CN105514191A - Method for preparing copper indium selenium photoelectric film through acetate system two-step method - Google Patents

Method for preparing copper indium selenium photoelectric film through acetate system two-step method Download PDF

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Publication number
CN105514191A
CN105514191A CN201510943201.XA CN201510943201A CN105514191A CN 105514191 A CN105514191 A CN 105514191A CN 201510943201 A CN201510943201 A CN 201510943201A CN 105514191 A CN105514191 A CN 105514191A
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film
parts
selenium
hydrazine hydrate
copper
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李静
刘科高
许超
徐勇
石磊
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Shandong Jianzhu University
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Shandong Jianzhu University
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/0248Semiconductor devices sensitive to infra-red 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
    • H01L31/0256Semiconductor devices sensitive to infra-red 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
    • H01L31/0264Inorganic materials
    • H01L31/032Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322Inorganic 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/541CuInSe2 material PV cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a method for preparing a copper indium selenium photoelectric film through an acetate system two-step method, and belongs to the technical field of preparation of the photoelectric film used for a solar cell. The copper indium selenium photoelectric film is obtained through the following steps that a tin dioxide conductive glass substrate is cleaned; then C6H5Na3O7.2H2O, Cu(CH3COO)2.H2O, In(CH3COO)3 and SeO2 are put in distilled water; a precursor film is obtained on the conductive glass substrate through an electrodeposition method and then naturally dried; the precursor film is put in a tube furnace in which hydrazine hydrate is added and the precursor film sample is enabled not to be contacted with hydrazine hydrate, selenium powder is added in hydrazine hydrate, and the sealed tube furnace is heated so that the precursor film is selenized; and finally the sample is taken out to be dried so that the copper indium selenium photoelectric film is obtained. The high vacuum condition is not required, the requirement for instruments and equipment is low, production cost is low, production efficiency is high and operation is easy. The obtained copper indium selenium photoelectric film has great continuity and uniformity, and the principal phase is CuInSe2 phase so that low-cost and large-scale industrial production can be realized.

Description

A kind of acetate system two-step method prepares the method for copper-indium-selenium optoelectronic film
Technical field
The invention belongs to optoelectronic film preparing technical field used for solar batteries, particularly relate to a kind of method that acetate system two-step method prepares copper-indium-selenium optoelectronic film.
Background technology
Along with society and expanding economy; the pollution that energy scarcity and consuming energy bring has become the outstanding problem in domestic social development; coal, oil etc. are non-renewable resources, therefore develop clean reproducible energy to protection of the environment, ensure sustainable economic development and construct harmonious society have important meaning.Photovoltaic generation have safe and reliable, noiseless, pollution-free, restriction less, the advantage such as failure rate is low, easy maintenance, can utilize the regenerative resource of this clean, safety of solar energy and environmental protection, therefore the research and development of solar cell comes into one's own day by day in recent decades.
Copper, indium and selenium film solar cell can think the most promising hull cell at present, this is because its absorbed layer material C uInSe 2there is a series of advantage: (1) is at CuInSe 2adulterate in basis other element, as made Ga or Al part replace In atom, replacing Se be namely prepared into Cu (In by S part 1-xga x) Se 2, Cu (In 1-xga x) (Se 2-ys y), Cu (In 1-xal x) (Se 2-xs x), its crystal structure remains chalcopyrite.Change the atomic ratio of wherein Ga/ (Ga+In) etc., its energy gap can be made to change between 1.04 ~ 1.72eV, comprise bandgap range 1.4 ~ 1.6eV that high efficiency absorbs sunlight; (2) CuInSe 2, Cu (In 1-xga x) Se 2be the semi-conducting material of direct band gap, very large to solar spectrum response characteristic, its absorption coefficient is very high, and absorptivity is up to 1 ~ 6 × 10 5cm -1, thus required CuInSe in battery 2, Cu (In 1-xga x) Se 2film thickness is very little, about 2 μm, is most suitable for thin film; (3) stoichiometric proportion CuInSe 2photo-quantum efficiency high; (4) high photoelectric conversion efficiency; (5) in wider composition range, resistivity is all less; (6) capability of resistance to radiation is strong, does not have photo attenuation effect, thus long service life; (7) Cu (In 1-xga x) Se 2be that many clones system easily made by battery.In 4 junction batteries, from light direction by the descending order arrangement of energy gap, the theoretical conversion efficiencies limit at this moment can more than 50%.(8) lattice structure of P type CIGS material can be mated with common N-type window material (as CdS, ZnO) with electron affinity.
Be in the Cu (In of advanced level at present 1-xga x) Se 2photovoltaic absorbing material is all deposit preparation under vacuum, mainly contains vacuum vapour deposition and (copper and indium alloy film) sputtering-selenizing method.CuInSe 2the need of production of base absorbed layer adopts the vacuum technique of the costliness of deposit alloy layer.In vacuum technique, complicated operation difficulty is large, and gained film is also uneven.Also uneven containing film in the technique of selenizing in addition, be difficult to the stoichiometric proportion controlling each component, wherein H 2the toxic gas pollution environment of Se and Se and harm operating personnel.
The same with method noted earlier, other method also has different defects.Related to the present invention also has as Publication about Document:
[1]M.Valdés,M.Vázquez,A.Goossens,ElectrodepositionofCuInSe 2andIn 2Se 3onflatandnanoporousTiO 2substrates,ElectrochimicaActa54(2008)524–529.
Essentially describe and prepare In respectively with electrodeposition process 2se 3and CuInSe 2film, and its performance is characterized.
[2]AmolC.Badgujar,SanjayR.Dhage,ShrikantV.Joshi,Processparameterimpactonpropertiesofsputteredlarge-areaMobilayersforCIGSthinfilmsolarcellapplications,ThinSolidFilms589(2015)79–84.
Essentially describe with sputtering method preparation sputtering CIGS, and have studied the impact of splash-proofing sputtering process parameter on its performance.
[3]Yin-HsienSu,Tsung-WeiChang,Wen-HsiLee,Bae-HengTseng,CharacterizationofCuInSe 2thinfilmsgrownbyphoto-assistedelectrodeposition,ThinSolidFilms535(2013)343–347.
Main description light assist in electrodeposition legal system is for CuInSe 2and the research of photoelectric properties.
[4]ArminE.Zaghi,MarieBuffière,JaseokKoo,GuyBrammertz,MariaBatuk,ChristopheVerbist,JokeHadermann,WooKyoungKim,MarcMeuris,JefPoortmans,JefVleugels,EffectofseleniumcontentofCuInSe xalloynanopowderprecursorsonrecrystallizationofprintedCuInSe 2absorberlayersduringselenizationheattreatment,ThinSolidFilms582(2015)11–17.
Main description selenizing heat treatment recrystallization is to CuInSe xthe impact of middle Se content, and performance characterization and formation mechanism study have been carried out to it.
[5]ChaehwanJeong,JinHyeokKim,FabricationofCuInSe 2thinfilmsolarcellwithselenizationofdoublelayeredprecursorsfromCu 2SeandIn 2Se 3binary,ThinSolidFilms550(2014)660–664.
Essentially describe and utilize Cu 2se and In 2se 3two yuan of selenizing legal systems are for CuInSe 2.
[6]MengxiWang,SudipK.Batabyal,HuiMinLim,ZhenggangLi,YengMingLam,FormationofCuIn(S xSe 1-x) 2microcrystalsfromCuInSe 2nanoparticlesbytwostepsolvothermalmethod,JournalofAlloysandCompounds618(2015)522–526.
Essentially describe two step solvent-thermal methods and prepare CuInSe 2film, and have studied CuIn (S xse 1-x) 2and CuInSe 2stuctures and properties difference.
[7]Jeng-ShinMa,SubrataDas,Che-YuanYang,Fuh-ShanChen,Chung-HsinLu,Hydrothermally-assistedselenizationofCuInSe 2thinfilmsoncopperfoils,CeramicsInternational40(2014)7555–7560.
Essentially describe and adopt hydro-thermal to assist selenizing legal system for CuInSe 2phase has also carried out pattern and constituent analysis.
[8]JaseokKoo,Chae-WoongKim,ChaehwanJeong,WooKyoungKim,RapidsynthesisofCuInSe 2fromsputter-depositedbilayerIn 2Se 3/Cu 2Seprecursors,ThinSolidFilms582(2015)79–84.
Essentially describe and prepare Cu with sputtering method respectively 2se and In 2se 3, then CuInSe is prepared in two yuan of selenizings 2.
[9]A.Shanmugavel,K.Srinivasan,K.R.Murali,Pulseelectrodepositedcopperindiumsulphoselenidefilmsandtheirproperties,MaterialsScienceinSemiconductorProcessing16(2013)1665–1671.
Essentially describe by pulse electrodeposition legal system for CuIn (S, Se) 2, and its performance is characterized.
[10]F.Caballero-Briones,A.Palacios-Padrós,FaustoSanz,CuInSe 2filmspreparedbythreesteppulsedelectrodeposition.Depositionmechanisms,opticalandphotoelectrochemicalstudies,ElectrochimicaActa56(2011)9556–9567.
Main description three pace pulse electrodeposition processes prepare CuInSe 2, and its structure and morphology is characterized.
Summary of the invention
The present invention is in order to solve existing preparation CuInSe 2film Problems existing, has invented a kind of method that acetate system two-step method prepares copper-indium-selenium optoelectronic film.
After the present invention adopts electro-deposition, selenizing legal system is for copper, indium and selenium film, adopts tin dioxide conductive glass to be substrate, with Cu (CH 3cOO) 2h 2o, In (CH 3cOO) 3, SeO 2for raw material, with C 6h 5na 3o 72H 2o is complexing agent, take distilled water as solvent, by fixed molar ratio preparation electric depositing solution, transistor potentiostat is first adopted to prepare precursor thin-film under certain potentials and time, take hydrazine hydrate as reducing agent, in hydrazine hydrate, add selenium powder ensure selenium atmosphere, heat in airtight tube type stove, make precursor thin-film selenizing and obtain target product.
Concrete preparation method of the present invention comprises the step of following order:
A. carrying out the cleaning of tin dioxide conductive glass substrate, is that the glass substrate of 20mm × 20mm puts into volume ratio acetone by size: the solution of distilled water=5:1, Ultrasonic Cleaning 30min; Again substrate is put into ethanol, Ultrasonic Cleaning 30min; In distilled water, glass substrate is used sonic oscillation 30min again; Being emitted in glass dish by glass substrate obtained above sends in baking oven, dries for masking at 100 DEG C.
B. by C 6h 5na 3o 72H 2o, Cu (CH 3cOO) 2h 2o, In (CH 3cOO) 3, SeO 2put into distilled water, obtain uniform and stable electric depositing solution.Specifically, can by 1.0 ~ 2.0 parts of C 6h 5na 3o 72H 2o, 5.0 ~ 10.0 parts of Cu (CH 3cOO) 2h 2o, 7.5 ~ 15.0 parts of In (CH 3cOO) 3, 6.0 ~ 12.0 parts of SeO 2put into the distilled water of 2700.0 ~ 5400.0 parts, make the substance dissolves in solution.
C. electric depositing solution described in step b is poured in three electrode assemblies, take saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, tin dioxide conductive glass is Electrode, adopt transistor potentiostat normal temperature deposit film under sedimentation potential is-0.5V, sedimentation time is 30min, and natural drying obtains precursor thin-film sample.
D. be placed on support by step c gained precursor thin-film sample, in hydrazine hydrate, add selenium powder, precursor thin-film sample does not contact with hydrazine hydrate, and precursor thin-film and hydrazine hydrate are put into tube furnace.It is 40.0 ~ 50.0 parts that hydrazine hydrate is put into, and selenium powder is 4.0 ~ 8.0 parts.By between diamond heating to 250 ~ 400 DEG C, temperature retention time 3 ~ 9h, then cool to room temperature takes out.
E. by steps d gains, after making its normal temperature natural drying, copper-indium-selenium optoelectronic film is namely obtained.
The present invention does not need high vacuum condition, and require low to instrument and equipment, production cost is low, and production efficiency is high, is easy to operation.Gained copper-indium-selenium optoelectronic film has good continuity and uniformity, and principal phase is CuInSe 2phase, can realize low cost large-scale industrial production.
Embodiment
Embodiment 1
A. the cleaning of tin dioxide conductive glass substrate: carry out cleaning glass substrate as previously mentioned, substrate size is 20mm × 20mm.
B. by 1.0 parts of C 6h 5na 3o 72H 2o, 5.0 parts of Cu (CH 3cOO) 2h 2o, 7.5 parts of In (CH 3cOO) 3, 6.0 parts of SeO 2put into the distilled water of 2700.0 parts, make the substance dissolves in solution.
C. above-mentioned electric depositing solution is poured in three electrode assemblies, take saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, tin dioxide conductive glass is Electrode, adopt transistor potentiostat normal temperature deposit film under sedimentation potential is-0.5V, sedimentation time is 30min, and natural drying obtains precursor thin-film sample.
D. be placed on support by precursor thin-film sample, in hydrazine hydrate, add selenium powder, precursor thin-film sample does not contact with hydrazine hydrate, and precursor thin-film and hydrazine hydrate are put into tube furnace.It is 40.0 parts that hydrazine hydrate is put into, and selenium powder is 4.0 parts.By diamond heating to 350 DEG C, temperature retention time 6h, then cool to room temperature takes out.
E. by steps d gains, carry out normal temperature natural drying, obtain copper-indium-selenium optoelectronic film.

Claims (4)

1. acetate system two-step method prepares a method for copper-indium-selenium optoelectronic film, comprises the step of following order:
A. the cleaning of tin dioxide conductive glass substrate;
B. by 1.0 ~ 2.0 parts of C 6h 5na 3o 72H 2o, 5.0 ~ 10.0 parts of Cu (CH 3cOO) 2h 2o, 7.5 ~ 15.0 parts of In (CH 3cOO) 3, 6.0 ~ 12.0 parts of SeO 2put into the distilled water of 2700.0 ~ 5400.0 parts, make the substance dissolves in solution;
C. adopt electrodeposition process to be deposited on electro-conductive glass sheet by solution described in step b and obtain precursor thin-film, natural drying, obtain precursor thin-film sample;
D. be placed on support by step c gained precursor thin-film sample, in hydrazine hydrate, add selenium powder, precursor thin-film sample does not contact with hydrazine hydrate, and precursor thin-film and hydrazine hydrate are put into tube furnace; By between diamond heating to 250 ~ 400 DEG C, temperature retention time 3 ~ 9h, then cool to room temperature takes out;
E. by steps d gains, natural drying, obtains copper-indium-selenium optoelectronic film.
2. a kind of acetate system two-step method as claimed in claim 1 prepares the method for copper-indium-selenium optoelectronic film, it is characterized in that, clean described in step a, is be 20mm × 20mm by electro-conductive glass substrate size, put into volume ratio acetone: the solution of distilled water=5:1, Ultrasonic Cleaning 30min; Again substrate is put into ethanol, Ultrasonic Cleaning 30min; In distilled water, glass substrate is used sonic oscillation 30min again; Being emitted in glass dish by glass substrate obtained above sends in baking oven, dries for masking at 100 DEG C.
3. a kind of acetate system two-step method as claimed in claim 1 prepares the method for copper-indium-selenium optoelectronic film, it is characterized in that, described in step c, being added by solution in three electrode assemblies, take saturated calomel electrode as reference electrode, and platinum electrode is auxiliary electrode, tin dioxide conductive glass is Electrode, adopt transistor potentiostat normal temperature deposit film under sedimentation potential is-0.5V, sedimentation time is 30min, and natural drying obtains precursor thin-film sample.
4. a kind of acetate system two-step method as claimed in claim 1 prepares the method for copper-indium-selenium optoelectronic film, it is characterized in that, puts into 40.0 ~ 50.0 parts of hydrazine hydrates, 4.0 ~ 8.0 parts of selenium powders in tube furnace described in steps d.
CN201510943201.XA 2015-12-16 2015-12-16 Method for preparing copper indium selenium photoelectric film through acetate system two-step method Pending CN105514191A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108831965A (en) * 2018-07-01 2018-11-16 山东建筑大学 A method of copper and iron selenium conductive film is prepared with nitrate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108831965A (en) * 2018-07-01 2018-11-16 山东建筑大学 A method of copper and iron selenium conductive film is prepared with nitrate

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