EP1576209A1 - Verfahren zur regeneration eines elektrolysebades zur herstellung einer i-iii-vi2 verbindung als dünnschicht - Google Patents

Verfahren zur regeneration eines elektrolysebades zur herstellung einer i-iii-vi2 verbindung als dünnschicht

Info

Publication number
EP1576209A1
EP1576209A1 EP03796179A EP03796179A EP1576209A1 EP 1576209 A1 EP1576209 A1 EP 1576209A1 EP 03796179 A EP03796179 A EP 03796179A EP 03796179 A EP03796179 A EP 03796179A EP 1576209 A1 EP1576209 A1 EP 1576209A1
Authority
EP
European Patent Office
Prior art keywords
bath
selenium
iii
active
electrolysis
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.)
Granted
Application number
EP03796179A
Other languages
English (en)
French (fr)
Other versions
EP1576209B1 (de
Inventor
Stéphane TAUNIER
Denis Guimard
Daniel Lincot
Jean-François GUILLEMOLES
Pierre-Philippe Grand
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.)
Electricite de France SA
Centre National de la Recherche Scientifique CNRS
Original Assignee
Electricite de France SA
Centre National de la Recherche Scientifique CNRS
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 Electricite de France SA, Centre National de la Recherche Scientifique CNRS filed Critical Electricite de France SA
Publication of EP1576209A1 publication Critical patent/EP1576209A1/de
Application granted granted Critical
Publication of EP1576209B1 publication Critical patent/EP1576209B1/de
Priority to CY20131100569T priority Critical patent/CY1114335T1/el
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes

Definitions

  • the present invention relates to the manufacture of semiconductors of type I-III-VI 2 in thin layers, in particular for the design of solar cells.
  • An object of the present invention is to provide a process for manufacturing thin layers of a compound 1-III-VI.y (where there is close to 2) by electrolysis, which ensures the stabilization and the reproducibility of the deposition conditions.
  • An underlying aim is to be able to carry out on large surfaces a large number of successive deposits of thin layers having the desired morphology and composition.
  • Another object of the present invention is to provide a process for manufacturing thin layers of the compound I-III-VI y , which ensures a satisfactory lifetime of the electrolysis bath, as well as an efficient regeneration of the raw materials consumed during electrolysis.
  • Another object of the present invention is to provide a process for manufacturing thin layers of the compound I-III-VI y , which ensures regeneration of the raw materials consumed during electrolysis, without however unbalancing the composition of the electrolysis bath. and then reduce its lifespan.
  • the method within the meaning of the invention further comprises a step c) of regeneration of selenium in active form in said bath, in order to increase a lifetime of said electrolysis bath.
  • a step c) of regeneration of selenium in active form in said bath in order to increase a lifetime of said electrolysis bath.
  • step c at least one new thin layer of I-III-VI y is formed .
  • step c) selenium is added to the bath to form an excess of active selenium in the bath.
  • step c) an oxidant of selenium is introduced into the bath, in order to regenerate selenium in active form.
  • the electrolysis bath when it ages during deposition, exhibits selenium colloids.
  • This selenium in the form of colloids has an oxidation state of 0 and, in the context of the present invention, is not capable of combining with elements I and III.
  • the bath comprises selenium in the form of colloids in step b)
  • the abovementioned oxidant is capable of regenerating selenium in the form of colloids, into selenium in active form.
  • the term “selenium in active form” is understood to mean selenium at the oxidation state IV, capable of being reduced to the electrode in ionic form Se 2 " and of combining naturally with the elements I and III to form the thin layers of I-III-VI y , and being distinguished from selenium of oxidation state 0, for example in the form of colloids in the bath solution, which does not combine with elements I and III.
  • said oxidant is hydrogen peroxide, preferably in concentration in the bath of an order of magnitude corresponding substantially to at least five times the initial concentration of selenium in the bath.
  • step c) is advantageously provided for regenerating the electrolysis bath by the introduction of oxides and / or of hydroxides of elements I and III.
  • FIG. 1 shows schematically a thin layer obtained by the implementation of the method according to the invention
  • FIG. 2 shows schematically an electrolysis bath for the implementation of the method according to the invention.
  • CO layers of copper and indium diselenide are obtained at ambient pressure and temperature by electrodeposition of a thin layer of precursors of suitable composition and morphology, on a glass substrate S covered with molybdenum MO.
  • precursor layer is understood to mean a thin layer of overall composition close to CuInSe 2 and directly obtained after deposition by electrolysis, without any subsequent treatment.
  • the electrodeposition is carried out from an acid bath B (FIG. 2), stirred by blades M, containing an indium salt, a copper salt and dissolved selenium oxide.
  • concentrations of these precursor elements are between 10 "4 and 10 " 2 M.
  • the pH of the solution is fixed between 1 and 4.
  • the difference in electrical potential applied to the molybdenum electrode is between -0.8 and -1.2 V compared to the reference electrode REF.
  • Layers of thickness between 1 and 4 microns are obtained, with current densities between 0.5 and 10 mA / cm 2 .
  • a typical deposit is made from a bath, the initial formulation of which is as follows:
  • the precursors are deposited by a cathodic reaction with an imposed potential, at ⁇ 1 V relative to the REF electrode.
  • the current density is -1 mA / cm 2 .
  • the bath is recharged with Cu, In and Se elements based on the number of coulombs indicated by a detection cell (not shown) which thus counts the number of ions having interacted in the bath solution.
  • This recharging keeps the concentration of the elements constant during successive electrodeposits.
  • the pH can also be readjusted by adding sodium hydroxide (such as NaOH, for a concentration such as 1M) but this measurement is not systematically necessary here, as will be seen below.
  • this separation disappears by regenerating the selenium bath, even before regenerating the Cu and In elements.
  • active selenium with degree of oxidation IV usually denoted Se (IV)
  • inactive selenium with degree of oxidation 0 which is generally observed in the form of colloids in the electrolysis bath. and usually noted Se (0).
  • the active selenium Se (IV) is the only one capable of being reduced to the Ca electrode in the ionic form Se 2 " and of combining, in this form, with the elements Cu and In to form the thin layers of CuInSe 2 .
  • an oxidant is used which allows the selenium to be re-oxidized in the form Se (0), in order to obtain selenium in the form Se (IV).
  • an oxidant is used which allows the selenium to be re-oxidized in the form Se (0), in order to obtain selenium in the form Se (IV).
  • use is preferably made of hydrogen peroxide H 2 0 2 , by putting a large excess of H 2 0 2 in the solution (concentration of the order of 10 "2 M, preferably close to 4.10 " 2 M).
  • the layers become adherent again for 4 to 5 successive deposits of thin layers, then peel off again.
  • the renewal of this operation also makes it possible to again obtain adherent layers.
  • the addition of hydrogen peroxide also makes it possible to obtain thin layers of relatively smoother morphology.
  • oxides or hydroxides of copper and / or indium are also added for regenerate the CuInSe 2 electrolysis bath into copper and / or indiu.
  • the layer of electrodeposited precursors contains the elements in composition close to the stoichiometry I-III-VI 2 .
  • the compositions and morphology are checked during electrolysis. These agents (excess of Se (IV) or H 2 0 2 ) can easily be used for any type of electrolysis bath allowing the electrodeposition of I-III-VI systems such as Cu-In-Ga-Al-Se- S.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Photovoltaic Devices (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Manufacture And Refinement Of Metals (AREA)
EP03796179.4A 2002-12-26 2003-12-05 Verfahren zur regeneration eines elektrolysebades zur herstellung einer i-iii-vi2 verbindung als dünnschicht Expired - Lifetime EP1576209B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CY20131100569T CY1114335T1 (el) 2002-12-26 2013-07-05 Μεθοδος αναγενησης ενος λουτρου ηλεκτρολυσης για την κατασκευη μιας ενωσης ι-ιιι-vi2 σε λεπτες στοιβαδες

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0216712A FR2849450B1 (fr) 2002-12-26 2002-12-26 Procede de regeneration d'un bain d'electrolyse pour la fabrication d'un compose i-iii-vi2 en couches minces
FR0216712 2002-12-26
PCT/FR2003/003608 WO2004067809A1 (fr) 2002-12-26 2003-12-05 Procede de regeneration d'un bain d'electrolyse pour la fabrication d'un compose i-iii-vi2 en couches minces

Publications (2)

Publication Number Publication Date
EP1576209A1 true EP1576209A1 (de) 2005-09-21
EP1576209B1 EP1576209B1 (de) 2013-05-29

Family

ID=32480206

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03796179.4A Expired - Lifetime EP1576209B1 (de) 2002-12-26 2003-12-05 Verfahren zur regeneration eines elektrolysebades zur herstellung einer i-iii-vi2 verbindung als dünnschicht

Country Status (11)

Country Link
US (1) US7273539B2 (de)
EP (1) EP1576209B1 (de)
JP (1) JP4418370B2 (de)
AU (1) AU2003298431B2 (de)
CA (1) CA2516166C (de)
CY (1) CY1114335T1 (de)
DK (1) DK1576209T3 (de)
ES (1) ES2420179T3 (de)
FR (1) FR2849450B1 (de)
PT (1) PT1576209E (de)
WO (1) WO2004067809A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100465351C (zh) * 2006-03-02 2009-03-04 桂林工学院 一种太阳能电池薄膜材料的电化学沉积制备工艺

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2886460B1 (fr) * 2005-05-25 2007-08-24 Electricite De France Sulfurisation et selenisation de couches de cigs electrodepose par recuit thermique
US8414961B1 (en) 2006-12-13 2013-04-09 Nanosolar, Inc. Solution deposited transparent conductors
FR2951022B1 (fr) * 2009-10-07 2012-07-27 Nexcis Fabrication de couches minces a proprietes photovoltaiques, a base d'un alliage de type i-iii-vi2, par electro-depots successifs et post-traitement thermique.
FR2957365B1 (fr) * 2010-03-11 2012-04-27 Electricite De France Procede de preparation d'une couche mince d'absorbeur pour cellules photovoltaiques
KR101129194B1 (ko) * 2010-07-20 2012-03-26 한국에너지기술연구원 고밀도를 갖는 태양전지용 ｃｉｓ계 화합물 박막의 제조방법 및 상기 ｃｉｓ계 화합물 박막을 이용한 박막 태양전지의 제조방법
US20140158021A1 (en) * 2012-12-11 2014-06-12 Wei Pan Electrochemical Synthesis of Selenium Nanoparticles

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4253919A (en) * 1980-01-21 1981-03-03 The International Nickel Company, Inc. Electrodeposition of cadmium-selenium semiconducting photoelectrodes from an acid citrate bath
US4687559A (en) * 1984-03-16 1987-08-18 Helsco Metals Inc. Treatment of residues for metal recovery
US5071568A (en) * 1990-10-31 1991-12-10 Union Oil Company Of California Selenium removal process
US5510040A (en) * 1994-11-21 1996-04-23 Nalco Chemical Company Removal of selenium from water by complexation with polymeric dithiocarbamates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004067809A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100465351C (zh) * 2006-03-02 2009-03-04 桂林工学院 一种太阳能电池薄膜材料的电化学沉积制备工艺

Also Published As

Publication number Publication date
JP4418370B2 (ja) 2010-02-17
JP2006512483A (ja) 2006-04-13
US20060084196A1 (en) 2006-04-20
US7273539B2 (en) 2007-09-25
EP1576209B1 (de) 2013-05-29
CA2516166C (fr) 2011-11-15
CY1114335T1 (el) 2016-08-31
DK1576209T3 (da) 2013-07-08
PT1576209E (pt) 2013-07-12
AU2003298431A8 (en) 2004-08-23
AU2003298431B2 (en) 2009-10-08
FR2849450A1 (fr) 2004-07-02
AU2003298431A1 (en) 2004-08-23
CA2516166A1 (fr) 2004-08-12
ES2420179T3 (es) 2013-08-22
FR2849450B1 (fr) 2005-03-11
WO2004067809A1 (fr) 2004-08-12

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