kaelin
Maxim Ganchev
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.)
Eidgenoessische Technische Hochschule Zurich ETHZ
Original Assignee
Eidgenoessische Technische Hochschule Zurich ETHZ
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 Eidgenoessische Technische Hochschule Zurich ETHZ filed Critical Eidgenoessische Technische Hochschule Zurich ETHZ
Priority to PCT/EP2007/059422 priority Critical patent/WO2009030281A1/fr
Publication of WO2009030281A1 publication Critical patent/WO2009030281A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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]
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
    • C23C16/4582—Rigid and flat substrates, e.g. plates or discs
    • C23C16/4583—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally
    • C23C16/4584—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally the substrate being rotated
    • 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 refers to the production of a ternary or greater compound thin film with properties suitable for use as a light absorbing layer in a photon to electricity conversion device at least containing elements from group I, III, VI of the periodic table of the elements. More specifically, the present invention refers to the production of chalcopyrite layers for thin film solar cells consisting of a stack of layers supported upon a substrate.
  • one or more layers of material are first deposited and then converted into a single layer with the desired morphology, phase and composition or compositional gradient by a conversion process consisting of one or more sequential treatments.
  • This approach is sometimes referred to in the art as the two stage process.
  • the initially deposited layer or layers are referred to as precursor layers and may be layers of elements (both metals and non- metals), binary and higher metallic alloys, binary and higher oxides, binary and higher non-oxide compounds (including chalcogenides and salts) and mixtures of these materials. More precisely, the material may be present in the form of continuous films or as particulates, which may be intercalated with another material in some embodiments of the process.
  • the precursor may include material that is not required in the light absorbing layer; this material is preferentially removed during the conversion process.
  • the conversion process may contain a treatment which supplies energy to facilitate phase changes, mixing and recrystallization within the precursor layer or layers. This energy is preferably supplied by heating within a furnace using lamps, resistive elements or inductive elements. The heating is performed within an atmosphere that ensures the desired layer is formed. Such an atmosphere may be at a pressure other than atmospheric pressure and may contain an inert gas, one or more chalcogen hydride gases, one or more chalcogen vapours, a reducing gas and/or an oxidising gas. An example of an industrial process is taught in reference [4].
  • the conversion process may also contain a treatment within which unwanted materials that are present in or upon the layer are removed by etching. Such an etching stage may utilise either a chemical etchant or an electrochemical process to remove the unwanted material.
  • the precursors are deposited using vacuum equipment.
  • the methods reported in the articles [5,6,7] use sputtering and thermal evaporation to deposit stacked elemental films, where the resulting layers are annealed, sometimes in the presence of a chalcogen, to form the desired light absorbing layer.
  • the precursor layers are deposited from solution baths.
  • a layer with composition close to that of CuInSe 2 or one of its alloys with gallium and sulphur may be deposited by electrodeposition and then annealed to form the desired light absorbing layer with reported efficiencies of up to 10.6%.
  • electroless deposition is described [9] where an additional vacuum step was required to produce cell efficiencies of up to 12.4%.
  • An alternative embodiment of the two-stage method uses spray techniques to deposit layers from solutions containing all of the required elements onto a heated substrate whereupon the constituents of the solution are pyrolysed to form the desired light absorbing layer whilst the unwanted materials are removed as volatile reaction products.
  • Solar cells based upon CuInSe 2 layers produced by this method were reported to yield efficiencies of up to 5% [10].
  • a two stage method [1 1] first layers of copper indium oxide were deposited by spray deposition and then converted into the desired light absorbing layer by annealing with selenium vapour.
  • Another alternative embodiment of the two-stage method uses metal salts as precursor materials [12] where inorganic salts of copper, indium and gallium are mixed in a solution with a binder and then doctor blade coated onto a substrate which was subsequently annealed with selenium vapour.
  • a further group of embodiments of the two stage method are concerned with the deposition of particulate precursors.
  • indium selenide layers are deposited and a copper flux is provided onto the layer held at 200°C and the selenium flux is provided onto the resulting layer held at 600°C.
  • the resulting solar cell is reported to have an efficiency of 13.7%.
  • Reference [16] showed that the resulting films may still contain binary chalcogenide phases, mainly copper selenide. These secondary phases can be removed by chemical etching and solar cells of reported efficiencies of 15-16% were prepared with this approach.
  • a group III chalcogenide layer is exposed to a flux of selenium and copper, which diffuses into the layer.
  • One object of the present invention is to provide a low-cost large area scalable method for the production of a thin film suitable for use as a light absorbing layer in a thin film solar cell. Furthermore, an object is to avoid some of the aforementioned problems, namely, the use of complex equipment and the maintenance of high processing temperatures for extended durations, both of which tend to increase the cost of said solar cells. Accordingly, the present invention proposes a process according the wording of claim one.
  • the present invention proposes a method for producing a ternary or greater thin film, said method comprising the steps:
  • the resulting structure may further be completed into a thin film solar cell by any method known to those skilled in the art, including an optional surface etching step, a partial electrolyte treatment, buffer layer deposition, transparent conducting electrode deposition, anti reflection layer, metal grid structure deposition.
  • the term substrate may refer to any material known to those skilled in the art as being suitable for the role such as, but not limited to, glass, metal or polyimide and additionally may include one or more thin films, such as e.g., but not limited to, a metallic electrode, a transparent conducting oxide electrode, a highly reflective layer, a diffusion barrier, a layer of dopant material or a layer designed to alter the interfacial properties between two such layers. Additionally, the substrate may provide material that is incorporated into the light absorbing layer, including but not limited to the case of an alkali dopant diffusing from soda lime glass.
  • any known method to produce thin films of chalcogenide compounds may be used including but not restricted to evaporation, spray pyrolysis, chemical vapour deposition, chemical bath deposition, electrodeposition, electroless deposition, sol-gel methods, atomic layer deposition, paste coating and chalcogenization.
  • copper or other group IB metals such as e.g. silver or gold are incorporated into a binary chalcogenide thin film or binary chalcogenide alloy thin film from its surroundings, which may be a liquid such as a solution or a gas.
  • a binary chalcogenide thin film or binary chalcogenide alloy thin film from its surroundings, which may be a liquid such as a solution or a gas.
  • a solution it may be maintained at a temperature less than or equal to its boiling point at the pressure of the container and can use different type of agitation such as ultrasonic or magnetic stirring.
  • Said pressure may be other than atmospheric pressure.
  • the incorporation of copper ions into the chalcogenide layer may be thought of as an exchange of cations between the chalcogenide layer and the surrounding media followed by diffusion of the ions or as an addition into the amorphous or microcrystalline structure of the chalcogenide layer.
  • the media from which the group IB atoms are incorporated into the chalcogenide layer may contain ingredients other than the source of group IB atoms, including but not limited to reagents to regulate the pH, chelating agents and ions of metals other than copper. Additionally, the concentration of group III metal ions in the media may increase throughout the process as they may leave the chalcogenide thin film to make vacancies by which the copper ions are incorporated into the thin film.
  • the stoichiometry of the light absorbing layer may be set during the incorporation of copper ions into the film by adjusting the concentration of ions in the media, the temperature at which the process is performed and the duration of the immersion of the chalcogenide layer into the process media.
  • an optional surface cleaning treatment with an adequate solvent agent can be performed.
  • an adequate solvent agent can be used as an example potassium chloride solution can be used to remove copper or copper salt rests.
  • the heat treatment in inert or chalcogen vapour or gas containg atmosphere allows the group IB atoms to diffuse into the layer and recrystallizes the material mainly into the chalcopyrite phase.
  • the used heating parameters and atmosphere influences the compositional gradient as known to those skilled in the art.
  • impurity binary chalcogenide phases may still remain in the layer.
  • Copper rich impurity phases are known to degrade the solar cell parameters.
  • this phase may effectively be removed via etching, e.g. by using a solution of potassium cyanide, which additionally improves the surface properties of the layer.
  • group IB rich phases may be neutralized by addition of group III chalcogenides as for example by chemical bath deposition, spray pyrolysis or evaporation.
  • Figure 1 through Figure 5 show cross sections of a solar cell throughout stages of the method of the invention
  • Figure 6 shows an x-ray photoelectron spectroscopy (XPS) depth profile of a binary chalcogenide layer after it has undergone the treatment to incorporate copper into the layer
  • XPS x-ray photoelectron spectroscopy
  • Figure 7 shows an x-ray photoelectron spectroscopy (XPS) depth profile of a layer prepared in an identical manner after it has undergone heat treatment in the presence of selenium vapour, and
  • Figure 8 shows the resulting Cu concentration in function of diffusion time measured with energy dispersive X-ray analysis after Ion in-diffusion and subsequent selenization, where the used solution was prepared with ethyleneglycol, wherein CuCl and KCl were dissolved at 17O 0 C
  • Figure 9 shows x-ray diffraction (XRD) patterns of a layer throughout various stages of the method of the present invention.
  • a clean soda lime glass plate (layer 1) is utilised as substrate and coated with a thin layer of molybdenum (layer 2), preferably 0.5-1 ⁇ m in thickness.
  • This layer is most often deposited via DC magnetron sputtering.
  • a thin film of a binary chalcogen compound (Figure 2, layer 3) such as In 2 Se 3 or an alloy of two or more such compounds, such as (In 5 Ga) 2 Se 3 , is deposited by physical vapour deposition.
  • This layer is preferably between 0.7 ⁇ m and 2 ⁇ m in thickness.
  • This layer and the substrate upon which it was deposited are then immersed in an aqueous solution containing a copper salt such as Cu(NO 3 ) 2 and a reagent to reduce the pH below 7, such as acetic acid.
  • a copper salt such as Cu(NO 3 ) 2
  • a reagent to reduce the pH below 7, such as acetic acid.
  • the solution is heated to 95°C for the desired duration, preferably between 20 and 60 minutes.
  • the layers and substrate are removed and rinsed in clean water.
  • the chalcogenide layer ( Figure 3, layer 4) contains sufficient copper atoms to produce the desired chalcogenide layer, however the copper atoms are distributed unevenly throughout the depth of the layer, with a peak in concentration towards the surface as shown by x-ray photoelectron spectroscopy (XPS) measurements ( Figure 6).
  • XPS x-ray photoelectron spectroscopy
  • the chalcogenide layer containing the copper atoms is then transferred to a furnace where it is heated in the presence of a source of selenium atoms, from a heated crucible of elemental selenium or with a stream of hydrogen-selenide/sulfide.
  • a source of selenium atoms from a heated crucible of elemental selenium or with a stream of hydrogen-selenide/sulfide.
  • the chalcogenide layer is converted to a chalcopyrite layer (Figure 4, layer 5),such as CuInSe 2 ,or Cu(In,Ga)Se2 with homogeneous copper concentration throughout its depth as confirmed by x-ray photoelectron spectroscopy (XPS) measurements ( Figure 7).
  • XPS x-ray photoelectron spectroscopy
  • Binary copper selenide impurity phases may still be present in the heat treated layer, especially for the case of copper concentrations exceeding stochiometry.
  • These copper selenides are removed by immersing the layer structure in a solution of 10% potassium cyanide at room temperature for a few seconds. After removal from the cyanide solution the layer structure is washed in clean water.
  • the structure is fabricated into a completed solar cell, as shown in Figure 5, by the application of a thin (20-200nm) cadmium sulphide film (layer 6) upon the chalcopyrite light absorbing layer, a layer of intrinsic zinc oxide and a layer of aluminium doped zinc oxide (100-lOOOnm combined thickness, layer 7) upon the cadmium sulphide layer and the application of a bilayer grid of nickel and aluminium over a small percentage of the surface (structured layer 8).
  • Possible techniques for the deposition of this layers are chemical bath deposition for the cadmium sulphide, radio- frequency magnetron sputtering for the zinc oxide layers and electron beam evaporation for the metal grid bilayer.
  • Curve 1 of Figure 8 shows the diffraction patterns of an evaporated indium-selenide layer corresponding to layer 3 of Figure 2. The pattern indicates a hexagonal ⁇ -In2Se3 phase.
  • curve 2 of Figure 8 was recorded. Comparison with curve 1 shows extra peaks at around 26.7° and 44.5° (2 theta). These peaks are identified as characteristic of copper rich copper selenide phases, such as Cu 2 . x Se.
  • the X-ray diffractogram of a sample after the heat treatment step is shown in curve 3 of Figure 8. All of the peaks in the diffractogram may be indexed to chalcopyrite CuInSe 2 .
  • the aqueous solution of the first embodiment is replaced with a high molecular weight alcoholic solvent allowing a higher process temperature to be employed at a given pressure.
  • the media is a solution containing ethyleneglycol and Cu + or Cu ++ salts such as CuCl, CuCl 2 , Cu(NOa) 2 or Cu(SO 4 ) 2 .
  • the temperature can be raised to 170°C and higher during immersion of the sample with negligible evaporation of the solvent. The increased temperature leads to much faster in-diffusion of the copper ions.
  • the media is a solution containing ethyleneglycol, 0.6M copperchloride (CuCl), and 2M potassium chloride (KCl).
  • CuCl copperchloride
  • KCl 2M potassium chloride
  • the Cu+ ions are stabilised by complexation with KCl which further improves the solubility of the CuCl.
  • Figure 9 shows the copper concentration (measured by EDX) before and after the heat treatment which evenly distributes the copper throughout the layer depth. Mainly the whole range of useful copper concentrations can be achieved with the disclosed process. A final desired Cu concentration in the range of 20-25% can be achieved with immersion times of a few minutes.
  • Thickness measurements before and after immersion treatments showed a slight increase in the layer thickness.
  • additional layers may be incorporated into the structure, including but not limited to: one or more barrier layers deposed between the initial substrate layer and the electrode layer with the function of electrically isolating the electrode layer from the substrate and/or with the function of limiting diffusion between these two layers; a layer of material intended to diffuse into the chalcogenide/chalcopyrite layer either during its deposition or during the heat treatment.
  • the replacement of some of the materials specified in the possible embodiments may be performed in order to achieve a conversion of the solar cell geometry from that of a substrate solar cell to that of either a superstrate solar cell or to that of a semi-transparent solar cell wherein light that is not absorbed is free to pass through the cell.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Selon la présente invention, le procédé de fabrication d'une couche mince composite ternaire ou supérieure comprend les étapes suivantes : dépôt d'une couche mince de chalcogénure du groupe IIIA binaire ou supérieur sur un substrat; incorporation d'atomes du groupe IB dans ladite couche de chalcogénure par la mise en contact de cette dernière avec des milieux contenant des atomes du groupe IB, et traitement thermique de la couche mixte résultante pour la convertir en une phase homogène.
PCT/EP2007/059422 2007-09-07 2007-09-07 Procédé de formation d'une pile solaire à couche mince Ceased WO2009030281A1 (fr)

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PCT/EP2007/059422 WO2009030281A1 (fr) 2007-09-07 2007-09-07 Procédé de formation d'une pile solaire à couche mince

Applications Claiming Priority (1)

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PCT/EP2007/059422 WO2009030281A1 (fr) 2007-09-07 2007-09-07 Procédé de formation d'une pile solaire à couche mince

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07283430A (ja) * 1994-04-12 1995-10-27 Matsushita Electric Ind Co Ltd 太陽電池の製造方法
JP2000269217A (ja) * 1999-03-18 2000-09-29 Kobe Steel Ltd 銅配線膜の形成方法
DE19917758A1 (de) * 1999-04-10 2000-10-19 Pmc Product Management Cousult CIS-Solarzelle und Verfahren zu ihrer Herstellung
US6323417B1 (en) * 1998-09-29 2001-11-27 Lockheed Martin Corporation Method of making I-III-VI semiconductor materials for use in photovoltaic cells
US20070151862A1 (en) * 2005-10-03 2007-07-05 Dobson Kevin D Post deposition treatments of electrodeposited cuinse2-based thin films

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07283430A (ja) * 1994-04-12 1995-10-27 Matsushita Electric Ind Co Ltd 太陽電池の製造方法
US6323417B1 (en) * 1998-09-29 2001-11-27 Lockheed Martin Corporation Method of making I-III-VI semiconductor materials for use in photovoltaic cells
JP2000269217A (ja) * 1999-03-18 2000-09-29 Kobe Steel Ltd 銅配線膜の形成方法
DE19917758A1 (de) * 1999-04-10 2000-10-19 Pmc Product Management Cousult CIS-Solarzelle und Verfahren zu ihrer Herstellung
US20070151862A1 (en) * 2005-10-03 2007-07-05 Dobson Kevin D Post deposition treatments of electrodeposited cuinse2-based thin films

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GABOR A M ET AL: "Band-gap engineering in Cu(In,Ga)Se2 thin films grown from (In,Ga)2Se3 precursors", SOLAR ENERGY MATERIALS AND SOLAR CELLS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 41-42, 1 June 1996 (1996-06-01), pages 247 - 260, XP004007944, ISSN: 0927-0248 *
WILSON K ET AL: "Implantation assisted copper diffusion: A different approach for the preparation of CuInS2/In2S3 p-n junction", APPLIED PHYSICS LETTERS, AIP, AMERICAN INSTITUTE OF PHYSICS, MELVILLE, NY, vol. 89, no. 1, 7 July 2006 (2006-07-07), pages 13510 - 013510, XP012085516, ISSN: 0003-6951 *

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