EP1966831A2 - Procede et installation de transformation de couches de precurseur metallique en couches de chalcopyrite de cellules solaires cigss - Google Patents

Procede et installation de transformation de couches de precurseur metallique en couches de chalcopyrite de cellules solaires cigss

Info

Publication number
EP1966831A2
EP1966831A2 EP06841601A EP06841601A EP1966831A2 EP 1966831 A2 EP1966831 A2 EP 1966831A2 EP 06841601 A EP06841601 A EP 06841601A EP 06841601 A EP06841601 A EP 06841601A EP 1966831 A2 EP1966831 A2 EP 1966831A2
Authority
EP
European Patent Office
Prior art keywords
reaction
reaction box
reaction chamber
box
sulfur
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Withdrawn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
EP06841601A
Other languages
German (de)
English (en)
Inventor
Christian Von Klopmann
Nilolaus Meyer
Ilka Luck
Dieter Schmid
Alexander Meeder
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.)
Sulfurcell Solartechnik GmbH
Original Assignee
Sulfurcell Solartechnik GmbH
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 Sulfurcell Solartechnik GmbH filed Critical Sulfurcell Solartechnik GmbH
Publication of EP1966831A2 publication Critical patent/EP1966831A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • 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
    • 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
    • H10F10/167—Photovoltaic cells having only PN heterojunction potential barriers comprising Group I-III-VI materials, e.g. CdS/CuInSe2 [CIS] heterojunction photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
    • 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
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0431—Apparatus for thermal treatment
    • H10P72/0434—Apparatus for thermal treatment mainly by convection
    • 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
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0431—Apparatus for thermal treatment
    • H10P72/0436—Apparatus for thermal treatment mainly by radiation
    • 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
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/06—Apparatus for monitoring, sorting, marking, testing or measuring
    • H10P72/0604—Process monitoring, e.g. flow or thickness monitoring
    • 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

Definitions

  • the invention relates to a method and a device for converting metallic precursor layers (referred to below as precursor) with sulfur and / or selenium to chalcopyrite layers of CIGSS solar cells in a reaction chamber of an RTP furnace.
  • precursor metallic precursor layers
  • the goal is the production of thin-film solar modules.
  • the precursors may preferably contain Cu and In / Ga or else Cu, Zn, Sn. You can also include other elements such as Ag, Sb, Sn, Zn or Fe.
  • the precursors may be thin layers (layer thicknesses of 0.1 to 5 ⁇ m) on support substrates, which may consist of glass, ceramic, metal or plastics.
  • the Tragersubstrate can already with barrier layers precoated to keep contaminants from the glass from the precursor.
  • barrier layers may be silicon interconnects, for example, silicon meitite.
  • the reaction of the metallic precursor layers takes place with an element of group VI, in the present process sulfur and / or selenium (referred to below as chalcogen).
  • the reaction (called in a further reaction) takes place at elevated temperatures while supplying energy in a so-called RTP oven (rapid thermal processing).
  • a chalcogen supply of precursor with gaseous chalcogen which is vaporized in separate sources from the liquid phase and introduced via suitable feeds into the reaction chamber, for example a selenium shower, is known, see for example Gabor et al., High-efficiency CuIn x Ga x Se 2 solar cells made from (x Ga x In) 2Se3 precursor films, Appl. Phys. Lett. 65 (2), 1994, 198-200.
  • the substrates coated with the precursor are introduced into a reaction space.
  • the reaction space can have any shape and can be made of metal, glass or graphite, which is uncoated or coated.
  • the reaction space may contain openings and valves
  • the substrates with the precursor can be introduced directly into the reaction space, in which they are placed on the ground or adjusted or mounted in suitable holders vertically or horizontally.
  • a device and a method for tempering precursor layers in an RTP furnace are known, according to which the coated substrate is introduced into a container which has a base and a lid made of glass ceramic.
  • the purpose of housing in the container is the targeted supply of energy to the substrate from one side and the precursor from the other side, wherein the transparent covers of the container form filters for a preferred radiation range.
  • the solar modules produced in this way have a still too low efficiency compared to the theoretically achievable or achieved on a laboratory scale values. For achievable values, see Siemer et al., Efficient CuInS2 solar cells from a rapid thermal process (RTP), Solar Energy Materials & Solar Cells 67 (2001), 159-166 and Probst et al. , CIGSSE Modules Pilot Processing: from Fundamental Investigations to Advanced Performance, WCPEC-3, Osaka, May 12-16, 2003.
  • the invention has for its object to provide a method and apparatus of the type mentioned, with which the efficiency of the solar cell produced therewith is further increased.
  • a substrate coated with the precursor and a sufficient amount of sulfur and / or selenium for the reaction are introduced into a sealingly closable reaction box provided with at least one outlet valve controllable outside the reaction chamber, which in turn is introduced into the reaction chamber of the RTP furnace.
  • the reaction space is evacuated, wherein the reaction box is evacuated, and heated the reaction box with the substrate in the reaction chamber to a designated temperature and held for a certain process time at this temperature. Also conceivable is a separate evacuation of the reaction box.
  • the pressure in the reaction box is measured and controlled via the at least one outlet valve.
  • a suitable device for carrying out the method consists of a coated with a precursor Substrate and one for the reaction sufficient amount of sulfur and / or selenium feedable, sealingly sealable and provided with at least one controllable from outside the reaction chamber outlet valve whose internal pressure can be measured with a sensor.
  • the reaction box can be made of metal, glass, ceramic, or graphite. It may be uncoated or coated and transparent or opaque.
  • the reaction box is tight, meaning that during the process no gases escape into the reaction chamber by itself and no gases enter the reaction box from the reaction chamber either.
  • the reaction box contains valves to adjust the pressure before and during the process. With the targeted pressure control, in particular the control of the sulfur pressure, the formation of destructive foreign phases is avoided in the process.
  • the reaction box can be used directly for process pressure measurement by measuring the deflection of the reaction box lid.
  • reaction box is evacuated before the start of the process, that is to say before heating. It is possible to set a defined background pressure with an inert gas in the box before the reaction starts.
  • the supply of the chalcogen (preferably sulfur and / or selenium) can • directly into the reaction space; For this purpose, a sufficient amount of chalcogen in the reaction space available posed,
  • the chalcogen can be placed on the bottom of the reaction space or reaction box.
  • the chalcogen can also be placed in boats, the boats can be open or partially closed.
  • the boats can be made of graphite, glass, ceramics or metal; they can be uncoated or coated.
  • the amount of chalcogen is adjusted to the consumption during the reaction. It is fed only as much chalcogen, as is consumed by the layer during the reaction, so that an economical consumption is ensured; Otherwise, excess chalcogen would otherwise precipitate on the walls of the reaction chamber or reaction box and / or be pumped out in the vacuum pumps of the reaction chamber.
  • the energy input for the reaction can be effected via radiators which are arranged above and / or below the reaction box in the reaction chamber.
  • the energy can also be supplied via flat heating elements, which are mounted in the reaction chamber, or can be done via electrical resistance heaters, which are mounted in the reaction chamber.
  • the energy is supplied in a controlled manner, so that the energy is provided according to the ongoing reactions.
  • the reaction volume that is, the volume that must be heated and which comes in contact with the chalcogen
  • the reaction pressure can be set by using a reaction box with pressure control defined be controlled and the reaction with it.
  • different chemical phases are passed through which can be selectively controlled and adjusted via the pressure and the temperature in the reaction box. This can avoid unwanted by-products of the reaction and preferably set the desired reactions.
  • the pressure in the reaction box can be determined very precisely via the deformation of the lid.
  • the pressure in the reaction chamber can be adjusted to the pressure in the reaction box.
  • any desired pressure in the reaction box can be adjusted during the reaction and specifically changed.
  • the invention will be explained below with reference to an exemplary embodiment even closer.
  • the accompanying drawing shows a reaction box used for the process, introduced into a reaction chamber of a RTP furnace, in a cross section.
  • the reaction box 1 is a flat graphite box with a transparent cover 2 made of glass ceramic.
  • the reaction box 1 is sealed against the lid 2 with a high temperature resistant seal.
  • a valve block containing the pressure relief valves 3 and a controllable valve 4, via which the desired pressure can be set software controlled during the process.
  • the lid 2 is removed.
  • the reaction box 1 is equipped with a carrier substrate 5 made of glass, from which a solar module is produced after the successful process.
  • the carrier substrate 5 is coated, for example, with molybdenum (0.1 to 2 ⁇ m layer thickness), copper (0.1 to 2 ⁇ m layer thickness) and indium (0.1 to 2 ⁇ m layer thickness).
  • molybdenum 0.1 to 2 ⁇ m layer thickness
  • copper 0.1 to 2 ⁇ m layer thickness
  • indium 0.1 to 2 ⁇ m layer thickness
  • the reaction box 1 is closed with the transparent cover 2 and then introduced into a reaction chamber 6 of an RTP furnace.
  • the reaction box 1 is evacuated by means of a vacuum pump 7, then the controllable valve 4 is closed and the reaction box 1 is heated. The heating takes place in the reaction chamber of the RTP furnace
  • Quartz radiators 8, which are mounted above and below the reaction box 1 in the Christskhunt 6. The reaction box 1 is moved from room temperature to process temperature during the process
  • the heating process takes between 1 and 60 minutes.
  • the current pressure in the reaction box 1 is measured permanently.
  • the bending of the elastic cover 2 is optically detected by a sensor 9.
  • the pressure in the reaction chamber 6 can be measured via a pressure sensor 10.
  • special pressure profiles are set and maintained over the entire course.
  • reaction box 1 defined pressures (between 0.1 and 100 hPa) are set before the beginning of the process via the supply of inert gas via a valve 11.
  • the precursor layers (copper and indium on molybdenum) undergo defined phases. About the intermediate phases Culn2; Cunlng and the precursor reacts with sulfur to form CuInS 2 and CU 2 S / CUS.
  • the temperature profile and above all the pressure profile are set in this way. that only the desired products (CuInS2 and CU2S / CUS) are formed from the starting materials and that no connections between In and S can occur.
  • the formation of In-rich phases in the Cu-InS system (eg CuIn 6 S 8 ) is prevented.
  • both the carrier substrate 5 and the precursor layers are heated, as well as the added elemental sulfur. This goes over the liquid into the gaseous phase.
  • the boiling point of sulfur can be set exactly over the previously set inert gas pressure.
  • the maximum pressure build-up in the reaction box is determined by the amount of added sulfur and the set temperature of the reaction box 1.
  • the quartz emitters 7 are turned off and the reaction box 1 is cooled to room temperature.
  • the excess sulfur is pumped out after opening the controllable valve 4 in the reaction chamber 6.
  • the amount of sulfur required depends exclusively on the thickness of the precursor and can be determined to less than 30% excess, practically even considerably less. This ensures a careful handling of resources (here the amount of process substances used).

Landscapes

  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne un procédé et une installation de transformation de couches de précurseur métallique contenant du soufre et/ou du sélénium en couches de chalcopyrite de cellules solaires CIGSS dans une chambre réactionnelle d'un four de recuit rapide RTP. L'invention vise en particulier à réaliser des modules solaires à couches fines. Selon l'invention, un substrat enduit du précurseur et une quantité de soufre et/ou de sélénium suffisante pour la réaction sont mis dans une enceinte réactionnelle pouvant être fermée de manière étanche et dotée d'au moins une soupape de sortie réglable de l'extérieur de la chambre réactionnelle, l'enceinte réactionnelle est placée dans l'espace réactionnel du four de recuit rapide RTP, le vide est fait dans l'espace réactionnel, l'enceinte réactionnelle contenant le substrat dans l'espace réactionnel est chauffée à une température définie et maintenue à cette température pendant une durée déterminée de traitement, durant laquelle la pression dans l'enceinte réactionnelle est mesurée et régulée au moyen de la soupape de sortie.
EP06841601A 2005-12-28 2006-12-22 Procede et installation de transformation de couches de precurseur metallique en couches de chalcopyrite de cellules solaires cigss Withdrawn EP1966831A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005062977A DE102005062977B3 (de) 2005-12-28 2005-12-28 Verfahren und Vorrichtung zur Umsetzung metallischer Vorläuferschichten zu Chalkopyritschichten von CIGSS-solarzellen
PCT/EP2006/070178 WO2007077171A2 (fr) 2005-12-28 2006-12-22 Procede et installation de transformation de couches de precurseur metallique en couches de chalcopyrite de cellules solaires cigss

Publications (1)

Publication Number Publication Date
EP1966831A2 true EP1966831A2 (fr) 2008-09-10

Family

ID=37857191

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06841601A Withdrawn EP1966831A2 (fr) 2005-12-28 2006-12-22 Procede et installation de transformation de couches de precurseur metallique en couches de chalcopyrite de cellules solaires cigss

Country Status (5)

Country Link
US (1) US20080305247A1 (fr)
EP (1) EP1966831A2 (fr)
CN (1) CN101346822B (fr)
DE (1) DE102005062977B3 (fr)
WO (1) WO2007077171A2 (fr)

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US20080305247A1 (en) 2008-12-11
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WO2007077171A2 (fr) 2007-07-12
WO2007077171A3 (fr) 2007-08-23

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