EP1576209B1 - 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 Download PDF

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Publication number
EP1576209B1
EP1576209B1 EP03796179.4A EP03796179A EP1576209B1 EP 1576209 B1 EP1576209 B1 EP 1576209B1 EP 03796179 A EP03796179 A EP 03796179A EP 1576209 B1 EP1576209 B1 EP 1576209B1
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EP
European Patent Office
Prior art keywords
selenium
bath
iii
concentration
active
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.)
Expired - Lifetime
Application number
EP03796179.4A
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English (en)
French (fr)
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EP1576209A1 (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
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Application filed by Electricite de France SA, Centre National de la Recherche Scientifique CNRS filed Critical Electricite de France SA
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Application granted granted Critical
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Priority to CY20131100569T priority Critical patent/CY1114335T1/el
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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 type I-III-VI 2 semiconductors in thin layers, in particular for the design of solar cells.
  • the compounds I-III-VI 2 of the CuIn x Ga (1-x) Se y S (2-y) type (where x is substantially between 0 and 1 and y is substantially between 0 and 2) are considered to be very low. promising and could be the next generation of thin-film photovoltaic cells. These compounds have a direct bandwidth of between 1.05 and 1.6 eV which allows a strong absorption of solar radiation in the visible.
  • An object of the present invention is to provide a method of manufacturing thin layers of a compound I-III-VI y (where y is close to 2) by electrolysis, which ensures the stabilization and reproducibility of the deposition conditions.
  • An underlying purpose is to be able to perform over large areas 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 the manufacture of thin layers of the compound I-III-VI y , which ensures a satisfactory life 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 a regeneration of the raw materials consumed during the electrolysis, without unbalancing the composition of the electrolysis bath. and then reduce its life.
  • the process in the sense of the invention further comprises a step c) regeneration of selenium in active form in said bath, to increase a lifetime of said electrolysis bath.
  • the regeneration of the active selenium bath is first carried out before regenerating it into element I (such as copper) and / or element III (such as indium or gallium).
  • element I such as copper
  • element III such as indium or gallium
  • 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) a selenium oxidant is introduced into the bath to regenerate selenium in active form.
  • the electrolysis bath as it ages during deposition, exhibits selenium colloids.
  • This selenium in the form of colloids has a degree of oxidation 0 and, in the context of the present invention, is not likely to combine with the elements I and III.
  • the aforementioned oxidant is capable of regenerating the selenium in the form of colloids, into selenium in the active form.
  • selenium in active form is understood to mean selenium at the oxidation state IV, which can be reduced to the ionic electrode Se 2- and to naturally combine with the elements I and III. to form the thin films of I-III-VI y , and differing from the 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 oxygenated water, 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 of regeneration of the electrolysis bath by introduction of oxides and / or of hydroxides of elements I and III.
  • precursor layer is intended to mean a thin layer of overall composition close to CuInSe 2 and directly obtained after electrolysis deposition, without any subsequent treatment.
  • Electrodeposition is carried out from an acid bath B ( figure 2 ), stirred by M blades, 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 set between 1 and 4.
  • the electric potential difference applied to the molybdenum electrode is between -0.8 and -1.2 V relative to the REF reference electrode.
  • Thickness layers between 1 and 4 microns are obtained, with current densities of between 0.5 and 10 mA / cm 2 .
  • the precursors are deposited by an imposed voltage cathode reaction at -1 V relative to the REF electrode.
  • the current density is -1 mA / cm 2 .
  • the Cu, In and Se elements are recharged on the basis of the number of coulombs indicated by a detection cell (not shown), which thus counts the number of ions that have interacted in the bath solution.
  • This refill makes it possible to keep constant the concentration of the elements during the successive electrodeposits.
  • the pH can also be readjusted by addition of sodium hydroxide (such as NaOH, for a concentration such as 1M) but this measure is not systematically necessary here, as will be seen later.
  • this detachment disappears by regeneration of the selenium bath, even before regenerating the elements Cu and In.
  • Se (IV) active selenium of degree of oxidation IV
  • Se (0) active selenium of degree of oxidation 0
  • the active selenium Se (IV) is the only one capable of being reduced to the Ca electrode in the Se 2 ion form and of combining, in this form, with the elements Cu and In to form the CuInSe thin layers. 2 .
  • an excess regeneration of Se (IV) is carried out in the bath.
  • dissolved selenium oxide is added to the electrolysis bath to retard the aging of the bath.
  • 1.8 ⁇ 10 -4 M of [H 2 SeO 3 ] it is theoretically necessary to add 1.8 ⁇ 10 -4 M of [H 2 SeO 3 ] to the solution to recover an initial selenium concentration of 1.7 ⁇ 10 -3 M
  • a double addition of this quantity ie 3.6 ⁇ 10 -4 M and therefore an excess of 1.8 ⁇ 10 -4 M of [H 2 SeO 3 ]
  • These thin layers have the composition (Table I) and the desired morphology. Overregeneration of 3.6 ⁇ 10 -4 M thus makes it possible to obtain a cycle of 4 to 5 layers of satisfactory adhesion before observing new debonding problems. After each peeling cycle, the renewal of this operation makes it possible to obtain adherent layers.
  • an oxidizer is used to re-oxidize the selenium in the form Se (0), to obtain selenium in the form Se (IV).
  • hydrogen peroxide H 2 O 2 is preferably used, by bringing a large excess of H 2 O 2 into the solution (concentration of the order of 10 -2 M, preferably close to 4.10 -2 M). The layers become adherent for 4 to 5 successive deposits of thin layers, then come off again. The renewal of this operation also makes it possible to obtain adherent layers again.
  • the addition of hydrogen peroxide also makes it possible to obtain thin layers of relatively more smooth morphology.
  • oxides or hydroxides of copper and / or indium are added to regenerate the CuInSe 2 electrolysis bath in copper and / or indium.
  • the electrodeposited precursor layer contains the composition elements close to the stoichiometry I-III-VI 2 .
  • the compositions and the morphology are controlled during the electrolysis. These agents (excess of Se (IV) or H 2 O 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.
  • the elements I and III initially introduced into the solution in the form of CuSO 4 and In 2 (SO 4 ) 3 may advantageously be introduced in the form of oxides or hydroxides of copper and indium for limit the pollution of the bath.

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  • 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)

Claims (10)

  1. Verfahren zur Herstellung einer Verbindung I-III-VIy in Dünnschichten für Elektrochemie, worin y ähnlich 2 ist und VI ein Selen umfassendes Element darstellt, das die folgenden Schritte umfasst:
    a) Vorsehen eines Elektrolysebades, das aktives Selen der Oxidationsstufe IV umfasst sowie mindestens zwei Elektroden und
    b) Anlegen einer Potentialdifferenz zwischen den zwei Elektroden, um eine Bewegung des aktiven Selens in Richtung einer der Elektroden merklich zu fördern und so die Bildung zumindest einer Dünnschicht von I-III-VIy in Gang zu setzen,
    dadurch gekennzeichnet, dass es weiterhin einen Schritt
    c) er Regeneration des Selens in aktiver Form in dem Bad aufweist, um die Lebensdauer des Elektrolysebades zu erhöhen.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass man in Schritt c) in das Bad ein Oxidationsmittel für Selen (Se(0)) einträgt, um das Selen in seiner aktiven Form (Se(IV)) zu regenerieren.
  3. Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, dass das Bad Selen (Se(0)) in kolloidaler Form in Schritt b) umfasst, wobei das Oxidationsmittel zum Regenerieren des Selens (Se(0)) in kolloidaler Form zu Selen (Se(IV)) in aktiver Form eingerichtet ist.
  4. Verfahren gemäß einem der Ansprüche 2 und 3, dadurch gekennzeichnet, dass das Oxidationsmittel Wasserstoffperoxid (H2O2) darstellt.
  5. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, dass die Konzentration des in das Bad gegebenen Wasserstoffperoxids in der Größenordnung ist, die etwa wenigstens 5 mal der Anfangskonzentration des Selens in dem Bad entspricht.
  6. Verfahren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man in Schritt c) Selen in das Bad zum Bilden eines Überschusses an aktivem Selen in dem Bad hinzufügt.
  7. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, dass man für etwa ein Zehntel der Konzentration des in Schritt a) verbrauchten Selens zur Herstellung wenigstens einer Dünnschicht in Schritt b) in Schritt c) etwa das doppelte der verbrauchten Konzentration in das Bad gibt.
  8. Verfahren gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass man nach Schritt c) zumindest eine neue Dünnschicht I-III-VIy bildet.
  9. Verfahren gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass für die Herstellung der Dünnschicht CuInSey das Bad in Schritt a) für eine Konzentrationseinheit Kupfer in dem Bad ungefähr 1,7 Konzentrationseinheiten aktiven Selens umfasst.
  10. Verfahren gemäß einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass es einen weiteren Schritt nach Schritt c) zur Regeneration des Elektrolysebades durch Einführen von Oxiden und/oder Hydroxiden der Elemente I (CuO; Cu(OH)2) und III (In2O3; In(OH)3) aufweist.
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 EP1576209A1 (de) 2005-09-21
EP1576209B1 true EP1576209B1 (de) 2013-05-29

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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

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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)

Families Citing this family (7)

* 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
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
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

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* 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

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JP4418370B2 (ja) 2010-02-17
JP2006512483A (ja) 2006-04-13
US20060084196A1 (en) 2006-04-20
US7273539B2 (en) 2007-09-25
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
EP1576209A1 (de) 2005-09-21
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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