EP2102898A2 - Réaction inter-bobine d'un film précurseur pour formation d'un absorbeur solaire - Google Patents

Réaction inter-bobine d'un film précurseur pour formation d'un absorbeur solaire

Info

Publication number
EP2102898A2
EP2102898A2 EP07872342A EP07872342A EP2102898A2 EP 2102898 A2 EP2102898 A2 EP 2102898A2 EP 07872342 A EP07872342 A EP 07872342A EP 07872342 A EP07872342 A EP 07872342A EP 2102898 A2 EP2102898 A2 EP 2102898A2
Authority
EP
European Patent Office
Prior art keywords
chamber
gas
continuous flexible
heating chamber
flexible workpiece
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Withdrawn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
EP07872342A
Other languages
German (de)
English (en)
Other versions
EP2102898A4 (fr
Inventor
Bulent M. Basol
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.)
SoloPower Inc
Original Assignee
SoloPower Inc
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 SoloPower Inc filed Critical SoloPower Inc
Publication of EP2102898A2 publication Critical patent/EP2102898A2/fr
Publication of EP2102898A4 publication Critical patent/EP2102898A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • 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
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67098—Apparatus for thermal treatment
    • H01L21/67109—Apparatus for thermal treatment mainly by convection
    • 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
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • 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
    • H01L31/0324—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIVBVI or AIIBIVCVI chalcogenide compounds, e.g. Pb Sn Te
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
    • H01L31/1844—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising ternary or quaternary compounds, e.g. Ga Al As, In Ga As P
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/544—Solar cells from Group III-V materials

Definitions

  • the present invention relates to method and apparatus for preparing thin films of semiconductor films for radiation detector and photovoltaic applications
  • Solar cells are photovoltaic devices that convert sunlight directly into electrical power
  • the most common solar cell material is silicon, which is in the form of single or polycrystalline wafers
  • the cost of electricity generated using silicon- based solar cells is higher than the cost of electricity generated by the more traditional methods Therefore, since early 1970's there has been an effort to reduce cost of solar cells for terrestrial use
  • One way of reducing the cost of solar cells is to develop low-cost thin film growth techniques that can deposit solar-cell-quahty absorber mate ⁇ als on large area substrates and to fab ⁇ cate these devices usmg high-throughput, low-cost methods
  • Group IBIIIAVIA compound semiconductors comprising some of the Group
  • the cell efficiency is a strong function of the molar ratio of IB/IIIA If there are more than one Group IIIA mate ⁇ als in the composition, the relative amounts or molar ratios of these IIIA elements also affect the properties For a Cu(In, Ga)(S 5 Se): absorber layer, for example, the efficiency of the device is a function of the molar ratio of Cu/(In+Ga) Furthermore, some of the important parameters of the cell, such as its open circuit voltage, short circuit current and fill factor vary with the molar ratio of the IIIA elements, i e the Ga/(Ga+In) molar ratio In general, for good device performance Cu/(In+Ga) molar ratio is kept at around or below 1 0 As the Ga/(Ga+In) molar ratio increases, on the other hand, the optical bandgap of the absorber layer increases and therefore the open circuit voltage of the solar cell increases while the short
  • One technique for growing Cu(In,Ga)(S,Se) 2 type compound thin films for solar cell applications is a two-stage process where metallic components of the Cu(In, Ga)(S,Se)2 material are first deposited onto a substrate, and then reacted with S and/or Se in a high temperature annealing process
  • metallic components of the Cu(In, Ga)(S,Se)2 material are first deposited onto a substrate, and then reacted with S and/or Se in a high temperature annealing process
  • thin layers of Cu and In are first deposited on a substrate and then this stacked precursor layer is reacted with Se at elevated temperature If the reaction atmosphere also contains sulfur, then a CuIn(S 1 Se) 2 layer can be grown
  • Addition of Ga in the precursor layer i e use of a Cu/In/Ga stacked film precursor, allows the growth of a Cu(In,Ga)(S,Se) 2 absorber
  • Two-stage process approach may also employ stacked layers comprising
  • Group VIA mate ⁇ als For example, a Cu(In 1 Ga)Se 2 film may be obtained by depositing In- Ga-Se and Cu-Se layers in an In-Ga-Se/Cu-Se stack and reacting them in presence of Se Similarly, stacks comprising Group VIA matenals and metallic components may also be used Stacks comprising Group VIA mate ⁇ als include, but are not limited to In-Ga-Se/Cu stack, Cu/In/Ga/Se stack, Cu/Se/In/Ga/Se stack, etc
  • Selemzation and/or sulfidation or sulfu ⁇ zation of precursor layers comprising metallic components may be earned out in various forms of Group VIA mate ⁇ al(s)
  • gases such as H 2 Se, H 2 S or their mixtures to react, either simultaneously or consecutively, with the precursor comp ⁇ sing Cu, In and/or Ga
  • a Cu(In, Ga)(S, Se) 2 film may be formed after annealing and reacting at elevated temperatures
  • Se vapors or S vapors from elemental sources may also be used for selemzation and sulfidation
  • Se and/or S may be deposited over the precursor layer comprising Cu, In and/or Ga and the stacked structure can be annealed at elevated temperatures to initiate reaction between the metallic elements or components and the Group VIA mate ⁇ al(s) to form
  • the present invention provides a method and integrated tool to form solar cell absorber layers on continuous flexible substrates
  • a roll-to-roll rapid thermal processing (RTP) tool including multiple chambers is used to react a precursor layer on a continuous flexible workpiece
  • An aspect of the present invention provides an integrated roll-to-roll RTP tool with multiple chambers for forming a solar cell absorber by reacting a precursor layer on a surface of a continuous flexible workpiece
  • the tool includes an elongated housing including a vacuum line to pull vacuum inside the elongated housing Further, a heating chamber of the elongated housing applies a predetermined temperature profile to the continuous flexible workpiece
  • the heating chamber extends between a first opening at a first end of the heating chamber and a second opening at a second end of the heating chamber, and includes a process gap defined by a top wall, a bottom wall, and side walls of the heating chamber
  • a gas mlet line disposed adjacent the first opening of the heating chamber delivers a process gas which may be inert or may comp ⁇ se a Group VIA mate ⁇ al into the heating chamber during the process
  • the continuous flexible workpiece is configured to be advanced through the process gap and between the first and the second openings during a process Depending on the speed of the flexible workpiece in the process
  • a moving mechanism holds and moves the continuous flexible workpiece within and through the process gap of the heating chamber, including a portion of the continuous flexible workpiece disposed within and processed in the process chamber, by feeding previously unrolled portions of the continuous flexible workpiece from the supply roll in the supply chamber and taking up and wrapping the processed portions of the continuous flexible workpiece in the receiving chamber
  • An exhaust line disposed adjacent one of first and the second opening of the heating chamber removes the process gas and gaseous byproducts from the process chamber
  • the gas mlet line and the exhaust line are configured to allow presence of the process gas flow over the front surface of the continuous flexible workpiece as the continuous flexible workpiece is moved within the process gap
  • FIG 1 is a cross-sectional view of a solar cell employing a Group IBIIIAVIA absorber layer
  • FIG 2 shows an apparatus to react precursor layers in a reel-to-reel fashion to form a Group IBIIIAVIA layer on a flexible foil base
  • FIG 3A shows an exemplary flexible structure comprising a flexible base and a precursor layer deposited on it
  • FIG 3B shows a base with a Group IBIIIAVIA absorber layer formed on it by reacting the precursor layer(s) of Figure 3 A
  • FIG 4 shows another apparatus to react precursor layers in a reel-to-reel fashion to form a Group IBIIIAVIA layer on a flexible foil base
  • FIG 5 A- 5 B show cross-sectional views of different reaction chambers with a flexible structure placed in them
  • FIG 5 C shows a cross-sectional view of a reaction chamber comprising an outer chamber and an inner chamber
  • FIG 6 shows such an exemplary version of the reactor of Figure 2
  • Reaction of precursors, comprising Group IB mate ⁇ al(s), Group HIA matenal(s) and optionally Group VIA mate ⁇ al(s) or components, with Group VIA mate ⁇ al(s) may be achieved in va ⁇ ous ways These techniques involve heating the precursor layer to a temperature range of 3 5 0-600 °C, preferably to a range of 400- 5 7 5 0 C, in the presence of at least one of Se, S, and Te provided by sources such as, i) solid Se, S or Te sources directly deposited on the precursor, and ii) HjSe gas, H 2 S gas, t ⁇ Te gas, Se vapors, S vapors, Te vapors etc forpe ⁇ ods ranging from 1 minute to several hours
  • the Se, S, Te vapors may be generated by heating solid sources of these mate ⁇ als away from the precursor also Hydride gases such as H 2 Se and H 2 S may be bottled gases Such hydride gases and short-lifetime gases such as t ⁇ T
  • Some of the preferred embodiments of forming a Cu(In, Ga)(S,Se) 2 compound layer may be summarized as follows 1) depositing a layer of Se on a metallic precursor comprising Cu, In and Ga forming a structure and reacting the structure in gaseous S source at elevated temperature, 11) depositing a mixed layer of S and Se or a layer of S and a layer of Se on a metallic precursor composing Cu, In and Ga forming a structure, and reacting the structure at elevated temperature in either a gaseous atmosphere free from S or Se, or in a gaseous atmosphere comprising at least one of S and Se, in) depositing a layer of S on a metallic precursor composing Cu, In and Ga forming a structure and reacting the structure in gaseous Se source at elevated temperature, iv) depositing a layer of Se on a metallic precursor composing Cu, In and Ga forming a structure, and reacting the structure at elevated temperature to form a Cu(In,Ga)Se2 layer and/or
  • mateoals are corrosive Therefore, mateoals for all parts of the reactors or chambers that are exposed to Group VIA materials or mateoal vapors at elevated temperatures should be properly selected These parts should be made of or should be coated by substantially inert mateoals such as ceramics, e g alumina, tantalum oxide, titania, zircoma etc , glass, quartz, stainless steel, graphite, refractory metals such as Ta, refractory metal nitrides and/or carbides such as Ta-mtode and/or carbide, Ti- mtode and/ or carbide, W-mtode and/or carbide, other mtodes and/or carbides such as Si- nitnde and/or carbide, etc
  • substantially inert mateoals such as ceramics, e g alumina, tantalum oxide, titania, zircoma etc , glass, quartz, stainless steel, graphite, refractory metals such as Ta,
  • Group VIA mateoal may be earned out m a reactor that applies a process temperature to the precursor layer at a low rate
  • rapid thermal processing RTP
  • RTP rapid thermal processing
  • inks comprising Group VIA nano particles may be prepared and these inks may be deposited to form a Group VIA mateoal layer within the precursor layer
  • Other liquids or solutions such as organometallic solutions composing at least one Group VIA mateoal may also be used Dipping into melt or ink, spraying melt or ink, doctor-bladmg or ink wn ⁇ ng techniques may be employed to deposit such layers
  • the precursor layer to be reacted in this reactor may comprise at least one Group IB material and at least one Group IIIA material
  • the precursor layer may be a stack of Cu/In/Ga, Cu-Ga/In, Cu-In/Ga, Cu/In-Ga, Cu-Ga/Cu-In, Cu-Ga/Cu-In/Ga, Cu/Cu- In/Ga, or Cu-Ga/In/In-Ga etc , where the order of various material layers within the stack may be changed
  • Cu-Ga, Cu-In, In-Ga mean alloys or mixtures of Cu and Ga, alloys or mixtures of Cu and In, and alloys or mixtures of In and Ga, respectively
  • the precursor layer may also include at least one Group VIA matenal There are many examples of such precursor layers Some of these are Cu
  • Annealing and/or reaction steps may be earned out m the reactors of the present invention at substantially the atmosphenc pressure, at a pressure lower than the atmospheric pressure or at a pressure higher than the atmosphenc pressure Lower pressures in reactors may be achieved through use of vacuum pumps
  • the reel-to-reel apparatus 100 of Figure 2 may compnse an elongated heating chamber 101 that is surrounded by a heater system 102 which may have one or more heating zones such as Zl, Z2, and Z3 to form a temperature profile along the length of the chamber 101 In between zones there are preferably buffer regions of low thermal conductivity so that a sharp temperature profile may be obtained Details of such use of buffer regions are discussed in US Application Senal No 11/ 5 49, 5 90 entitled Method and Apparatus for Converting Precursor layers into Photovoltaic Absorbers, filed on October 13, 2006, which is incorporated herein by reference
  • the chamber 101 is integrally sealably attached to a first port 103 and a second port 104 Integrally sealably means that the internal volume of chamber, the first port and the second port are sealed from air atmosphere, therefore, any gases used in the internal volume does not leak out (except at designated exhaust ports) and no air leaks into the internal volume In other words the integration of the chamber, first and second ports are vacuum tight A first spool 1
  • the flexible structure 106A before the reaction may be a base with a precursor film deposited on at least one face of the base
  • the flexible structure 106B after the reaction composes the base and a Group IBIIIAVIA compound layer formed as a result of reaction of the precursor layer
  • the substrate of the base may be a flexible metal or polyme ⁇ c foil
  • the precursor film on the base comprises at least Cu, In, and Ga and optionally a Group VIA material such as Se
  • the back side 2OA of the flexible structure 106 may or may not touch a wall of the chamber 101 as it is moved through the chamber 101.
  • ACu(In,Ga)(Se,S) 2 absorber layer may be formed using the single chamber reactor design of Figure 2.
  • An exemplary flexible structure 106A before the reaction is shown in Figure 3A.
  • the base 20 may be similar to the base 20 of Figure 1.
  • a precursor layer 200 is provided on the base 20.
  • the precursor layer 200 comprises Cu, and at least one of In and Ga.
  • Preferably the precursor layer 200 comprises all of Cu, In and Ga.
  • a Se layer 201 may optionally be deposited over the precursor layer 200 forming a Se-bearing precursor layer 202. Se may also be mixed in with the precursor layer 200 (not shown) forming another version of a Se-bearing precursor layer.
  • the flexible structure after the reaction step is shown in Figure 3B.
  • the flexible structure 106B comprises the base 20 and the Group IBIIIAVIA compound layer 203 such as a Cu(In,Ga)(Se,S)2 film that is obtained by reacting the precursor layer 200 or the Se-bearing precursor layer 202.
  • the Group IBIIIAVIA compound layer 203 such as a Cu(In,Ga)(Se,S)2 film that is obtained by reacting the precursor layer 200 or the Se-bearing precursor layer 202.
  • one end of the web may be fed through the chamber 101, passing through the gaps 111 of the slits 110, and then wound on the second spool 10 5 B. Doors (not shown) to the first port 103 and the second port 104 are closed and the system (including the first port 103, the second port 104 and the chamber 101) is evacuated to eliminate air. Alternately the system may be purged through the exhaust 112 with an inert gas such as N 2 coming through any or all of the gas inlets or gas lines for a period of time. After evacuating or purging, the system is filled with the inert gas and the heater system 102 may be turned on to establish a temperature profile along the length of the chamber 101. When the desired temperature profile is established, the reactor is ready for process.
  • an inert gas such as N 2 coming through any or all of the gas inlets or gas lines for a period of time.
  • a gas comprising Se vapor or a source of Se such as H2Se may be introduced into the chamber, preferably through chamber gas inlet 113.
  • the exhaust 112 may now be opened by opening its valve so that Se bearing gas can be directed to a scrubber or trap (not shown).
  • Se is a volatile material and at around the typical reaction temperatures of 400-600 C its vapor tends to go on any cold surface present and deposit in the form of solid or liquid Se.
  • Se vapors may pass into the first port 103 and/or the second port 104 and deposit on all the surfaces there including the unreacted portion of the web in the first port 103 and the already reacted portion of the web in the second port 104.
  • the introduced gas may be a Se-bea ⁇ ng and/or S-bea ⁇ ng gas that does not breakdown into Se and/or S at low temperature, but preferably the introduced gas is an inert gas such as N 2 and it pressurizes the two ports establishing a flow of inert gas from the ports towards the chamber 101 through the gaps 111 of the slits 110
  • the velocity of this gas flow can be made high by reducing the gaps 111 of the slits 110 and/or increasing the flow rate of the gas into the ports This way diffusion of Se vapor into the ports is reduced or prevented, directing such vapors to the exhaust 112 where it can be trapped away from the processed web
  • the preferred values for the gap 111 of the slits 110 may be in the range of 0 5 - 5 mm, more preferably in the range of 1-3 mm
  • Flow rate of the gas into the ports may be adjusted depending on the width of the slits which in turn depends on the width of the flexible structure 106 or web Typical web widths may be in the range of 1-4 ft
  • the flexible structure 106 may be moved from the first port 103 to the second port 104 at a pre-determined speed This way, an unreacted portion of the flexible structure 106 comes off the first roll 1O 5 A, enters the chamber 101, passes through the chamber 101, gets reacted forming a Cu(In,Ga)S ⁇ 2 absorber layer on the base of the web and gets rolled onto the second spool 1O 5 B in the second port 104 It should be noted that there may be an optional cooling zone (not shown) within the second port 104 to cool the reacted web before winding it on the second spool 105B [0039]
  • the above discussion is also applicable to the formation of absorber layers containing S For example, to form a Cu(In,Ga)S 2 layer the Se-beanng gas of the above discussion may be replaced with a S-bea ⁇ ng gas such as H2S To form a
  • the reaction gas composition may also be changed m the multi-step reaction approach described above
  • a first gas such as tbSe may be used in the chamber 101 to form a selemzed precursor layer
  • another gas such as H2S may be introduced in the chamber 101
  • the selemzed precursor layer may be reacted with S as the web is moved from the second spool 1O 5 B to the first spool 1O 5 A and thus a Cu(In,Ga)(Se,S)2 layer may be grown by converting the already selemzed precursor layer mto sulfo-selemde
  • Selecting the gas concentrations, web speeds and reaction temperatures the amount of Se and S in the absorber layer may be controlled For example, S/(Se+S)
  • a Cu(In 1 Ga)(Se 1 S) 2 absorber layer may be formed usmg the three-section chamber reactor of Figure 4 After loading the unreacted flexible structure 106, pumping and purging the system as desc ⁇ bed m Example 1, the process may be initiated Sections A, B and C of the three-section chamber 450 may have temperatures of Tl, T2 and T3 which may or not be equal to each other Furthermore, each of the sections A, B and C may have a temperature profile rather than just a constant temperature along their respective lengths During processing, a first process gas such as N 2 may be introduced mto the low-volume segment 410 in section B through inlet 403, while a second process gas and a third process gas may be introduced in sections A and C, respectively, through inlets 401 and 402, respectively
  • the second process gas and the third process gas may be the same gas or two different gases
  • the second process gas may comp ⁇ se Se and the third process gas may comprise S
  • the precursor layer on the portion starts reacting with Se forming a selenized precursor layer on the portion
  • portion enters the low-volume segment 410 it gets annealed m the N 2 gas (if section B is heated) within this segment until it enters section C In section C sulfidation or sulfunzation takes place due to presence of gaseous S species, and a Cu(In 1 Ga)(Se 1 S) 2 absorber layer is thus formed on the portion before the portion exits the three-section chamber 4 5 0 through the second gap 11 IB of the second slit HOB
  • the S/(Se+S) molar ratio in the absorber layer may be controlled by
  • the length and/or the temperature of section C may be increased Reverse may be done to reduce the S/(Se+S) molar ratio
  • Reverse may be done to reduce the S/(Se+S) molar ratio
  • FIG. 5A and 5 B A variety of different cross sectional shapes may be used for the chambers of the present invention
  • Substantially cylindrical reaction chambers with circular cross section are good for pulling vacuum in the chamber even if the chamber is made from a material such as glass or quartz
  • the circular chambers however, get very large as the substrate or web width increases to lft, 2 ft or beyond
  • Temperature profiles with sharp temperature changes cannot be sustained using such large cylindrical chambers and thus roll-to-roll RTP process cannot be carried out on wide flexible substrates such as substrates that may be 1-4 ft wide or even wider
  • the chamber 50 0B includes a rectangular gap defined by the top wall 51OA, bottom wall 5 1OB, and the side walls 51OC
  • the chamber is preferably constructed of metal because for pulling vacuum in such a chamber without breaking it requires very thick walls (half an inch and larger) if the chamber is contracted of quartz or glass
  • the top wall 5 1OA and the bottom wall 51OB are substantially parallel to each other, and the flexible structure 106 is placed between them
  • Chambers with rectangular cross section or configuration is better for reducing reactive gas consumption since the height of such chambers may be reduced to below 10 mm, the width being approximately close to the width of the flexible structure (which may be 1-4 ft)
  • Such small height also allows reaction in Group VIA vapor without the need to introduce too much Group VIA mate ⁇ al into the chamber
  • the height of the chamber 5 00B, i e , gap size is the distance between the top and the bottom walls and small gap size is necessary to keep a high overpressure of Group VIA mate
  • another preferred chamber design includes a dual chamber 500C where an inner chamber 50 IB with rectangular cross section is placed within a cylindrical outer chamber 501 A with circular cross section
  • the flexible structure 106 or web passes through the inner chamber 50 IB which may be orthorhombic in shape and all the gas flows are preferably directed to and through the inner chamber 5 01B which has a much smaller volume than the outer chamber 50 IA
  • the whole chamber may be easily evacuated because of the cylindrical shape of the outer chamber 501B, even though the chamber may be made out of a material such as quartz Heaters (not shown) in this case may be placed outside the inner chamber 50 IB, but inside the outer chamber 501 A
  • This way sharp temperature profiles can be sustained along the length of the rectangular cross section chamber while having the capability to evacuate the reactor body
  • FIG. 6 shows such an exemplary version of the reactor of Figure 2 Only the chamber portion is shown for simplifying the drawing
  • the dual-chamber 600 comp ⁇ ses a cylindrical chamber 601 and an orthorhombic chamber 602 which is placed in the cylindrical chamber 601 Gas inlet 113 and exhaust 112 are connected to the orthorhombic chamber 602
  • the cylindrical chamber 601 may not be hermetically sealed from the orthorhombic chamber so that when the overall chamber is pumped down, pressure equilibrates between the cylindrical chamber 601 and the orthorhombic chamber Otherwise, if these chambers are sealed from each other, they may have to be pumped down together at the same time so that there is not a large pressure differential between them
  • Solar cells may be fabricated on the compound layers formed in the reactors of the present invention using mate ⁇ als and methods well known in the field For example a thin ( ⁇ 0 1 microns) CdS layer may be deposited on the surface of the compound layer using the chemical dip method A transparent window of ZnO may be deposited over the CdS layer using MOCVD or sputtering techniques A metallic finger pattern is optionally deposited over the ZnO to complete the solar cell

Landscapes

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

Abstract

Outil de traitement thermique rapide inter-bobine ( roll-to-roll rapid thermal processing/RTP) à chambres multiples pour formation d'un absorbeur solaire par réaction d'une couche précurseur sur une pièce souple continue. L'outil RTP est constitué d'un boîtier de forme allongée comprenant une chambre de chauffage au profil thermique prédéterminé, une chambre d'alimentation et une chambre réceptrice. La chambre de chauffage comporte un petit espace de traitement dans lequel on fait réagir la couche précurseur avec un matériau du Groupe VIA pour former une couche d'absorbeur. La pièce souple continue est déroulée et amenée dans la chambre de chauffage où elle est traitée avant d'être transférée et enroulée dans la chambre réceptrice.
EP07872342A 2006-11-10 2007-11-12 Réaction inter-bobine d'un film précurseur pour formation d'un absorbeur solaire Withdrawn EP2102898A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US86538506P 2006-11-10 2006-11-10
PCT/US2007/084432 WO2008085604A2 (fr) 2006-11-10 2007-11-12 Réaction inter-bobine d'un film précurseur pour formation d'un absorbeur solaire

Publications (2)

Publication Number Publication Date
EP2102898A2 true EP2102898A2 (fr) 2009-09-23
EP2102898A4 EP2102898A4 (fr) 2011-06-29

Family

ID=39609232

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07872342A Withdrawn EP2102898A4 (fr) 2006-11-10 2007-11-12 Réaction inter-bobine d'un film précurseur pour formation d'un absorbeur solaire

Country Status (6)

Country Link
EP (1) EP2102898A4 (fr)
JP (1) JP2010509779A (fr)
KR (1) KR20090110293A (fr)
CN (1) CN101578707B (fr)
TW (1) TW200832726A (fr)
WO (1) WO2008085604A2 (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2008297944A1 (en) * 2007-09-11 2009-03-19 Centrotherm Photovoltaics Ag Method and apparatus for thermally converting metallic precursor layers into semiconducting layers, and also solar module
US8323408B2 (en) 2007-12-10 2012-12-04 Solopower, Inc. Methods and apparatus to provide group VIA materials to reactors for group IBIIIAVIA film formation
US8163090B2 (en) * 2007-12-10 2012-04-24 Solopower, Inc. Methods structures and apparatus to provide group VIA and IA materials for solar cell absorber formation
KR20110097908A (ko) * 2008-11-28 2011-08-31 볼커 프로브스트 반도체 층 또는 원소 셀레늄 및/또는 황으로 처리된 코팅 기판, 특히 평면 기판의 제조 방법
DE102009009022A1 (de) * 2009-02-16 2010-08-26 Centrotherm Photovoltaics Ag Verfahren und Vorrichtung zur Beschichtung von flachen Substraten mit Chalkogenen
TWI509107B (zh) * 2009-03-06 2015-11-21 Centrotherm Photovoltaics Ag 利用氧族元素源將金屬先驅物薄膜熱轉變成半導體薄膜之方法及裝置
DE102009011496A1 (de) * 2009-03-06 2010-09-16 Centrotherm Photovoltaics Ag Verfahren und Vorrichtung zur thermischen Umsetzung metallischer Precursorschichten in halbleitende Schichten mit Chalkogenrückgewinnung
DE102009049570B3 (de) 2009-10-15 2011-02-17 Fhr Anlagenbau Gmbh Anordnung zur Gasseparation und deren Verwendung
TWI398013B (zh) * 2009-12-18 2013-06-01 Jenn Feng New Energy Co Ltd Method and system for forming non-vacuum copper indium gallium sulphide selenium absorption layer and cadmium sulfide buffer layer
JP2013529378A (ja) * 2010-04-19 2013-07-18 韓国生産技術研究院 太陽電池の製造方法
US9087954B2 (en) * 2011-03-10 2015-07-21 Saint-Gobain Glass France Method for producing the pentanary compound semiconductor CZTSSe, and thin-film solar cell
JP2012222157A (ja) * 2011-04-08 2012-11-12 Hitachi Kokusai Electric Inc 基板処理装置、及び、太陽電池の製造方法
ES2527644B1 (es) 2012-02-29 2016-04-27 Alliance For Sustainable Energy, Llc SISTEMAS Y MÉTODOS PARA FORMAR CÉLULAS SOLARES CON PELÍCULAS DE CuInSe2 y Cu(In,Ga)Se2
CN103361603A (zh) * 2012-03-29 2013-10-23 常熟卓辉光电科技有限公司 一种半导体薄膜材料的真空蒸发设备及oled导电层的制备方法
DE102012205378A1 (de) * 2012-04-02 2013-10-02 Robert Bosch Gmbh Verfahren zur Herstellung von Dünnschichtsolarmodulen sowie nach diesem Verfahren erhältliche Dünnschichtsolarmodule
KR101461315B1 (ko) * 2012-06-19 2014-11-12 가부시키가이샤 스크린 홀딩스 열처리 장치 및 열처리 방법
JP5933837B2 (ja) 2012-07-09 2016-06-15 サン−ゴバン グラス フランスＳａｉｎｔ−Ｇｏｂａｉｎ Ｇｌａｓｓ Ｆｒａｎｃｅ 基板を処理するためのシステムと方法
KR101373314B1 (ko) 2012-12-31 2014-03-12 (주)피앤테크 태양전지 웨이퍼용 도핑 프로세스튜브의 배기 응축 장치
DE102014116696B4 (de) * 2014-11-14 2016-10-20 Von Ardenne Gmbh Vakuumkammer und Verfahren zum Betreiben einer Vakuumprozessieranlage

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4723507A (en) * 1986-01-16 1988-02-09 Energy Conversion Devices, Inc. Isolation passageway including annular region
EP0782176A2 (fr) * 1995-12-22 1997-07-02 Canon Kabushiki Kaisha Procédé pour la formation de films déposés et dispositif pour la formation de films déposés
US20040063320A1 (en) * 2002-09-30 2004-04-01 Hollars Dennis R. Manufacturing apparatus and method for large-scale production of thin-film solar cells
US20040161533A1 (en) * 1998-04-20 2004-08-19 Tadashi Sawayama Processing apparatus, exhaust processing process and plasma processing process

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02148715A (ja) * 1988-11-29 1990-06-07 Canon Inc 半導体デバイスの連続形成装置
JP2819056B2 (ja) * 1990-07-24 1998-10-30 キヤノン株式会社 堆積膜形成方法及び装置
EP0662247B1 (fr) * 1992-09-22 1999-03-10 Siemens Aktiengesellschaft Procede rapide de realisation d'un semi-conducteur en chalcopyrite sur un substrat
JP3402637B2 (ja) * 1992-12-28 2003-05-06 キヤノン株式会社 太陽電池の製造方法、その製造装置及び長尺シート基板の製造方法
JP3571785B2 (ja) * 1993-12-28 2004-09-29 キヤノン株式会社 堆積膜形成方法及び堆積膜形成装置
JPH11135811A (ja) * 1997-10-28 1999-05-21 Yazaki Corp Ｃｉｓ系太陽電池モジュール及びその製造方法
EP1428243A4 (fr) * 2001-04-16 2008-05-07 Bulent M Basol Procede de formation d'une couche mince de compose semiconducteur destinee a la fabrication d'un dispositif electronique, et couche mince produite par ledit procede

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4723507A (en) * 1986-01-16 1988-02-09 Energy Conversion Devices, Inc. Isolation passageway including annular region
EP0782176A2 (fr) * 1995-12-22 1997-07-02 Canon Kabushiki Kaisha Procédé pour la formation de films déposés et dispositif pour la formation de films déposés
US20040161533A1 (en) * 1998-04-20 2004-08-19 Tadashi Sawayama Processing apparatus, exhaust processing process and plasma processing process
US20040063320A1 (en) * 2002-09-30 2004-04-01 Hollars Dennis R. Manufacturing apparatus and method for large-scale production of thin-film solar cells

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2008085604A2 *

Also Published As

Publication number Publication date
KR20090110293A (ko) 2009-10-21
JP2010509779A (ja) 2010-03-25
CN101578707B (zh) 2012-08-22
WO2008085604B1 (fr) 2008-12-24
CN101578707A (zh) 2009-11-11
TW200832726A (en) 2008-08-01
WO2008085604A3 (fr) 2008-10-16
WO2008085604A2 (fr) 2008-07-17
EP2102898A4 (fr) 2011-06-29

Similar Documents

Publication Publication Date Title
US9103033B2 (en) Reel-to-reel reaction of precursor film to form solar cell absorber
EP2102898A2 (fr) Réaction inter-bobine d'un film précurseur pour formation d'un absorbeur solaire
US20080175993A1 (en) Reel-to-reel reaction of a precursor film to form solar cell absorber
EP1938360B1 (fr) Procede et appareil permettant de convertir des couches de precurseurs en absorbeurs photovoltaiques
US8323408B2 (en) Methods and apparatus to provide group VIA materials to reactors for group IBIIIAVIA film formation
US20090183675A1 (en) Reactor to form solar cell absorbers
US8163090B2 (en) Methods structures and apparatus to provide group VIA and IA materials for solar cell absorber formation
US7858151B2 (en) Formation of CIGS absorber layer materials using atomic layer deposition and high throughput surface treatment
US20100226629A1 (en) Roll-to-roll processing and tools for thin film solar cell manufacturing
US9915475B2 (en) Assembled reactor for fabrications of thin film solar cell absorbers through roll-to-roll processes
US20120258567A1 (en) Reaction methods to form group ibiiiavia thin film solar cell absorbers
US8153469B2 (en) Reaction methods to form group IBIIIAVIA thin film solar cell absorbers
US20100139557A1 (en) Reactor to form solar cell absorbers in roll-to-roll fashion
WO2010078088A1 (fr) Réacteur pour former des absorbeurs de cellules solaires selon un mode de rouleau à rouleau
WO2005081789A2 (fr) Formation de materiaux à couches absorbantes de cigs faisant intervenir un depot de couche atomique et un traitement de surface a haut debit

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090609

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20110526

17Q First examination report despatched

Effective date: 20120605

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20140603