CN103388139A - Method for preparing copper-zinc-tin-sulfur optoelectronic film - Google Patents

Method for preparing copper-zinc-tin-sulfur optoelectronic film Download PDF

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CN103388139A
CN103388139A CN2013103008956A CN201310300895A CN103388139A CN 103388139 A CN103388139 A CN 103388139A CN 2013103008956 A CN2013103008956 A CN 2013103008956A CN 201310300895 A CN201310300895 A CN 201310300895A CN 103388139 A CN103388139 A CN 103388139A
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film
tin
zinc
substrate
copper
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CN2013103008956A
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CN103388139B (en
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刘科高
石璐丹
李静
石磊
许斌
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Shandong Jianzhu University
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Shandong Jianzhu University
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Abstract

The invention relates to a preparation method for a copper-zinc-tin-sulfur optoelectronic film, and belongs to the field of preparation technology of optoelectronic films. The copper-zinc-tin-sulfur optoelectronic film is obtained by the following steps of firstly washing a substrate; then dissolving CuCl2.2H2O, ZnCl2.2H2O, SnCl2.2H2O and CH4N2S in a solvent; spin-coating the solution on the substrate to obtain a precursor film; drying the precursor film; putting the precursor film in an airtight container containing hydrazine hydrate, the precursor film sample being not contacted with hydrazine hydrate; and finally drying. The method is in no need of high temperature and high vacuum conditions, has low requirements for equipment, is low in production cost and high in production efficiency, and can be operated easily. The obtained copper-zinc-tin-sulfur optoelectronic film has good continuity and uniformity. The novel process can easily control composition and structure of a target product and provides a preparation method which is low in cost and can achieve industrialization, for high-performance copper-zinc-tin-sulfur optoelectronic film.

Description

A kind of method for preparing the copper-zinc-tin-sulfur optoelectronic film
Technical field
The invention belongs to the optoelectronic film preparing technical field, relate in particular to a kind of preparation method who prepares the copper-zinc-tin-sulfur optoelectronic film.
Background technology
Along with society and expanding economy; China's total energy consumption increases severely; the pollution that energy scarcity and the consumption energy bring has become the outstanding problem in domestic social development, and therefore developing clean energy to protection of the environment, sustainable economic development and construct harmonious society has important meaning.In order to utilize more fully the renewable resources of this cleaning of sun power, safety and environmental protection, the research and development of photoelectric material in recent years comes into one's own day by day.
In film photovoltaic material, quaternary sulfide Cu 2ZnSnS 4(CZTS), have the custerite structure, and the rich content of each element in the earth's crust, preparation cost is low, and CZTS is the direct band gap material, and its photoabsorption coefficient is higher than 10 4cm -1, in battery, material requested thickness is less, and energy gap is 1.05~1.50eV approximately, and needed best energy gap 1.50eV mates with solar cell, so it is the ideal material of solar cell.The CZTS hull cell that dopes economic environmental protection according to battery source abundance, unit cells materials'use amount, battery conversion efficiency etc. can become following main flow battery, in photovoltaic field from now on, is rapidly developed.
At present, copper-zinc-tin-sulfur polycrystal manufacture technology is a lot, comprise vacuum method and antivacuum method, vacuum method comprises method of evaporation, sputtering method, pulsed laser deposition etc., and antivacuum method comprises galvanic deposit, spray pyrolysis method, Sol-gel method, chemical deposition, silk screen print method etc.This experiment adopts the chemical co-reducing process of spin coating one to prepare the copper-zinc-tin-sulfur optoelectronic film.
Method is the same as previously described, and other method also has different defects.Related to the present invention also has as Publication about Document:
[1]Abermann?S.Non-vacuum?processed?next?generation?thin?film?photovoltaics:Towards?marketable?efficiency?and?production?of?CZTS?based?solar?cells.Solar?Energy,2013,94:37-70.
Preparation photovoltaic generation film of future generation under antivacuum condition mainly described in article, mainly told about the effect of producing the market of CZTS solar cell, summarized the premium properties of CZTS solar cell.
[2]Moholkar?A?V,?Shinde?S?S,Babar?A?R,et?al.Development?of?CZTS?thin?films?solar?cells?by?pulsed?laser?deposition:Influence?ofpulse?repetition?rate.Solar?Energy,2011,85(7):1354-1363.
Mainly reported the film with pulsed laser deposition solar cell CZTS, and the change of having studied the repetition rate of pulse changes the crystal type of film and the impact of photoelectric properties, in repetition rate be the structure type of CZTS film under the condition of 10Hz by unformed to crystalline transformation efficiency raising 2%.
[3]A.I?Inamdar,Seulgi?Lee,Ki-Young?Jeon,Chong?Ha?Lee,S.M.Pawar,Optimized?fabrication?of?sputter?deposited?Cu 2ZnSnS 4(CZTS)thin?films,Solar?Energy?91(2013)196-203.
Article reported with the method for rf magnetron sputtering and prepared the CZTS solar energy film, and studied the impact of annealing temperature on the film the Nomenclature Composition and Structure of Complexes, mainly studied the impact of annealing temperature on Cu/ (Zn+Sn) and S/ (Cu+Zn+Sn).
[4]K.V.?Gurav,J.H.Yun,S.M.Pawar,S.W.Shin,M.P.?Suryawanshi,Y.?K.Kim,G.?L.?Agawane,P.?S.Patil,J.H.Kim,Pulsed?electrodeposited?CZTS?thin?Films:effect?ofduty?cycle,S0167-577X(13)00873-2.
This paper has mainly described by impulse electrodeposition technology and has prepared the CZTS film, and mainly research is to change the impact of the time length of pulsed voltage on the stoichiometric number of film composition.
[5]Shinde?N?M,Dubal?D?P,?Dhawale?D?S,et?al.Room?temperature?novel?chemical?synthesis?of?Cu 2ZnSnS 4(CZTS)absorbing?layer?for?photovoltaic?application[J].Materials?Research?Bulletin,2012,47(2):302-307.
Be continuous ionic layer absorption reaction method (SILAR) preparation CZTS absorption layer film with novel chemical synthesis process in paper, and described the film for preparing have higher specific absorption (10 under annealing temperature 673K 4cm -1), the p-type battery, energy gap is 1.55eV.
Summary of the invention
The present invention is in order to solve the deficiencies in the prior art, and invented a kind of diversely with preparation method prior art, and the copper-zinc-tin-sulfur solar cell is with the preparation technology of thin-film material.
The present invention adopts the chemical co-reducing process of spin coating one to prepare the copper-zinc-tin-sulfur film material, and adopting soda-lime glass sheet or silicon chip is substrate, with CuCl 22H 2O, ZnCl 22H 2O, SnCl 22H 2O and CH 4N 2S is raw material, and the mixture of one or more in deionized water, ethanol, ethylene glycol, hydrochloric acid is solvent, and (element metering ratio is as Cu first take spin-coating method, to prepare certain thickness copper-zinc-tin-sulfur 2ZnSeS 4) precursor thin-film, take hydrazine hydrate as reductive agent, heating at a lower temperature in encloses container, make the concurrent intercrescence of precursor thin-film reduction become reaction to obtain target product.
Concrete preparation method of the present invention comprises the step of following order:
A. carrying out the cleaning of substrate, is that 2mm * 2mm glass substrate or silicon substrate are put into trichloromethane by volume with size: the solution of ethanol=5: 1, ultrasonic cleaning 30min; Again substrate is put into acetone: the solution of distilled water=5: 1, ultrasonic cleaning 30min; Substrate is used again ultra-sonic oscillation 30min in distilled water; Substrate obtained above is emitted in glass dish to send in baking oven dries for masking.
B. with CuCl 22H 2O, SnCl 22H 2O, ZnCl 22H 2O and CH 4N 2S puts into solvent, and the material in solution is evenly mixed.Specifically, can be with 2.0~4.0 parts of CuCl 22H 2O, 1.0~2.0 parts of ZnCl 22H 2O, 1.3~2.6 parts of SnCl 22H 2O and 1.77~3.53 parts of CH 4N 2S puts into the solvent of 30~120 parts, and the material in solution is evenly mixed, and wherein solvent is one or more the mixture in deionized water, ethanol, ethylene glycol, hydrochloric acid.
C. make the outside evenly substrate of the described solution of smearing step b, and oven dry, the precursor thin-film sample obtained.Above-mentioned solution can be dripped on the substrate that is placed on sol evenning machine, restart sol evenning machine with 200~3500 rev/mins of rotation certain hours, make on dripping solution coat evenly after, and after substrate is dried, dry again after again repeating to drip upper aforementioned solution and spin coating, so repeat 2~15 times, so obtained certain thickness precursor thin-film sample on substrate.
D. step c gained precursor thin-film sample is placed on support, but puts into the encloses container of hydrazine hydrate, the precursor thin-film sample is not contacted with hydrazine hydrate.The hydrazine hydrate amount of putting into is 40.0~90.0 parts.The above-mentioned encloses container that the precursor thin-film sample is housed is put into baking oven, be heated between 160~220 ℃, soaking time 10~60 hours, then cool to room temperature takes out.
E., with the steps d products therefrom, after carrying out seasoning, namely obtain the copper-zinc-tin-sulfur optoelectronic film;
The present invention does not need the high temperature high vacuum condition, and low to the plant and instrument requirement, production cost is low, and production efficiency is high, easy handling.Gained copper-zinc-tin-sulfur optoelectronic film has continuity and homogeneity preferably, this novel process is easily controlled the composition and structure of target product, a kind of method that low cost is provided, can have realized large-scale industrial production for preparing high performance copper-zinc-tin-sulfur optoelectronic film.
Embodiment
Embodiment 1
A. the cleaning of substrate: (size is 2mm * 2mm) to clean as previously mentioned silicon substrate.
B. with 1.97 parts of CuCl of part 22H 2O, 1.0 parts of ZnCl 22H 2O, 1.31 parts of SnCl 22H 2O and 1.77 parts of CH 4N 2S puts into vial, adds 37.037 parts of ethanol, more than utilizing ultrasonic vibration 30min, the material in solution is evenly mixed.
C. above-mentioned solution is dripped on the silicon substrate that is placed on sol evenning machine, restart sol evenning machine, sol evenning machine rotated 5 seconds with 200 rev/mins, with 3000 rev/mins of rotations 15 seconds, make on dripping solution coat evenly after, after substrate is dried, dry again after again repeating to drip upper aforementioned solution and spin coating, so repeat 12 times, so obtained certain thickness precursor thin-film sample on substrate.
D. the precursor thin-film sample of above-mentioned technique gained is put into sealable container, and put into 58.03 parts of hydrazine hydrates, the precursor thin-film sample is placed on support it is not contacted with hydrazine hydrate, the encloses container that the precursor thin-film sample is housed is put into baking oven, be heated to 200 ℃, soaking time 20 hours, then cool to room temperature takes out.
E. with above-mentioned steps d product, after carrying out seasoning, namely obtain the copper-zinc-tin-sulfur optoelectronic film;
Embodiment 2
A. the cleaning of substrate: (size is 2mm * 2mm) to clean as previously mentioned glass substrate.
B. with 3.41 parts of CuCl 22H 2O, 1.72 parts of ZnCl 22H 2O, 2.26 parts of SnCl 22H 2O and 3.04 parts of CH 4N 2S puts into vial, adds 74.074 parts of ethylene glycol, more than utilizing ultrasonic vibration 30min, the material in solution is evenly mixed.
C. above-mentioned solution is dripped on the glass substrate that is placed on sol evenning machine, restart sol evenning machine, sol evenning machine rotated 9 seconds with 500 rev/mins, make on dripping solution coat evenly after, after substrate is dried, dry again after again repeating to drip upper aforementioned solution and spin coating, so repeat 4 times, so obtained certain thickness precursor thin-film sample on glass substrate.
D. the precursor thin-film sample of above-mentioned technique gained is put into sealable container, and put into 89.76 parts of hydrazine hydrates, the precursor thin-film sample is placed on support it is not contacted with hydrazine hydrate, the encloses container that the precursor thin-film sample is housed is put into baking oven, be heated to 180 ℃, soaking time 60 hours, then cool to room temperature takes out.
E., with the steps d products therefrom, after carrying out seasoning, namely obtain the copper-zinc-tin-sulfur optoelectronic film.

Claims (5)

1. method for preparing the copper-zinc-tin-sulfur optoelectronic film comprises the step of following order:
A. the cleaning of glass substrate or silicon substrate;
B. with 2.0~4.0 parts of CuCl 22H 2O, 1.0~2.0 parts of ZnCl 22H 2O, 1.3~2.6 parts of SnCl 22H 2O and 1.77~3.53 parts of CH 4N 2S puts into the solvent of 30~120 parts, and the material in solution is evenly mixed;
C. make the outside evenly substrate of the described solution of smearing step b, and oven dry, the precursor thin-film sample obtained;
D. step c gained precursor thin-film sample is placed on support, but put into the encloses container of hydrazine hydrate, the precursor thin-film sample is not contacted with hydrazine, the encloses container that the precursor film sample is housed is put into baking oven, be heated between 160~220 ℃, soaking time 10~60h hour, then cool to room temperature takes out;
E., with the steps d products therefrom, carry out seasoning, obtain the copper-zinc-tin-sulfur optoelectronic film.
2. a kind of method for preparing the copper-zinc-tin-sulfur optoelectronic film as claimed in claim 1, it is characterized in that the described cleaning of step a is to be 2mm * 2mm glass substrate or silicon substrate with size, put into the volume ratio trichloromethane: the solution of ethanol=5: 1, ultrasonic cleaning; Again substrate is put into acetone: the solution of distilled water=5: 1, ultrasonic cleaning; Again in distilled water with the substrate ultra-sonic oscillation; Substrate obtained above is emitted in glass dish to send in baking oven dries for masking.
3. a kind of method for preparing the copper-zinc-tin-sulfur optoelectronic film as claimed in claim 1, is characterized in that, the described solvent of step b is at least a in deionized water, ethanol, ethylene glycol, hydrochloric acid.
4. a kind of method for preparing the copper-zinc-tin-sulfur optoelectronic film as claimed in claim 1, it is characterized in that, the substrate of the described even coating of step c, by the sol evenning machine spin coating, sol evenning machine is with 200~3500 rev/mins of rotations, then after substrate being dried, again so repeat 2~15 times, obtained certain thickness precursor thin-film sample.
5. a kind of method for preparing the copper-zinc-tin-sulfur optoelectronic film as claimed in claim 1, is characterized in that, puts into 40.0~9.0 parts of hydrazine hydrates in the described encloses container of steps d.
CN201310300895.6A 2013-07-09 2013-07-09 A kind of method preparing copper zinc tin sulfide optoelectronic film Expired - Fee Related CN103388139B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109574096A (en) * 2018-10-31 2019-04-05 南京邮电大学 A kind of preparation method and application of metal sulfide

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CN102169910A (en) * 2011-01-14 2011-08-31 南开大学 Thin film solar cell based on sulfur compound nanocrystalline
CN102569443A (en) * 2012-01-04 2012-07-11 范东华 Band gap tunable copper zinc tin sulfur semiconductor film and preparation method thereof
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CN102169910A (en) * 2011-01-14 2011-08-31 南开大学 Thin film solar cell based on sulfur compound nanocrystalline
CN102569443A (en) * 2012-01-04 2012-07-11 范东华 Band gap tunable copper zinc tin sulfur semiconductor film and preparation method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109574096A (en) * 2018-10-31 2019-04-05 南京邮电大学 A kind of preparation method and application of metal sulfide

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