EP2684212A1 - Procédé de fabrication du semi-conducteur composé pentanaire cztsse et cellule solaire à couche mince - Google Patents

Procédé de fabrication du semi-conducteur composé pentanaire cztsse et cellule solaire à couche mince

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Publication number
EP2684212A1
EP2684212A1 EP12709818.4A EP12709818A EP2684212A1 EP 2684212 A1 EP2684212 A1 EP 2684212A1 EP 12709818 A EP12709818 A EP 12709818A EP 2684212 A1 EP2684212 A1 EP 2684212A1
Authority
EP
European Patent Office
Prior art keywords
precursor layer
sulfur
selenium
interface
compound semiconductor
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Withdrawn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
EP12709818.4A
Other languages
German (de)
English (en)
Inventor
Stephan Jost
Jörg Palm
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.)
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Original Assignee
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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 Saint Gobain Glass France SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Priority to EP12709818.4A priority Critical patent/EP2684212A1/fr
Publication of EP2684212A1 publication Critical patent/EP2684212A1/fr
Withdrawn legal-status Critical Current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
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • 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
    • H10F77/128—Active materials comprising only Group I-II-IV-VI kesterite materials, e.g. Cu2ZnSnSe4 or Cu2ZnSnS4
    • 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
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/13—Photovoltaic cells having absorbing layers comprising graded bandgaps
    • 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
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • 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
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/203—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using transformation of metal, e.g. oxidation or nitridation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3424—Deposited materials, e.g. layers characterised by the chemical composition being Group IIB-VIA materials
    • H10P14/3428—Sulfides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3424—Deposited materials, e.g. layers characterised by the chemical composition being Group IIB-VIA materials
    • H10P14/3431—Selenides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3436—Deposited materials, e.g. layers characterised by the chemical composition being chalcogenide semiconductor materials not being oxides, e.g. ternary compounds
    • 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

Definitions

  • the invention is in the technical field of the production of thin film solar cells and relates to a method for producing a compound semiconductor of pentane kesterite / stannite of the type Cu 2 ZnSn (S, Se) 4 , and a thin film solar cell with a pentane kerenite / stannite absorber of the Cu type 2 ZnSn (S, Se) 4 with a defined sulfur depth profile.
  • Cu (In, Ga) (S, Se) 2 proved to be advantageous, in particular copper indium diselenide (CuInSe 2 ) is characterized by its particularly adapted to the spectrum of sunlight band gap by a particularly high absorption coefficient.
  • CZTSSe pentanaric Cu 2 ZnSn (S, Se) 4
  • CZTSe quaternary Cu 2 ZnSnSe 4
  • CZTSe quaternary Cu 2 ZnSnS 4
  • CZTS Copper Tin Oxide
  • These semiconductor layers have a high absorption coefficient in visible light in the size of order of 10 4 cm 1 and a direct band gap in the order of 1.5 eV.
  • Lausanne, CH, Vol. 517, No. 7, February 2, 2009, pages 2455- 2460, XP025928657 describes a method for producing the quaternary CZTS compound semiconductor.
  • the elements Cu, Zn and Sn are deposited by co-sputtering and then reacted by heat treatment in an S-containing atmosphere to the compound semiconductor.
  • the object of the present invention consists in processes known in the art for preparing a compound semiconductor from pentane-type kestritite / stannite of the type Cu 2 ZnSn (S, Se) 4 or CZTSSe and to develop speaking compound semiconductors in an advantageous manner.
  • a process for producing a compound semiconductor of pentane kesterite / stannite of the Cu 2 ZnSn (S, Se) 4 type is shown, which is preferably part of a process for producing a thin-film solar cell or a thin-film solar module .
  • the connection ⁇ semiconductor contains the metals copper (Cu), zinc (Zn), and tin (Sn) and the chalcogens of sulfur (S) and selenium (Se).
  • the term "thin-film solar cell” here and hereinafter refers to photovoltaic layer systems with thicknesses of only a few micrometers. Such coating systems Benö ⁇ term carrier substrates to provide a sufficient mechanical strength.
  • Carriers known substrates for thin film solar cells include inorganic glass, polymers, or metal alloys, and may be designed in function of the layer thickness and material properties than rigid Plat ⁇ th or flexible films.
  • the method according to the invention comprises the following
  • the metals Kup ⁇ fer in two Stu ⁇ fen by depositing the metals Kup ⁇ fer in two Stu ⁇ fen, wherein the first precursor layer is produced in a first stage (Cu), zinc (Zn), and tin (Sn) on a body and in a second stage, the second precursor layer Herge ⁇ provides is selected by depositing at least one chalcogen, sulfur (S) and selenium (Se) on the first precursor layer.
  • the second precursor layer made by precipitating sulfur or alternatively by precipitating selenium or alternatively by precipitating sulfur and selenium in combination.
  • the notation "Cu 2 ZnSn (S, Se) 4" means that the chalcogens sulfur (S) and selenium (Se) are contained in combination in the connection ⁇ semiconductors.
  • the heat treatment of the at least one precursor layer stack takes place in a process gas atmosphere which, at least temporarily, at least one chalcogen, namely
  • S Sulfur
  • Se selenium
  • chalcogen-containing compound in which sulfur and / or
  • Selenium is contained in bound form contains.
  • one or more process gases containing min ⁇ (least an elemental chalcogen selected from sulfur and selenium, and / or at least one chalcogen restroom compound in which sulfur and / or selenium is in bound form, for example, sulfur hydrogen H 2 S ) or Se ⁇ lenwasserstoff (H 2 Se) or other sulfur- or selenhal- term gases, at least temporarily cavities supplied to the process during the heat treatment of at least one precursor layer stack.
  • chalcogen selected from pivoting ⁇ fel and selenium, (ie, sulfur, or alternatively, selenium), in the process gas, the other one chalcogen and / or the other of Chalcogen containing compound is included, or alternatively, if in the second precursor layer, the two chalcogens sulfur and selenium in Combination contained in the process gas sulfur and / or selenium and / or a sulfur-containing compound
  • the invention shows a novel method for the manufacture of the lung ⁇ pentanary compound semiconductor Cu 2 ZnSn (S, Se) 4, where in a (two-stage) the first step, the metals are copper, zinc and tin, and then the chalcogens
  • Sulfur and / or selenium are deposited.
  • the thermal processing takes place in a chalcogen-containing environment for the conversion of the precursor layers into the pentanic compound semiconductor.
  • a definable or defined sulfur depth profile (based on the total content of selenium and sulfur) in the pentane compound semiconductor Cu 2 ZnSn (Se, S) 4 are formed.
  • sulfur contained in the process gas in the second precursor layer displaces selenium, so that the sulfur content decreases with increasing depth and the selenium content increases in a complementary manner.
  • Sulfur contained can slide cheumble ⁇ by selenium in the process gas in the compound semiconductors in the second precursor layer are displaced, so that the sulfur content with increasing depth increases and decreases in a complementary manner, the selenium content. It is therefore not introduced by the chalcogen (sulfur or selenium) in the process gas in the reacted compound semiconductors, so the composition of the compound semiconductor influenced, but also by the displacement of the other chalcogen (selenium or sulfur), in the second precursor is holding layer ent ⁇ , the sulfur depth profile, based on the total content of sulfur and selenium, specifically set ⁇ to. Due to the chalcogen in the process gas can thus the
  • a sulfur depth profile can be set with a maximum value of the ratio S / (Se + S) at the absorber surface and decreasing value of the ratio S / (Se + S) to the absorber interior.
  • the resulting increased band gap at the absorber surface leads in the thin-film solar cell to an increase in the open-circuit voltage.
  • the height of the short- circuit current is determined by the minimum of the band gap in the absorber interior.
  • the sulfur depth profile in the pentagonal compound semiconductor can be adjusted in a targeted manner with regard to the band gap and the crystal quality.
  • the sulfur depth profile may be formed from a surface of the compound semiconductor toward an interface with the body such that
  • the sulfur content at the semiconductor surface has a maximum value, decreases toward the body interface, and has a minimum value at the body interface;
  • the sulfur content at the semiconductor surface has a minimum value, increases towards the body interface, and has a maximum value at the body interface;
  • the sulfur content at the semiconductor surface has a first maximum value, decreases toward the body interface down to a minimum value, and then increases again, and has a second maximum value at the body interface;
  • the sulfur content at the semiconductor surface has a first minimum value, increases toward the body interface up to a maximum value, and then decreases again, and has a second minimum value at the body interface.
  • the sulfur depth profile is preferably designed such that a relative change in the sulfur content at least over a partial region of the depth profile, ie over at least a partial region of the layer thickness of the compound semiconductor, in particular of the semiconductor semiconductor.
  • area is to body interface, at least 10%, Wenig ⁇ least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80%.
  • Particularly preferred is the relative change of
  • Sulfur content at least 20%.
  • the at least one process gas can be continuously fed to the process space during a first time interval of the heat treatment or else only during one or more second time intervals, which are shorter than the first time interval.
  • the at least one process gas can be fed into the process space in an earlier and / or a later phase of the heat treatment.
  • the body during deposition of the second precursor layer advantageously has a temperature of less than 150 ° C, Staer ⁇ ker preferably less than 100 ° C, whereby an unintentional (part) already be reliably prevented reaction during deposition of the precursor materials can.
  • Both the deposition of the metals copper, zinc and tin as well as the deposition of the at least one chalcogen, one or more dopants (eg sodium) can be deposited.
  • a layer stack of individual layers of the metals copper, zinc and tin each individual layer consists of a single metal
  • a layer stack of individual layers of chalcogens sulfur and selenium is deposited several times in succession.
  • the first precursor layer can generally be formed such that - the copper content is less than the summary Ge ⁇ halt of zinc and tin, or
  • the copper content is equal to the total content of zinc and tin, or
  • the copper content is greater than the total content of zinc and tin.
  • the first precursor layer can in principle be formed such that
  • the zinc content is less than the tin content, or - the zinc content is equal to the tin content, or
  • the zinc content is greater than the tin content.
  • the first precursor layer is formed so that the copper content is less than the sum marische content of zinc and tin, and at the same time the Zinkge ⁇ is just greater than the tin content, wherein it is assumed that by this measure a favorable influence on the crystal quality and the efficiency of the thin-film solar cell ⁇ can be achieved.
  • the two precursor layers are formed such that the ratio of the total content of chalcogens to the total content of metals is greater than or equal to 1 for the preparation of the pentanic compound semiconductor CZTSSe. Also by this measure, a favorable influence on the crystal quality and the effect ⁇ degree of thin-film solar cell can be achieved.
  • the invention further extends to a thin film solar cell having a compound semiconductor formed from ⁇ absorber pentanärem kesterite / Stannit type Cu 2 ZnSn (S, Se) 4 on a body, wherein the absorber of a semiconductor surface to a body interface through a definable or defined sulfur depth profile (based on a total content of selenium and sulfur).
  • the sulfur depth profile is designed so that
  • the sulfur content at the semiconductor surface has a maximum value, decreases toward the body interface, and has a minimum value at the body interface;
  • the sulfur content at the semiconductor surface has a minimum value, increases towards the body interface, and has a maximum value at the body interface;
  • the sulfur content at the semiconductor surface has a first maximum value, decreases toward the body interface down to a minimum value, and then increases again, and has a second maximum value at the body interface;
  • the sulfur content at the semiconductor surface has a first minimum value, increases toward the body interface up to a maximum value, and then decreases again, and has a second minimum value at the body interface.
  • the sulfur depth profile is formed such that a relative change in the sulfur content at least over a partial region of the depth profile, ie over at least a portion of the layer thickness of the compound ⁇ semiconductors, in particular from the semiconductor surface to the body interface, at least 10%, at least 20 %, we ⁇ iquess 30%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80%. Most preferably, the relative change in sulfur content is at least 20%.
  • the invention extends to the use of the above-described method for manufacturing a compound semiconductor from pentanärem kesterite / Stannit type Cu 2 ZnSn (S, Se) 4 for the production of the semiconductor layer (absorber BER) of a thin film solar cell or a Dünn GmbHo ⁇ larmoduls.
  • Fig. 1 is a sectional view illustrating the general process for producing an absorber of a thin-film solar cell composed of the compound semiconductor CZTSSe;
  • Fig. 2-4 are sectional views illustrating specific procedures for producing the pentanic compound semiconductor
  • Thin-film solar module is illustrated. It is understood that the layer structure 1 can serve to produce a multiplicity of thin-film solar cells which are connected in series in a monolithically integrated manner in a large-area arrangement.
  • the layer structure 1 has a substrate configuration in which a layer structure 7 consisting of a plurality of thin layers is applied to a (support) substrate 3.
  • the substrate 3 is made here, for example of inorganic glass, with other isolie ⁇ yield materials with sufficient strength, as well as inert behavior towards the carried out in the production of thin film solar cell process steps can be used equally, for example, plastics, insbeson ⁇ particular polymers or metals, particularly metal ⁇ alloy prof gene. depending on the layer thickness and the specific material properties of the substrate 3 can be configured as a rigid board or flexible sheet.
  • ⁇ from the layer thickness of the substrate is for example 1 to 5 mm.
  • the pressure applied to the substrate 3 layer structure 7 comprises a back electrode layer 4, which is arranged on a lichteinstory- surface of the substrate 3 and play, consists of an opaque metal in ⁇ . It can be, for example, by vapor deposition or sputtering magnet feldun- ter realizede on the substrate 3 to ⁇ eliminated.
  • the back electrode layer 4 is in ⁇ play, molybdenum (Mo), aluminum (Al), copper (Cu), titanium (Ti) or of a multilayer system with such a metal, for example molybdenum (Mo).
  • the layer thickness of the back electrode layer 4 is less than 1 ⁇ here, preferably in the range of 300 nm to 600 nm and is for example about 500 nm.
  • the back electrode ⁇ layer 4 serves as back contact or back electrode the thin-film solar cell.
  • an alkali barrier can be angeord ⁇ net, which consists for example of Si 3 N 4 , SiON or SICN. This is not shown in detail in Fig. 1.
  • the back electrode layer 4 On the back electrode layer 4 is an ers ⁇ te precursor or precursor layer 5 and a second pre ⁇ Läufer- or precursor layer 6 are successively disposed.
  • the two precursor layers 5, 6 can be reactively reacted by a heat treatment indicated by arrow 8 in the photovoltaically active absorber 2.
  • the layer thickness of the absorber 2 is, for example, in the range of 1-5 ⁇ and is in particular about 2 ⁇ .
  • the layer structure 1 shown in FIG. 1 represents an intermediate product in the production of the thin-film solar cell. The further processing of the layer structure 1 is not necessary for the understanding of the invention, so that it need not be discussed in more detail.
  • a front electrode layer which serves as Vordersei ⁇ tentitle or front electrode and is transparent to radiation in the visible spectral range (“window layer”).
  • a doped metal oxide (TCO Transparent Conductive Oxi ⁇ en) is used for the front electrode layer used, for example, n-type, aluminum (Al) - doped zinc oxide (ZnO), boron (B) -doped zinc oxide (ZnO), or gallium (Ga) -doped zinc oxide (ZnO).
  • a thin buffer layer is disposed in the rule which, for example, CdS, In x S y, (In, Ga, Al) x (S, Se) y, ZnS, Zn (0, S), Zn (Mg, O), optionally in combination with intrinsic i-ZnO, be ⁇ stands.
  • CdS, In x S y, (In, Ga, Al) x (S, Se) y, ZnS, Zn (0, S), Zn (Mg, O), optionally in combination with intrinsic i-ZnO be ⁇ stands.
  • the front electrode layer to the absorber 2 can be lent with regard lattice constant and band profile can be achieved.
  • Front electrode, buffer, absorber and back electrode layers together form a heterojunction, ie one Sequence of layers of opposite conductivity type.
  • the layer thickness of the front electrode layer is ⁇ example, about 300 to 1500 nm, the buffer layer ⁇ example, about 50 nm.
  • ⁇ existing plastic layer encapsulating
  • a polyvinyl butyral (PVB), ethylene vinyl acetate (EVA) or DNP for example, a polyvinyl butyral (PVB), ethylene vinyl acetate (EVA) or DNP.
  • a transparent cover plate for sunlight comprising at ⁇ play, from extra-white glass (front glass) with a low iron content and may have a thickness of for example 1 to 4 mm, be provided.
  • the structure described a thin film solar cell or a thin-film solar module to the expert beispielswei ⁇ se from commercially available thin film solar cells and thin film solar modules well known and has also been extensively described in numerous publications in the patent literature (eg DE 19956735 B4).
  • the back electrode layer 4 adjoins the substrate 3.
  • the layered structure 1 may equally have a superstrate configuration, in which the substrate 3 transparent, and the front electrode layer on istwanden ei ⁇ ner the light incident side surface of the sub ⁇ strats 3 is arranged.
  • the layer structure 1 can serve for the production of integrated series-connected thin-film solar cells, the layer structure 1 being known per se by different structuring lines ("PI" for back electrode, "P2" for contact front electrode / back electrode and "P3" for separation the front electrode) is structured.
  • PI for back electrode
  • P2 for contact front electrode / back electrode
  • P3 for separation the front electrode
  • a structure of the front-electrode and grid thin-film solar cells may be provided.
  • the method serves for the manufacture ⁇ development of a light-absorbing thin-film semiconductor layer or from the absorber 2 or Kesterit- Stannit type, wherein the absorber 2 is composed of CZTSSe.
  • the first precursor layer 5 consists of the metals Cu, Zn and Sn and is deposited from purely metallic sources on the back electrode layer 4 or a (multilayer) body 12 consisting of substrate 3 and back electrode layer 4 (and optionally further layers) ,
  • a deposition of the metals Cu, Zn, Sn on the body 12 can be realized, in particular, by the methods mentioned below, wherein optionally one or more dopants (eg Na) can be supplied.
  • the element targets each have a clean ⁇ ness of> 4N, more preferably> 5N on.
  • ⁇ th alloy target
  • the alloy targets each a clean ⁇ ness of> 4N, more preferably> 5N on.
  • the element sources each have a purity of> 4N, more preferably> 5N.
  • the alloy sources each have a purity of> 4N, more preferably> 5N.
  • the first precursor layer 5 comprises a plurality of individual metallic layers, each single layer consisting of Cu, Zn or Sn.
  • the individual layers can be deposited in the layer sequence Cu / Zn / Sn, but other layer sequences are also possible.
  • a layer sequence consisting of individual layers of the metals Cu, Zn, Sn, beispiels-, Cu / Zn / Sn, several times in succession is deposited, so that the first precursor layer 5 made of a stack of n moving ⁇ chen or different Layer sequences (eg nx Cu / Zn / Sn) exists.
  • the metals Cu, Zn, Sn means Legie ⁇ approximately targets or alloy sources comprising the first pre ⁇ cursor layer 5 one or several metallic individual layers which elements of a binary or ternary alloy ele- Cu, Zn and / or Sn , If it is additionally deposited from Ele ⁇ ment targets or element sources, the individual layers can also elemental Cu, Zn and / or Sn.
  • the metallic individual layers can be defined in a ten layer sequence are deposited.
  • a layer sequence consisting of Einzella ⁇ conditions of binary or ternary alloys of the metals Cu, Zn and / or Sn (and optionally elemental Cu, Zn and / or Sn) is deposited several times in succession, so that the first precursor layer 5 consists of a stack of n moving ⁇ chen or different position sequences.
  • the first precursor layer 5 consists of a stack of n moving ⁇ chen or different position sequences.
  • the first precursor layer 5 can be formed so that its composition
  • the first precursor layer 5 be formed in the layer structure 1 that their interaction ⁇ reduction
  • the zinc content is less than the tin content (Zn / Sn ⁇ 1), or alternatively
  • zinc rich meaning that zinc content is greater than the tin content (Zn / Sn> 1).
  • the first precursor layer 5 is formed so that its composition is low in copper (Cu / (Zn + Sn) ⁇ 1) and at the same time rich in zinc (Zn / Sn> 1).
  • the second precursor layer 6 is deposited on the first precursor layer 5.
  • the second precur sor ⁇ layer 6 is composed of at least one chalcogen, namely lent S and / or Se.
  • the at least one chalcogen is deposited without metallic components or binary metal-chalcogen compounds.
  • the temperature of the substrate 3 during deposition of the at least one chalcogen is lower than 150 ° C, more preferably lower than 100 ° C, thereby advantageously already starting partial reaction of the metals of the first precursor layer 5 with the at least one chalcogen of the second Precursor layer 6 can be prevented.
  • the deposition of S and / or Se can be realized, for example, by the methods mentioned below, wherein one or more dopants (eg Na) can be optionally fed in all processes: Thermal evaporation (PVD) of S and / or Se (sequential or simultaneously) sources of one or two evaporation ⁇ , optional (with Dotierstoffzugäbe eg Na) by evaporation of the dopant or a dotierstoffhalti- gen compound.
  • PVD Thermal evaporation
  • the two precursor layers 5, 6 together form a precursor layer stack 11.
  • the precursor layer stack 11 is deposited several times in succession (multiple sequence). This measure may be particularly advantageous for the formation of crystals and / or adjustment of a desired depth profile of sulfur (based on the Automatchalcogenmenge) of pentanary Ver ⁇ bond semiconductor CZTSSe.
  • the two precursor layers 5, 6 are subjected to a heat treatment in the form of a rapid thermal processing (commonly known as "Rapid Thermal Processing” (RTP)), whereby a reactive transformation of the metals Cu, Zn, Sn and S and / or Se to the pentanic compound semiconductor CZTSSe is effected.
  • RTP Rapid Thermal Processing
  • the heat treatment of the two precursor layers 5, 6 is carried out, at least temporarily, in a chalcogen-containing atmosphere within a process space 13 containing the layer structure 1, one or more process gases (sulfur and / or selenium and / or hydrogen sulphide) depending on the compound semiconductor to be produced (H 2 S) and / or Selenwas ⁇ hydrogen (H 2 Se) or combinations thereof) in a controlled manner the process chamber 13 are supplied.
  • Each process gas is supplied in the heat treatment during at least one (predetermined) time ⁇ interval, wherein the time interval is shorter than the period of the entire heat treatment or corresponds to the period of the entire heat treatment.
  • the amount of each process gas supplied per unit time may be unchanged or varied during the addition.
  • the composition of the chalcogen-containing atmosphere during the heat treatment may be unchanged or vary.
  • the heat treatment requires:
  • Controlled process gas supply eg H 2 , N 2 , Ar, S gas, Se gas, H 2 S, H 2 Se and combinations thereof, with ge ⁇ suitable gas temperature-time profiles.
  • the heat treatment of the two precursor layers 5, 6 may e.g. using a process box accommodating the layer structure 1 in a tunnel or within a process hood surrounding the layer structure 1.
  • a process box accommodating the layer structure 1 in a tunnel or within a process hood surrounding the layer structure 1.
  • Layer structures 1 with parallel substrates 3 are arranged side by side or one above the other (dual-substrate or multi-level process).
  • the heat treatment of the two precursor layers 5, 6 is preferably carried out using a controlled temperature-process gas profile, so that the ratio S / (Se + S), i. the sulfur content related to the total content of S and Se, and the absorber 2 has a defined depth profile.
  • (sulfur) depth profile the sulfur content or course of the value of the quotient S / (Se + S) in the absorber 2 along a linear dimension of the absorber 2, starting from an (absorber) surface 9 facing away from the substrate 3 an interface 10 facing the substrate 3 a direction perpendicular to the stacking sequence of the layer structure 7 or in the direction of the layer thickness.
  • the heat treatment is carried out so that the depth profile over the layer thickness has a decreasing course, i. the value of the ratio S / (Se + S) is maximum at the surface 9 and decreases from the surface 9 toward the interface 10, so that the value of the ratio S / (Se + S) at the interface 10 is minimum.
  • the heat treatment is performed such that the depth profile over the layer thickness has an increasing course, ie the value of the ratio S / (Se + S) is minimal at the surface 9 and decreases from the surface 9 toward the interface 10, so that the value of the ratio S / (Se + S) at the interface 10 is maximum.
  • the heat treatment is carried out in such a way that the depth profile initially has a decreasing course over the layer thickness and then an increasing course, ie the value of the ratio S / (Se + S) has on the surface 9 a first maximum value, decreases from the surface 9 towards the interface 10 first, and increases between the surface and interfacial 9, 10 a (single) minimum value, and then increases again so that the value of behaves ⁇ Nisses S / (Se + S) assumes a second maximum value at the boundary surface 10, wherein the second maximum value to the first
  • the heat treatment is carried out in such a way that the depth profile initially has an increasing course over the layer thickness and then a decreasing course, ie the value of the ratio S / (Se + S) has on the surface 9 a first minimum value increases initially from the surface 9 to the interface 10 and assumes a (single) maximum value between the upper and the interface 9, 10, and then decreases again, so that the value of the ratio S / (Se + S) assumes a second mini ⁇ malwert at the interface 10, the second minimum value for the first minimum value may be equal, but in general is different.
  • etching is optional, for example, provided with KCN to remove particularly in kup ⁇ ferreicher processing (Cu / (Zn + Sn)> 1) Kupferselenide and / or copper sulfides.
  • kup ⁇ ferreicher processing Cu / (Zn + Sn)> 1
  • Kupferselenide and / or copper sulfides are presented of Fig. 1 indicated.
  • FIG. 2 illustrates a first procedure for producing the absorber 2 consisting of the pentane compound semiconductor CZTSSe.
  • the first precursor layer 5 is deposited on the back ⁇ electrode layer 4, for example, by sputtering of the elements Cu, Zn, Sn of three elemental targets consisting of Cu, Zn and Sn, where appropriate, an additional dopant deposition ⁇ takes place.
  • the individual layers of the metals Cu, Zn, Sn are deposited, for example, in the layer sequence Cu / Zn / Sn, but other layer sequences are also possible.
  • a certain position sequence for example Cu / Zn / Sn, is deposited several times (preferably 2-20 times) in succession, wherein the position sequences may be the same or different from one another.
  • the Chalcogen Selenium is made second precursor layer 6 deposited on the first precursor layer 5, which can be done for example by thermal evaporation Ver ⁇ (PVD).
  • the layer structure 7 accordingly comprises the precursor elements or precursor phases Cu-Zn-Sn / Se, hereinafter referred to as "Cu-Zn-Sn / Se precursor".
  • the Cu-Zn-Sn / Se precursor is subjected to rapid thermal processing (RTP processing) in a sulfur-containing atmosphere.
  • RTP processing rapid thermal processing
  • S-gas and / or H 2 S gas is supplied to the process space 13 containing the layer structure 1.
  • the temperature in the heat treatment is preferably higher than 400 ° C, particularly preferably higher than 500 ° C.
  • the heat treatment causes a reactive conversion of the Cu-Zn-Sn / Se precursor to the pentane compound semiconductor Cu 2 ZnSn (S, Se) 4 , which forms the absorber 2.
  • the processing of the selenium-containing Cu-Zn-Sn / Se precursor in a sulfur-containing atmosphere allows an exchange process of selenium and sulfur between the second precursor layer 6 and the process atmosphere. This allows the sulfur content and thus the band gap of the formed
  • Cu 2 ZnSn (S, Se) 4-compound semiconductor can be specifically influenced during the layer ⁇ education process.
  • a time- and / or concentration-dependent variation of the sulfur content in the reaction gas atmosphere during thermal processing in the desired manner a defined concentration profile (depth profile) along the
  • Layer thickness of the formed Cu 2 ZnSn (S, Se) 4 -Veritatis- semiconductors are generated. Due to the generated band gap ⁇ profile of the absorber 4, an improvement of the effect ⁇ degree of thin-film solar cell can be achieved.
  • an inert process gas eg nitrogen (N 2 ) or argon (Ar)
  • S gas and / or H 2 S Gas or other S-containing gas
  • S-gas and / or H 2 S-gas could be supplied to the heat treatment only in a second half of the time interval, whereby the time interval of the supply line may last until the end of the heat treatment or may end sooner.
  • a sulfur profile is produced by incorporation of S and subsequent diffusion processes so that the ratio S / (Se + S) at the surface 9 is maximum and decreases towards the interface 10 ,
  • the increased band gap of the surface 9 (maximum ratio S / (Se + S)) into the thin-film solar cell to a raised stabili ⁇ hung the open circuit voltage.
  • the height of the short-circuit current is determined by the minimum of the band gap in the interior of the absorber 2.
  • Inert gas is added to influence the sulfur depth profile in a targeted manner.
  • Fig. 3 is another method for producing the pentane compound semiconductor CZTSSe existing
  • deposition of the chalcogen S is provided instead of deposition of Se for the production of the second precursor layer 6, so that the layer structure 7 contains the precursor elements Cu-Zn-Sn / S (Cu-Zn-Sn / S precursor).
  • the Cu-Zn-Sn / S precursor undergoes rapid thermal processing in a Se-containing atmosphere.
  • Se gas and / or H 2 Se gas is supplied to the process space 13 containing the layer structure 1.
  • a reactive Encrypt ⁇ development of the Cu ZnSn / S precursor to pentanary compound semiconductor ⁇ ZnSn Cu 2 (S, Se) is caused to 4, which forms the absorber. 2
  • the processing of the S-containing Cu-Zn-Sn / S precursor in Se-containing atmosphere allows an exchange process of S and Se between the second precursor layer 6 and the gas phase.
  • Stratification process can be influenced.
  • an inert gas eg nitrogen (N 2 ) or argon (Ar)
  • Se gas and / or H 2 Se gas could be heat-treated only in a second half of the time interval.
  • Se gas and / or H 2 Se gas during a (earlier) first phase for example, but not necessarily, during the first half of the time interval
  • ⁇ in a second phase of the process an inert gas is supplied ⁇ leads to affect the sulfur-depth profile in a controlled manner.
  • two time intervals could where Se gas and / or H 2 Se gas is supplied into the supplied through a time interval, only inert gas may be underbro ⁇ chen. It would be conceivable, however, that also Se gas and / or H 2 Se gas is supplied during the complete heat treatment.
  • FIG. 4 shows another method for producing the pentane compound semiconductor CZTSSe
  • the layer structure 7 contains the precursor elements Cu-Zn-Sn / S-Se (Cu-Zn-Sn / S-Se precursor).
  • the second precursor layer 6 may contain at least two individual layers of S and Se or Se and S.
  • the second precursor layer 6 comprises a plurality n (n> 2) of layer sequences, each consisting of two individual layers S and Se or Se and S (nx S / Se or nx Se / S).
  • the Cu-Zn-Sn / S-Se precursor undergoes rapid thermal processing in an S and / or Se-containing atmosphere.
  • Se gas and / or H 2 Se gas (or other selenium-containing gas) and / or S gas and / or H 2 S gas (or other sulfur-containing gas) is added to the process space 13 containing the layer structure 1 fed. Due to the heat treatment becomes a reactive Conversion of the Cu-Zn-Sn / S-Se precursor to the pentane Ver ⁇ bonding semiconductor Cu 2 ZnSn (S, Se) 4 causes, which forms the absorber 2.
  • the processing of the sulfur-containing and selenium-containing Cu-Zn-Sn / S-Se precursor in S and / or Se-containing atmosphere allows an exchange process of S and Se between the second precursor layer 6 and the gas phase.
  • the sulfur content of the formed Cu 2 ZnSn (S, Se) are influenced during the layer forming process aims ge ⁇ 4 -Verbin- dung semiconductor.
  • Se and S in the second precursor layer 6 it is possible to influence the reaction kinetics in the RTP process, in which case positive effects with regard to a process time minimization are probable (eg due to a preferred reaction of Cu with S).
  • the process gas used may be Se gas and / or H 2 Se gas (or another selenium-containing gas) and / or S gas and / or H 2 S gas ( or other sulfur-containing gas) and in a second (later) Pro ⁇ zessphase an inert gas are supplied to the process chamber containing the layer structure 1. 13
  • Se gas and / or H 2 Se gas and / or S gas and / or H 2 S gas it would be possible for Se gas and / or H 2 Se gas and / or S gas and / or H 2 S gas to be present in a (later) second phase and possibly in an earlier first phase Inert gas are supplied to the process chamber 13.

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  • Photovoltaic Devices (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Recrystallisation Techniques (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un semi-conducteur composé à partir de kësterite/stannite pentanaire de type Cu2ZnSn(S, Se)4, comprenant les étapes suivantes : production d'au moins un empilage de couches de précurseurs constitué d'une première couche de précurseur et d'une deuxième couche de précurseur, la première couche de précurseur étant réalisée dans une première étape par dépôt des métaux cuivre, zinc et étain sur un corps et la deuxième couche de précurseur étant réalisée dans une deuxième étape par dépôt des chalcogènes soufre et/ou sélénium sur la première couche de précurseur; traitement thermique du ou des empilages de couches de précurseurs dans un espace de processus de telle manière que les métaux de la première couche de précurseur et le ou les chalcogènes de la deuxième couche de précurseur réagissent entre eux pour former le semi-conducteur composé; introduction d'au moins un gaz de processus pendant le traitement thermique du ou des empilages de couches de précurseurs dans l'espace de processus. Lorsque la deuxième couche de précurseur contient un chalcogène, choisi parmi le soufre et le sélénium, le gaz de processus contient l'autre chalcogène respectif et/ou un composé contenant l'autre chalcogène respectif, ou, lorsque la deuxième couche de précurseur contient les deux chalcogènes soufre et sélénium, le gaz de processus contient du soufre et/ou du sélénium et/ou un composé contenant du soufre et/ou un composé contenant du sélénium. L'invention concerne en outre une cellule solaire à couche mince comprenant un absorbeur constitué du semi-conducteur composé pentanaire Cu2ZnSn(S, Se)4 sur un corps, ledit absorbeur comportant depuis une surface du semi-conducteur en direction d'une surface limite du corps un profil de profondeur du soufre de différentes classes pouvant être prédéfini.
EP12709818.4A 2011-03-10 2012-02-22 Procédé de fabrication du semi-conducteur composé pentanaire cztsse et cellule solaire à couche mince Withdrawn EP2684212A1 (fr)

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EP12709818.4A EP2684212A1 (fr) 2011-03-10 2012-02-22 Procédé de fabrication du semi-conducteur composé pentanaire cztsse et cellule solaire à couche mince
PCT/EP2012/052993 WO2012119857A1 (fr) 2011-03-10 2012-02-22 Procédé de fabrication du semi-conducteur composé pentanaire cztsse et cellule solaire à couche mince

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BR (1) BR112013018999A2 (fr)
WO (1) WO2012119857A1 (fr)
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US20150037927A1 (en) * 2012-04-27 2015-02-05 Saint-Gobain Glass France Method for producing the pentanary compound semiconductor cztsse doped with sodium
CN103094422A (zh) * 2013-01-29 2013-05-08 电子科技大学 铜锌锡硫硒薄膜制备中的掺杂工艺
JP6061765B2 (ja) * 2013-04-16 2017-01-18 ソーラーフロンティア株式会社 太陽電池の製造方法
EP2800146A1 (fr) * 2013-05-03 2014-11-05 Saint-Gobain Glass France Substrat de contact arrière pour module ou cellule photovoltaïque
CN104701394B (zh) * 2013-12-09 2017-02-15 北京有色金属研究总院 一种具有择优取向的Cu2ZnSn(S1‑xSex)4薄膜
US9240501B2 (en) * 2014-02-12 2016-01-19 Solar Frontier K.K. Compound-based thin film solar cell
EP2947682A1 (fr) * 2014-05-20 2015-11-25 IMEC vzw Procédé de formation de couches de chalcogénures
KR101656842B1 (ko) * 2014-08-18 2016-09-13 재단법인대구경북과학기술원 태양전지용 CZTS/CZTSe계 박막 및 제조방법 및 그 방법에 의해 제조된 CZTS/CZTSe계 박막
US9530908B2 (en) 2014-11-13 2016-12-27 International Business Machines Corporation Hybrid vapor phase-solution phase growth techniques for improved CZT(S,Se) photovoltaic device performance
KR101733438B1 (ko) 2015-02-11 2017-05-11 한국과학기술연구원 경사조성형 칼코제나이드 박막 및 그 제조방법
CN104979429B (zh) * 2015-06-11 2016-10-05 岭南师范学院 一种微米级球形铜锌锡硫硒单晶颗粒的制备方法
KR102075633B1 (ko) 2018-11-08 2020-02-10 재단법인대구경북과학기술원 CZTSSe계 박막 제조방법 및 이를 이용한 박막 태양전지 제조방법
KR102284740B1 (ko) 2018-11-23 2021-08-03 재단법인대구경북과학기술원 CZTSSe계 광흡수층의 제조방법 및 이를 포함하는 태양전지의 제조방법
KR101978110B1 (ko) 2019-02-01 2019-05-13 재단법인대구경북과학기술원 화합물 광흡수층의 제조방법 및 이를 포함하는 태양전지의 제조방법
CN112899652A (zh) * 2019-11-19 2021-06-04 中国科学院微电子研究所 一种原子层沉积制备薄膜材料的装置和方法
KR102420408B1 (ko) * 2020-07-31 2022-07-13 전남대학교산학협력단 무기박막태양전지용 p형 화합물 반도체층 제조방법 및 상기 방법으로 제조된 p형 화합물 반도체층을 포함하는 무기박막태양전지

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US9087954B2 (en) 2015-07-21
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KR101522128B1 (ko) 2015-05-20
CN103403851A (zh) 2013-11-20
BR112013018999A2 (pt) 2017-01-31
ZA201305821B (en) 2014-04-30
US20140053896A1 (en) 2014-02-27
KR20130143109A (ko) 2013-12-30

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