WO2013160356A1 - Method for manufacturing a semiconductor thin film - Google Patents

Method for manufacturing a semiconductor thin film Download PDF

Info

Publication number
WO2013160356A1
WO2013160356A1 PCT/EP2013/058509 EP2013058509W WO2013160356A1 WO 2013160356 A1 WO2013160356 A1 WO 2013160356A1 EP 2013058509 W EP2013058509 W EP 2013058509W WO 2013160356 A1 WO2013160356 A1 WO 2013160356A1
Authority
WO
WIPO (PCT)
Prior art keywords
thin film
annealing
film
precursor
etching
Prior art date
Application number
PCT/EP2013/058509
Other languages
French (fr)
Inventor
Marina MOUSEL
Alex Redinger
Susanne Siebentritt
Original Assignee
Université Du Luxembourg
Tdk Corporation
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 Université Du Luxembourg, Tdk Corporation filed Critical Université Du Luxembourg
Publication of WO2013160356A1 publication Critical patent/WO2013160356A1/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02491—Conductive materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H01L21/02554—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H01L21/02557—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H01L21/0256—Selenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02656—Special treatments
    • H01L21/02664—Aftertreatments
    • 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
    • H01L31/0256—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 the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4

Definitions

  • the present invention relates to a method for manufacturing semiconductor thin films.
  • it relates to the manufacturing of (Ag x Cui_ x ) 2 ZnZ(SySei_ y )4 thin films, wherein x and y can be selected between 0 and 1 , and wherein Z is selected from Sn, Pb, Ge and Si.
  • a Cu 2 ZnSn(SySei_ y )4 absorber layer is considered the leading candidate to replace a Cu(ln,Ga)(S,Se) 2 absorber layer in thin films solar cells because it only contains cheap, and abundant elements.
  • Cu 2 ZnSn(SySei_y) 4 solar cells have reached power conversion efficiencies of 10.1 %, clearly showing the potential of the material (Aaron et al. , Prog. Photovolt. Res. Appl., 201 1. DOI: 10.1002/pip.1 160).
  • Cu 2 ZnSn(SySei_ y )4 thin films for solar cell applications can be produced by a variety of different techniques.
  • deposition techniques e.g. evaporation techniques, sputtering, E-beam, electrodeposition, spray pyrolisis, photo-chemical deposition, spin coating, the iodine transport method, printing, pulsed laser deposition etc.
  • a first possibility is to deposit all elements or binary compounds at elevated temperatures such that the absorber is formed in one step.
  • a further technique involves all elements or binary compounds being deposited at once (at room or elevated temperature) and then heated to re-crystallize. Finally, all elements or binary compounds may be deposited sequentially, and then heated to intermix and crystallize.
  • the Cu 2 ZnSn(SySei_ y ) 4 semiconductor compound is spontaneously formed on a heated substrate (e.g. coevaporation, sputtering technique) in a single step.
  • the metals or binaries are first deposited near room temperature and are then, in a further step, annealed in a furnace comprising a S/Se atmosphere in order to form
  • a precursor film containing the metals or the metals together with selenium and/or sulphur is provided in a first step.
  • the precursor film is annealed, or heat- treated, in an S/Se atmosphere according to the proposal by Katagiri et al., Solar Energy Materials and Solar Cells 49 (1997) 407-414.
  • High quality material is typically achieved through heating the precursor film at high temperatures of 500°C to 600°C.
  • Annealing in furnaces is typically performed in an S/Se vapour together with different gases: Ar, N 2 , H 2 , H 2 /N 2 .
  • Annealing in N 2 gas plus elemental sulfur vapour has been described by Araki et al., Thin Solid Films, 517 (2008) 1457-1460.
  • Annealing in N 2 and 5wt% H 2 S gas is disclosed in Katagiri et al., Solar Energy Materials and Solar Cells, 49 (1997) 407-414.
  • Annealing in N 2 and 20wt% H 2 S gas is described in Katagiri et al., Applied Physics Express, 1 (2008) 041201 .
  • Annealing in Ar and elemental S vapour and, alternatively, annealing in Ar and 5wt% H2S gas has been suggested by Scragg et al., Thin Solid Films, 517 (2009) 2481-2484. Annealing in N 2 + 10wt%H 2 and elemental S vapor has been disclosed in Scragg et al., Journal of Electroanalytical Chemistry, 646 (2010) 52-59. Some annealing experiments have also been carried out under vacuum.
  • Solar cells based on co-evaporated (Ag x Cui_ x ) 2 ZnSn(SySei_y) 4 thin films which are produced in a single step without annealing, have been recently shown to achieve an efficiency of 9.15%.
  • the corresponding thin films have a Cu-rich growth period, (I. Repins, et al., Solar Energy Materials and Solar Cells, 2012).
  • the Cu-rich growth period is achieved while tuning the fluxes during the co-evaporation process.
  • the elements are deposited at higher temperature in order to avoid the annealing step.
  • a Cu-rich growth period of the thin film appears to be beneficial for the efficiency of solar cells.
  • using a precursor thin film that is characterized by a Cu-rich growth period has so far not lead to promising solar cells using the two-step fabrication process, wherein the precursor thin film is subsequently annealed at high temperature.
  • a method for manufacturing a (Ag x Cui_ x ) 2 ZnZ(S y Sei_ y )4 thin film wherein both x and y are selected in between 0 and 1 , and wherein Z is selected from Sn, Ge, Si, Pb.
  • the method comprises the following steps:
  • a thin film comprising Ag and/or Cu, the thin film further comprising Zn and Z, the thin film further comprising S and/or Se,
  • the thin film presents a (Ag x Cui -x ) / (Zn + Z) ratio that is greater than 1 ;
  • the annealing of the thin film may occur at a temperature between 450 and 600 °C. In an embodiment, the annealing occurs at 500 °C. The annealing may occur at a temperature range of between 300 and 1000 °C, preferably between 400 and 800 °C, and more preferably between 500 and 600 °C.
  • the etching solution may preferably comprise KCN, and more preferably 10% KCN.
  • the step of annealing may comprise annealing the thin film in an atmosphere, which more preferably may comprise S and/or Se.
  • the step of annealing further may comprise enclosing the thin film, together with said atmosphere, in an inert enclosure.
  • An opening may preferably be provided in the enclosure, through which S and/or Se is supplied.
  • the thin film may preferably be provided on a substrate, which may preferably be molybdenum.
  • a semiconductor thin film is provided, which is produced using the described method.
  • a device comprising a semiconductor thin film produced using the described method is provided.
  • the device may preferably be a photovoltaic cell, which may preferably exhibit an efficiency of at least 6 %.
  • the method according to the present invention provides an efficient way of producing (Ag x Cui_ x ) 2 ZnZ(SySei_y)4 semiconductor thin films from Cu-rich precursor films whereby the formation of Cu-Sn-Se compounds, such as for example Cu 2 SnSe 3 , on the surface of the annealed film is largely inhibited.
  • Solar cells that incorporate semiconductor thin films manufactured according to the present invention exhibit an improved open circuit voltage and efficiency as compared to solar cells that incorporate known (Ag x Cui_ x ) 2 ZnZ(S y Sei_ y )4 thin films produced from Cu- rich precursors, which are annealed at high temperature..
  • Figure 1 is a flow chart illustrating a preferred embodiment of the method according to the present invention.
  • Figure 2 is a schematic illustration of a preferred embodiment according to the present invention.
  • Figure 3 shows experimental results of a precursor film produced according to a preferred embodiment of the method according to the present invention, prior to etching and annealing.
  • Figure 4 shows experimental results of thin film after annealing, without prior etching.
  • Figure 5a and 5b show experimental results of a device produced according to a preferred embodiment of the method according to the present invention. Detailed Description
  • a method for manufacturing a (Ag x Cui -x ) 2 ZnZ(S y Sei- y )4 thin film is provided.
  • Z is selected to be one of Sn, Pb, Ge or Si while both x and y are select in between 0 and 1.
  • a precursor thin film 20 is provided in a first step, 100.
  • the precursor thin film comprises Ag and/or Cu, comprises Zn and Z, and further comprises S and/or Se.
  • the film may be produced by any methods known in the art.
  • the precursor presents an (Ag x Cui -x ) / (Zn+Z) ratio that is greater than 1 , it is therefore (Ag x Cui -x )-rich.
  • the method further comprises the sequential steps of etching the thin film with an etching solution, 200, prior to annealing the film at a high temperature 300.
  • the precursor film may be provided on a substrate 10.
  • the annealing of the thin film may preferably take place in an atmosphere comprising S and/or Se.
  • Both the thin film and the atmosphere may be enclosed in an inert enclosure 30. At least one opening is provided in the enclosure, through which S and/or Se or other compounds may be introduced into the atmosphere.
  • the composition of the corresponding precursor thin film is described by Cu 2 ZnSnSe 4 , CZTSe.
  • the Cu excess in the Cu-rich precursor film has been shown to lead to a copper selenide, Cu-Se, phase at the surface of the precursor film.
  • the copper selenide phase incorporates tin and turns into secondary phases, the most likely being the ternary Cu 2 SnSe 3 .
  • the ternary Cu 2 SnSe 3 phase is suspected to limit the open circuit voltage of a solar cell using the resulting semiconductor thin film.
  • KCN is known to be able to remove copper selenide, Cu-Se, compounds. Examples of such compounds are CuSe and Cu 2 Se.
  • Cu-Se copper selenide
  • Cu 2 Se copper selenide
  • the Cu-Se phases on the surface of the thin film are largely removed.
  • the removed Cu-Se phases can no longer act as sources for the production of new secondary phases during annealing. It has been observed that after annealing, the pre-etched thin film presents less of the detrimental secondary phases on its surface.
  • a solar cell incorporating the resulting thin film presents an improved efficiency and open circuit voltage as compared to solar cells using known thin films produced from Cu-rich precursor films.
  • Etching the precursor film prior to annealing has the further advantage that the Cu-Se phases at the surface of the Cu-rich precursor film do not interdiffuse into the thin film during annealing.
  • Etching the film only after annealing can only remove the Cu-Se secondary phases that are present on the surface of the film after annealing.
  • the secondary phases may diffuse deeper into the film.
  • the precursor film is etched before being annealed, less of the Cu-Se secondary phases are formed during the annealing, and therefore less of these secondary phases tend to diffuse into the film.
  • the proposed method is efficient in producing thin film semiconductors with less Cu-Se secondary phases throughout the film than known methods. This outlines the underlying principle of the present invention in general terms. Further specific embodiments according to the present invention are described without further limiting the scope of the invention.
  • a CZTSe precursor film is first produced in a molecular beam epitaxy system with Cu, Zn, Sn evaporation sources and Se is supplied via a valved source.
  • the deposition temperature is set to 320 °C and all four elements are coevaporated on a molybdenum coated soda lime glass substrate. This corresponds to step 100.
  • the CZTSe precursor film does not decompose. Indeed CZTSe is known to decompose according to the following equation at temperatures higher than 350°C.
  • Fig 3 shows a secondary ion mass spectrometry, SI MS, analysis of the Cu-rich precursor film according to sample A, which has neither been etched nor annealed.
  • the sputtering time on the x-axis corresponds to different depths of the layer from the surface of the thin film (left) to the molybdenum substrate (right). It can be concluded that a copper selenide phase is present at the surface of the precursor film.
  • Fig 4 shows a SI MS analysis of sample A after it has been annealed at a high temperature of 500-600 °C in a graphite box, without prior etching of the sample.
  • the annealing takes place in an H 2 /N 2 atmosphere at a pressure of 1 mbar.
  • the atmosphere further contains 15mg of SnSe and 20 mg of Se in order to avoid the decomposition according to equation (1 ) to take place.
  • the annealed absorber presents a Cu- and Sn-rich interface. This leads to the model that during annealing, the copper selenide phase at the surface of the precursor film incorporates tin and turns into secondary phases, the most likely being the ternary Cu 2 SnSe 3 phases.
  • the ternary Cu 2 SnSe 3 phase is suspected to limit the open circuit voltage of a solar cell using the resulting semiconductor thin film.
  • sample A and B have been etched during 30 seconds to 1 minute in a 10% KCN etching solution, corresponding to step 200. This is done before proceeding to annealing, which corresponds to step 300.
  • the films have been characterized at various stages of the production process using scanning electron microscopy, SEM, equipped with an energy dispersive X-Ray, EDX, analyser. The resulting composition ratios are given in Table I for sample A and Table II for sample B.
  • Solar cells have been built as follows using the semiconductor thin films resulting from the above production method, based on sample A and B.
  • the annealed thin film is etched in KCN for 30 seconds in order to remove any remaining Cu x Se or Se impurities. This step is followed by chemical bath deposition of CdS.
  • the n-type window layer is sputtered via RF-magnetron sputtering from intrinsic and Al-doped ZnO, followed by e-beam evaporation of Aluminium grids.
  • the resulting solar cells have been characterised with current-voltage, IV, measurements and quantum efficiency, QE, measurements, as usual in the art.
  • the current-voltage measurements have been performed with a halogen lamp, which has been adjusted to 100 mW/cm 2 .
  • Photoluminescence at room temperature is used to determine the bandgap of the resulting absorber layer in the near surface region. Photoluminescence is performed with an Ar-lon Laser with a spotsize of 1 ⁇ . For SIMS analysis, an area with a diameter of 250 ⁇ has been analysed and 8 keV Cs + ions have been used. The solar cell results based on pre-etched sample A are shown in Fig 5a and 5b. The solar cell parameters based on pre-etched sample A are given in Table I I I. A maximum solar cell efficiency of 6.1 % has been achieved. A maximum open circuit voltage of 353 mV has been achieved. It is noted that a solar cell produced from the annealed precursor of sample A without etching prior to the annealing step, did not result in a working solar cell.
  • the present invention provides a method for manufacturing a (Ag x Cui_ x )2ZnZ(SySei_ y )4 thin film, wherein Z is selected from Sn, Ge, Si, Pb.
  • the method comprises the steps of providing a Cu-rich precursor film, etching the precursor film and subsequently annealing the etched film.
  • the method results in thin film semiconductors that allow to increase the efficiency of solar cells which incorporate them.

Landscapes

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

Abstract

The present invention relates to a method for manufacturing semiconductor thin films. In particular, it relates to the manufacturing of (Ag x Cu1- x )2ZnZ(S y Se1- y )4 thin films, wherein x and y can be selected between 0 and 1, and wherein Z is selected from Sn, Pb, Ge and Si. The method according to the present invention provides an efficient way of producing (Ag x Cu1- x )2ZnZ(S y Se1- y )4 semiconductor thin films from Cu-rich precursor films.

Description

METHOD FOR MANUFACTURING A SEMICONDUCTOR THIN FILM
Field of the invention The present invention relates to a method for manufacturing semiconductor thin films. In particular, it relates to the manufacturing of (AgxCui_x)2ZnZ(SySei_y)4 thin films, wherein x and y can be selected between 0 and 1 , and wherein Z is selected from Sn, Pb, Ge and Si. Technical Background of the invention
A Cu2ZnSn(SySei_y)4 absorber layer is considered the leading candidate to replace a Cu(ln,Ga)(S,Se)2 absorber layer in thin films solar cells because it only contains cheap, and abundant elements. Cu2ZnSn(SySei_y)4 solar cells have reached power conversion efficiencies of 10.1 %, clearly showing the potential of the material (Aaron et al. , Prog. Photovolt. Res. Appl., 201 1. DOI: 10.1002/pip.1 160).
Cu2ZnSn(SySei_y)4 thin films for solar cell applications can be produced by a variety of different techniques. For the production of thin films a large number of different deposition techniques are used (e.g. evaporation techniques, sputtering, E-beam, electrodeposition, spray pyrolisis, photo-chemical deposition, spin coating, the iodine transport method, printing, pulsed laser deposition etc.). A first possibility is to deposit all elements or binary compounds at elevated temperatures such that the absorber is formed in one step. A further technique involves all elements or binary compounds being deposited at once (at room or elevated temperature) and then heated to re-crystallize. Finally, all elements or binary compounds may be deposited sequentially, and then heated to intermix and crystallize.
In some cases the Cu2ZnSn(SySei_y)4 semiconductor compound is spontaneously formed on a heated substrate (e.g. coevaporation, sputtering technique) in a single step. In other cases the metals or binaries are first deposited near room temperature and are then, in a further step, annealed in a furnace comprising a S/Se atmosphere in order to form
Cu2ZnSn(SySei_y)4.
In state of the art (AgxCui_x)2ZnSn(SySei_y)4 (x, y = 0...1 ) absorber layer fabrication, in a first step a precursor film containing the metals or the metals together with selenium and/or sulphur is provided. In a second step, the precursor film is annealed, or heat- treated, in an S/Se atmosphere according to the proposal by Katagiri et al., Solar Energy Materials and Solar Cells 49 (1997) 407-414. High quality material is typically achieved through heating the precursor film at high temperatures of 500°C to 600°C. Annealing in furnaces is typically performed in an S/Se vapour together with different gases: Ar, N2, H2, H2/N2. Annealing in N2 gas plus elemental sulfur vapour has been described by Araki et al., Thin Solid Films, 517 (2008) 1457-1460. Annealing in N2 and 5wt% H2S gas is disclosed in Katagiri et al., Solar Energy Materials and Solar Cells, 49 (1997) 407-414. Annealing in N2 and 20wt% H2S gas is described in Katagiri et al., Applied Physics Express, 1 (2008) 041201 . Annealing in Ar and elemental S vapour and, alternatively, annealing in Ar and 5wt% H2S gas has been suggested by Scragg et al., Thin Solid Films, 517 (2009) 2481-2484. Annealing in N2 + 10wt%H2 and elemental S vapor has been disclosed in Scragg et al., Journal of Electroanalytical Chemistry, 646 (2010) 52-59. Some annealing experiments have also been carried out under vacuum.
K.Timmo et al. (Proceedings PVSC, 2010 35th IEEE DOI: 10.1 109/PVSC.2010.561641 1 ) have studied the chemical etching of manufactured absorbers for solar cells.
Solar cells based on co-evaporated (AgxCui_x)2ZnSn(SySei_y)4 thin films, which are produced in a single step without annealing, have been recently shown to achieve an efficiency of 9.15%. The corresponding thin films have a Cu-rich growth period, (I. Repins, et al., Solar Energy Materials and Solar Cells, 2012). The Cu-rich growth period is achieved while tuning the fluxes during the co-evaporation process. The elements are deposited at higher temperature in order to avoid the annealing step.
A Cu-rich growth period of the thin film appears to be beneficial for the efficiency of solar cells. However, using a precursor thin film that is characterized by a Cu-rich growth period, has so far not lead to promising solar cells using the two-step fabrication process, wherein the precursor thin film is subsequently annealed at high temperature.
Schubert, B.-A. et al. "Cu2ZnSnS4 thin film solar cells by fast coevaporation", Prog. Photovolt: Res. Appl. (2010) is an example of a number of disclosures which describe the formation of a Cu-rich thin film and etching the thin film where subsequent drying may be contemplated (but is not disclosed). However, it is to be realised that annealing and drying are substantially different chemical processes. It is therefore an object of the present invention to overcome or alleviate at least some of the disadvantages of the known methods of manufacturing (AgxCui_x)2ZnSn(SySei_y)4 semiconductor thin films. Summary of the invention
According to a first aspect of the present invention, there is provided a method for manufacturing a (AgxCui_x)2ZnZ(SySei_y)4 thin film, wherein both x and y are selected in between 0 and 1 , and wherein Z is selected from Sn, Ge, Si, Pb. The method comprises the following steps:
providing a thin film comprising Ag and/or Cu, the thin film further comprising Zn and Z, the thin film further comprising S and/or Se,
wherein the thin film presents a (AgxCui-x) / (Zn + Z) ratio that is greater than 1 ;
etching the thin film with an etching solution; and
- subsequent to the etching, annealing the thin film.
The annealing of the thin film may occur at a temperature between 450 and 600 °C. In an embodiment, the annealing occurs at 500 °C. The annealing may occur at a temperature range of between 300 and 1000 °C, preferably between 400 and 800 °C, and more preferably between 500 and 600 °C.
The etching solution may preferably comprise KCN, and more preferably 10% KCN.
Preferably, the step of annealing may comprise annealing the thin film in an atmosphere, which more preferably may comprise S and/or Se.
Even more preferably, the step of annealing further may comprise enclosing the thin film, together with said atmosphere, in an inert enclosure. An opening may preferably be provided in the enclosure, through which S and/or Se is supplied.
The thin film may preferably be provided on a substrate, which may preferably be molybdenum.
According to a further aspect of the present invention, a semiconductor thin film is provided, which is produced using the described method. According to a third aspect of the present invention, a device comprising a semiconductor thin film produced using the described method is provided.
The device may preferably be a photovoltaic cell, which may preferably exhibit an efficiency of at least 6 %.
The method according to the present invention provides an efficient way of producing (AgxCui_x)2ZnZ(SySei_y)4 semiconductor thin films from Cu-rich precursor films whereby the formation of Cu-Sn-Se compounds, such as for example Cu2SnSe3, on the surface of the annealed film is largely inhibited.
Solar cells that incorporate semiconductor thin films manufactured according to the present invention exhibit an improved open circuit voltage and efficiency as compared to solar cells that incorporate known (AgxCui_x)2ZnZ(SySei_y)4 thin films produced from Cu- rich precursors, which are annealed at high temperature..
Brief description of the drawings
These and other aspects of the invention will now be further described, by way of example only, with reference to the accompanying figures.
Figure 1 is a flow chart illustrating a preferred embodiment of the method according to the present invention. Figure 2 is a schematic illustration of a preferred embodiment according to the present invention.
Figure 3 shows experimental results of a precursor film produced according to a preferred embodiment of the method according to the present invention, prior to etching and annealing.
Figure 4 shows experimental results of thin film after annealing, without prior etching.
Figure 5a and 5b show experimental results of a device produced according to a preferred embodiment of the method according to the present invention. Detailed Description
According to the present invention, a method for manufacturing a (AgxCui-x)2ZnZ(SySei-y)4 thin film is provided. Z is selected to be one of Sn, Pb, Ge or Si while both x and y are select in between 0 and 1. With reference to Fig 1 and Fig 2, a precursor thin film 20 is provided in a first step, 100. The precursor thin film comprises Ag and/or Cu, comprises Zn and Z, and further comprises S and/or Se. The film may be produced by any methods known in the art. The precursor presents an (AgxCui-x) / (Zn+Z) ratio that is greater than 1 , it is therefore (AgxCui-x)-rich. The method further comprises the sequential steps of etching the thin film with an etching solution, 200, prior to annealing the film at a high temperature 300.
The precursor film may be provided on a substrate 10. The annealing of the thin film may preferably take place in an atmosphere comprising S and/or Se. Both the thin film and the atmosphere may be enclosed in an inert enclosure 30. At least one opening is provided in the enclosure, through which S and/or Se or other compounds may be introduced into the atmosphere.
Without loss of generality, the invention is described on the basis that Z is selected to be Sn, x = 0 and y = 0. The composition of the corresponding precursor thin film is described by Cu2ZnSnSe4, CZTSe.
The Cu excess in the Cu-rich precursor film has been shown to lead to a copper selenide, Cu-Se, phase at the surface of the precursor film. During annealing, the copper selenide phase incorporates tin and turns into secondary phases, the most likely being the ternary Cu2SnSe3. The ternary Cu2SnSe3 phase is suspected to limit the open circuit voltage of a solar cell using the resulting semiconductor thin film.
KCN is known to be able to remove copper selenide, Cu-Se, compounds. Examples of such compounds are CuSe and Cu2Se. By etching the precursor thin film prior to annealing, the Cu-Se phases on the surface of the thin film are largely removed. The removed Cu-Se phases can no longer act as sources for the production of new secondary phases during annealing. It has been observed that after annealing, the pre-etched thin film presents less of the detrimental secondary phases on its surface. Also, a solar cell incorporating the resulting thin film presents an improved efficiency and open circuit voltage as compared to solar cells using known thin films produced from Cu-rich precursor films.
Etching the precursor film prior to annealing has the further advantage that the Cu-Se phases at the surface of the Cu-rich precursor film do not interdiffuse into the thin film during annealing. Etching the film only after annealing can only remove the Cu-Se secondary phases that are present on the surface of the film after annealing. However, during the annealing step the secondary phases may diffuse deeper into the film. As according to the present invention the precursor film is etched before being annealed, less of the Cu-Se secondary phases are formed during the annealing, and therefore less of these secondary phases tend to diffuse into the film. The proposed method is efficient in producing thin film semiconductors with less Cu-Se secondary phases throughout the film than known methods. This outlines the underlying principle of the present invention in general terms. Further specific embodiments according to the present invention are described without further limiting the scope of the invention.
In a preferred embodiment, a CZTSe precursor film is first produced in a molecular beam epitaxy system with Cu, Zn, Sn evaporation sources and Se is supplied via a valved source. The deposition temperature is set to 320 °C and all four elements are coevaporated on a molybdenum coated soda lime glass substrate. This corresponds to step 100. At this temperature, the CZTSe precursor film does not decompose. Indeed CZTSe is known to decompose according to the following equation at temperatures higher than 350°C.
Cu2ZnSnSe4(s)→ Cu2Se(s)+ ZnSe(s)+ SnSe(g)+ ½ Se2(g) (1 )
The equation applies for selenium, sulphur or mixed selenium/sulphur thin films.
Two sample precursor films are produced. For sample A, the stoichiometry of the precursor is set to Cu/(Zn+Sn) = 1.39 and Zn/Sn = 1 .27. For sample B, the stoichiometry of the precursor is set to Cu/(Zn+Sn) = 1.10 and Zn/Sn = 1.13. Fig 3 shows a secondary ion mass spectrometry, SI MS, analysis of the Cu-rich precursor film according to sample A, which has neither been etched nor annealed. The sputtering time on the x-axis corresponds to different depths of the layer from the surface of the thin film (left) to the molybdenum substrate (right). It can be concluded that a copper selenide phase is present at the surface of the precursor film.
Fig 4 shows a SI MS analysis of sample A after it has been annealed at a high temperature of 500-600 °C in a graphite box, without prior etching of the sample. The annealing takes place in an H2/N2 atmosphere at a pressure of 1 mbar. The atmosphere further contains 15mg of SnSe and 20 mg of Se in order to avoid the decomposition according to equation (1 ) to take place. It can be observed that the annealed absorber presents a Cu- and Sn-rich interface. This leads to the model that during annealing, the copper selenide phase at the surface of the precursor film incorporates tin and turns into secondary phases, the most likely being the ternary Cu2SnSe3 phases. The ternary Cu2SnSe3 phase is suspected to limit the open circuit voltage of a solar cell using the resulting semiconductor thin film.
Therefore, sample A and B have been etched during 30 seconds to 1 minute in a 10% KCN etching solution, corresponding to step 200. This is done before proceeding to annealing, which corresponds to step 300. The films have been characterized at various stages of the production process using scanning electron microscopy, SEM, equipped with an energy dispersive X-Ray, EDX, analyser. The resulting composition ratios are given in Table I for sample A and Table II for sample B.
Figure imgf000009_0001
Table II It is observed that the etched precursors have a similar Cu-poor composition after the annealing as compared to the non-etched precursors.
Solar cells have been built as follows using the semiconductor thin films resulting from the above production method, based on sample A and B. The annealed thin film is etched in KCN for 30 seconds in order to remove any remaining CuxSe or Se impurities. This step is followed by chemical bath deposition of CdS. Finally, the n-type window layer is sputtered via RF-magnetron sputtering from intrinsic and Al-doped ZnO, followed by e-beam evaporation of Aluminium grids. The resulting solar cells have been characterised with current-voltage, IV, measurements and quantum efficiency, QE, measurements, as usual in the art. The current-voltage measurements have been performed with a halogen lamp, which has been adjusted to 100 mW/cm2.
Photoluminescence at room temperature is used to determine the bandgap of the resulting absorber layer in the near surface region. Photoluminescence is performed with an Ar-lon Laser with a spotsize of 1 μηη. For SIMS analysis, an area with a diameter of 250 μηη has been analysed and 8 keV Cs+ ions have been used. The solar cell results based on pre-etched sample A are shown in Fig 5a and 5b. The solar cell parameters based on pre-etched sample A are given in Table I I I. A maximum solar cell efficiency of 6.1 % has been achieved. A maximum open circuit voltage of 353 mV has been achieved. It is noted that a solar cell produced from the annealed precursor of sample A without etching prior to the annealing step, did not result in a working solar cell.
Figure imgf000010_0001
Table II I
Similar results have been observed for the solar cell based on sample B, which is slightly Cu-rich. The solar cell based on the annealed precursor without prior etching resulted in a working cell having an efficiency of 3.2 % and an open circuit voltage of 270 mV. The solar cell based on sample B, which was etched prior to the annealing step, resulted in a working cell having an improved efficiency of 5.8 % and an improved open circuit voltage of 342 mV. Devices made according to embodiments of the invention have been annealed at a temperature of 500 °C. However, it is to be realised that a range of temperatures in the annealing are permissible and dependent on various factors. In further embodiments, the annealing occurs at a temperature range of between 300 and 1000 °C, preferably between 400 and 800 °C, and more preferably between 450 and 600 °C.
The present invention provides a method for manufacturing a (AgxCui_x)2ZnZ(SySei_y)4 thin film, wherein Z is selected from Sn, Ge, Si, Pb. The method comprises the steps of providing a Cu-rich precursor film, etching the precursor film and subsequently annealing the etched film. The method results in thin film semiconductors that allow to increase the efficiency of solar cells which incorporate them.
No doubt many other effective alternatives will occur to the skilled person. It will be understood that the invention is not limited to the embodiments described herein and encompasses modifications apparent to those skilled in the art lying within the spirit and scope of the claims appended hereto.
References
[1 ] Todorov, T. K., Reuter, K. B. & Mitzi, D. B. High-Efficiency Solar Cell with Earth- Abundant Liquid-Processed Absorber Adv. Mater. 22, 1-4 (2010).
[2] Friedlmeier, T., Wieser, N., Walter, T., Dittrich, H. & Schock, H. Heterojunctions based on Cu2ZnSnS4 and Cu2ZnSnSe4 thin films Proceedings of the 14th European Photovotlaic Specialists Conference, Barcelona, 1242-1245 (1997).
[3] Ahn, S. et al. Determination of band gap energy (Eg) of Cu2ZnSnSe4 thin films: On the discrepancies of reported band gap values Appl. Phys. Lett. 97, 021905 (2010).
[4] Weber, A., Mainz, R. & Schock, H. W. On the Sn loss from thin films of the material system Cu-Zn-Sn-S in high vacuum J. Appl. Phys. 107, 013516 (2010).
[5] Redinger, A. & Siebentritt, S. Coevaporation of Cu2ZnSnSe4 thin films Appl. Phys. Lett. 97, 0921 1 1 (2010).
[6] Lewis, N. Toward Cost-Effective Solar Energy Use Science 315, 798 (2007).
[7] Wang, K. et al. Thermally evaporated Cu2ZnSnS4 solar cells Appl. Phys. Lett. 97, 143508 (2010).
[8] Schubert, B.-A. et al. Cu2ZnSnS4 thin film solar cells by fast coevaporation Prog. Photovolt: Res. Appl. (2010).
[9] Katagiri, H. et al. Enhanced Conversion Efficiencies of Cu2ZnSnS4-Based Thin Film Solar Cells by Using Preferential Etching Technique Applied Physics Express 1 , 041201 (2008).
[10] Probst, V. et al. New developments in Cu(ln,Ga)(S,Se)2 thin film modules formed by rapid thermal processing of stacked elemental layers Solar Energy Materials and Solar Cells 90, 31 15-3123 (2006).
[1 1 ] Piacente, V., Foglia, S. & Scardala, P. Sublimation study of the tin sulphides SnS2, Sn2S3 and SnS Journal of Alloys and Compounds 177, 17 (1991 ).
[12] Zocchi F, & Piacente V. Sublimation enthalpy of tin monoselenide J. Mater. Sci. Lett. 14, 235 (1995).
[13] Aaron et al., Prog. Photovolt. Res. Appl., 201 1. DOI: 10.1002/pip.1 160
[14] I. Repins, et al., Solar Energy Materials and Solar Cells, 2012.
[15] K. Timmo et al., Proceedings PVSC, 2010 35th IEEE DOI:
10.1 109/PVSC.2010.561641 1

Claims

1 . A method for manufacturing a (AgxCui_x)2ZnZ(SySei_y)4 thin film, wherein
0 < x,y < 1 , and wherein Z is selected from Sn, Ge, Si, Pb, the method comprising - providing a thin film(10) comprising Ag and/or Cu, the thin film further comprising
Zn and Z, the thin film further comprising S and/or Se,
wherein the thin film presents a (AgxCui-x) / (Zn + Z) ratio that is greater than 1 (100);
the method further comprising
- etching (200) the thin film with an etching solution; and
- subsequent to the etching, annealing (300) the thin film.
2. The method according to claim 1 wherein annealing (300) of the thin film occurs at a temperature between 500 and 600 °C.
3. The method according to claim 1 , wherein the etching solution comprises KCN.
4. The method according to claim 2, wherein the etching solution comprises 10% KCN.
5. The method according to any of the preceding claims, wherein the step of annealing comprises annealing the thin film in an atmosphere.
6. The method according to claim 5, wherein the atmosphere comprises S and/or Se.
7. The method according to claim 5 or claim 6, wherein the step of annealing further comprises enclosing the thin film (20), together with said atmosphere, in an inert enclosure (30).
8. The method in accordance with claim 7, wherein at least one opening is provided in the enclosure, through which S and/or Se is supplied.
9. The method in accordance any one of the preceding claims, wherein the thin film (20) is provided on a substrate (10).
10. The method in accordance with claim 9, wherein the substrate (10) is molybdenum.
1 1 . A semiconductor thin film produced using the method according to any of the preceding claims.
12. A device comprising a semiconductor thin film produced using the method according to any of claims 1 to 10.
13. A device according to claim 12 wherein said device is a photovoltaic cell.
14. A device according to claim 13 wherein said device is a photovoltaic cell having an efficiency of at least 6 %.
PCT/EP2013/058509 2012-04-26 2013-04-24 Method for manufacturing a semiconductor thin film WO2013160356A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
LU91987 2012-04-26
LU91987A LU91987B1 (en) 2012-04-26 2012-04-26 Method for manufacturing a semiconductor thin film

Publications (1)

Publication Number Publication Date
WO2013160356A1 true WO2013160356A1 (en) 2013-10-31

Family

ID=48236908

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/058509 WO2013160356A1 (en) 2012-04-26 2013-04-24 Method for manufacturing a semiconductor thin film

Country Status (2)

Country Link
LU (1) LU91987B1 (en)
WO (1) WO2013160356A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106960906A (en) * 2017-02-24 2017-07-18 江苏理工学院 A kind of Cu Sn Se nano phase change thin-film materials and its production and use
US20180006173A1 (en) * 2016-06-30 2018-01-04 International Business Machines Corporation Technique for Achieving Large-Grain Ag2ZnSn(S,Se)4 Thin Films

Non-Patent Citations (27)

* Cited by examiner, † Cited by third party
Title
AARON ET AL., PROG. PHOTOVOLT. RES. APPL., 2011
AHN, S. ET AL.: "Determination of band gap energy (Eg) of Cu2ZnSnSe4 thin films: On the discrepancies of reported band gap values", APPL. PHYS. LETT., vol. 97, 2010, pages 021905
ARAKI ET AL., THIN SOLID FILMS, vol. 517, 2008, pages 1457 - 1460
BÃR M ET AL: "Impact of KCN etching on the chemical and electronic surface structure of CuZnSnSthin-film solar cell absorbers", APPLIED PHYSICS LETTERS, AIP, AMERICAN INSTITUTE OF PHYSICS, MELVILLE, NY, US, vol. 99, no. 15, 10 October 2011 (2011-10-10), pages 152111 - 152111, XP012152471, ISSN: 0003-6951, [retrieved on 20111013], DOI: 10.1063/1.3650717 *
BJÖRN-ARVID SCHUBERT ET AL: "Cu2ZnSnS4 thin film solar cells by fast coevaporation", PROGRESS IN PHOTOVOLTAICS: RESEARCH AND APPLICATIONS, vol. 19, no. 1, 31 May 2010 (2010-05-31), pages 93 - 96, XP055001284, ISSN: 1062-7995, DOI: 10.1002/pip.976 *
FRIEDLMEIER, T.; WIESER, N.; WALTER, T.; DITTRICH, H.; SCHOCK, H.: "Heterojunctions based on Cu2ZnSnS4 and Cu2ZnSnSe4 thin films", PROCEEDINGS OF THE 14TH EUROPEAN PHOTOVOTLAIC SPECIALISTS CONFERENCE, BARCELONA, 1997, pages 1242 - 1245, XP001136286
HIRONORI KATAGIRI ET AL: "Enhanced conversion efficiencies of Cu2ZnSnS4-based thin film solar cells by using preferential etching technique", APPLIED PHYSICS EXPRESS, THE JAPAN SOCIETY OF APPLIED PHYSICS, vol. 1, no. 4, 4 April 2008 (2008-04-04), pages 41201 - 1, XP001517129, ISSN: 1882-0778, DOI: 10.1143/APEX.1.041201 *
K. TIMMO ET AL., PROCEEDINGS PVSC, vol. 35TH, 2010
K.TIMMO ET AL., PROCEEDINGS PVSC, vol. 35TH, 2010
KATAGIRI ET AL., APPLIED PHYSICS EXPRESS, vol. 1, 2008, pages 041201
KATAGIRI ET AL., SOLAR ENERGY MATERIALS AND SOLAR CELLS, vol. 49, 1997, pages 407 - 414
KATAGIRI, H. ET AL.: "Enhanced Conversion Efficiencies of Cu2ZnSnS4-Based Thin Film Solar Cells by Using Preferential Etching Technique", APPLIED PHYSICS EXPRESS, vol. 1, 2008, pages 041201
LEWIS, N.: "Toward Cost-Effective Solar Energy Use", SCIENCE, vol. 315, 2007, pages 798, XP055226891
PIACENTE, V.; FOGLIA, S.; SCARDALA, P.: "Sublimation study of the tin sulphides SnS2, Sn2S3 and SnS", JOURNAL OF ALLOYS AND COMPOUNDS, vol. 177, 1991, pages 17, XP024176019, DOI: doi:10.1016/0925-8388(91)90053-X
PRASHANT K SARSWAT ET AL: "CZTS thin films on transparent conducting electrodes by electrochemical technique", THIN SOLID FILMS, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 520, no. 6, 21 July 2011 (2011-07-21), pages 1694 - 1697, XP028444220, ISSN: 0040-6090, [retrieved on 20110729], DOI: 10.1016/J.TSF.2011.07.052 *
PROBST, V. ET AL.: "New developments in Cu(In,Ga)(S,Se)2 thin film modules formed by rapid thermal processing of stacked elemental layers", SOLAR ENERGY MATERIALS AND SOLAR CELLS, vol. 90, 2006, pages 3115 - 3123, XP028002285, DOI: doi:10.1016/j.solmat.2006.06.031
REDINGER, A.; SIEBENTRITT, S.: "Coevaporation of Cu2ZnSnSe4 thin films", APPL. PHYS. LETT., vol. 97, 2010, pages 092111
REPINS ET AL., SOLAR ENERGY MATERIALS AND SOLAR CELLS, 2012
SCHUBERT, B.-A. ET AL.: "Cu2ZnSnS4 thin film solar cells by fast coevaporation", PROG. PHOTOVOLT: RES. APPL., 2010
SCRAGG ET AL., JOURNAL OF ELECTROANALYTICAL CHEMISTRY, vol. 646, 2010, pages 52 - 59
SCRAGG ET AL., THIN SOLID FILMS, vol. 517, 2009, pages 2481 - 2484
SCRAGG J J ET AL: "A 3.2% efficient Kesterite device from electrodeposited stacked elemental layers", JOURNAL OF ELECTROANALYTICAL CHEMISTRY, ELSEVIER, AMSTERDAM, NL, vol. 646, no. 1-2, 15 July 2010 (2010-07-15), pages 52 - 59, XP027141897, ISSN: 1572-6657, [retrieved on 20100118] *
TODOROV, T. K.; REUTER, K. B.; MITZI, D. B.: "High-Efficiency Solar Cell with Earth-Abundant Liquid-Processed Absorber", ADV. MATER., vol. 22, 2010, pages 1 - 4
WANG, K. ET AL.: "Thermally evaporated Cu2ZnSnS4 solar cells", APPL. PHYS. LETT., vol. 97, 2010, pages 143508, XP012137203, DOI: doi:10.1063/1.3499284
WANGPERAWONG A ET AL: "Aqueous bath process for deposition of CuZnSnSphotovoltaic absorbers", THIN SOLID FILMS, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 519, no. 8, 24 November 2010 (2010-11-24), pages 2488 - 2492, XP028132120, ISSN: 0040-6090, [retrieved on 20101204], DOI: 10.1016/J.TSF.2010.11.040 *
WEBER, A.; MAINZ, R.; SCHOCK, H. W.: "On the Sn loss from thin films of the material system Cu-Zn-Sn-S in high vacuum", J. APPL. PHYS., vol. 107, 2010, pages 013516
ZOCCHI F; PIACENTE V: "Sublimation enthalpy of tin monoselenide", J. MATER. SCI. LETT., vol. 14, 1995, pages 235

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180006173A1 (en) * 2016-06-30 2018-01-04 International Business Machines Corporation Technique for Achieving Large-Grain Ag2ZnSn(S,Se)4 Thin Films
US10079321B2 (en) * 2016-06-30 2018-09-18 International Business Machines Corporation Technique for achieving large-grain Ag2ZnSn(S,Se)4thin films
CN106960906A (en) * 2017-02-24 2017-07-18 江苏理工学院 A kind of Cu Sn Se nano phase change thin-film materials and its production and use
CN106960906B (en) * 2017-02-24 2019-02-19 江苏理工学院 A kind of Cu-Sn-Se nano phase change thin-film material and its preparation method and application

Also Published As

Publication number Publication date
LU91987B1 (en) 2013-10-28

Similar Documents

Publication Publication Date Title
US7018858B2 (en) Light absorbing layer producing method
Ratz et al. Physical routes for the synthesis of kesterite
Wang Progress in thin film solar cells based on Cu2ZnSnS4
US6323417B1 (en) Method of making I-III-VI semiconductor materials for use in photovoltaic cells
Ilari et al. Cu2ZnSnSe4 solar cell absorbers spin-coated from amine-containing ether solutions
EP1654769B1 (en) Method for the preparation of group ib-iiia-via quaternary or higher alloy semiconductor films
Romeo et al. Low substrate temperature CdTe solar cells: A review
US9087954B2 (en) Method for producing the pentanary compound semiconductor CZTSSe, and thin-film solar cell
Caballero et al. CuIn1− xGaxSe2‐based thin‐film solar cells by the selenization of sequentially evaporated metallic layers
Kauk et al. Effects of sulphur and tin disulphide vapour treatments of Cu2ZnSnS (Se) 4 absorber materials for monograin solar cells
Jeong et al. CZTSSe/Zn (O, S) heterojunction solar cells with 9.82% efficiency enabled via (NH4) 2S treatment of absorber layer
JP2014505993A (en) Method for manufacturing a semiconductor thin film
Wang et al. Fabrication of high-efficiency Cu 2 (Zn, Cd) SnS 4 solar cells by a rubidium fluoride assisted co-evaporation/annealing method
US8912037B2 (en) Method for making photovoltaic devices using oxygenated semiconductor thin film layers
JP2004342678A (en) METHOD OF MANUFACTURING Cu(In1-xGax)Se2 FILM AND SOLAR BATTERY
WO2013160356A1 (en) Method for manufacturing a semiconductor thin film
Zhang et al. Investigation on Sb-doped induced Cu (InGa) Se2 films grain growth by sputtering process with Se-free annealing
WO2013160369A1 (en) Method for manufacturing a semiconductor thin film
KR101583027B1 (en) Method of manufacturimg of CZTS-based solar cell light absorber and CZTS-based solar cell light absorber thereby
US10446703B1 (en) Method for manufacturing CIGS thin film for solar cell
CN114203842A (en) Wide-bandgap copper-gallium-selenium light absorption layer, preparation method thereof and solar cell
Miyazawa et al. Effect of UV irradiation on Cu2ZnSnS4 thin films prepared by the sol–gel sulfurization method
KR101388458B1 (en) Preparation method for cigs thin film using rapid thermal processing
KR102584673B1 (en) Flexible thin film solar cell and method for manufacturing the same
KR102596328B1 (en) Preparation method for CZTS thin film solar cell absorbing layer, CZTS thin film solar cell absorbing layer prepared therefrom

Legal Events

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

Ref document number: 13719795

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13719795

Country of ref document: EP

Kind code of ref document: A1