CN103400893B - A kind of method preparing copper zinc tin sulfide optoelectronic film - Google Patents

Abstract

A preparation method for copper-zinc-tin-sulfur film, belong to optoelectronic film preparing technical field, the present invention obtains as follows, first cleans substrate, then by CuCl ₂2H ₂o, ZnCl ₂2H ₂o and SnCl ₂2H ₂o puts into solvent, adopts spin-coating method to obtain precursor thin-film on substrate, dries, what be placed with hydrazine hydrate and sublimed sulfur can in closed container, precursor thin-film sample is not contacted with sublimed sulfur with hydrazine hydrate, finally carries out drying, obtain copper zinc tin sulfide optoelectronic film.The present invention does not need high temperature 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 zinc tin sulfide optoelectronic film has good continuity and uniformity, the composition and structure of the easy control objectives product of this new technology, for prepare high performance copper zinc tin sulfide optoelectronic film provide a kind of cost low, industrialized preparation method can be realized.

Description

A kind of method preparing copper zinc tin sulfide optoelectronic film

Technical field

The invention belongs to optoelectronic film preparing technical field, particularly relate to a kind of preparation method preparing copper zinc tin sulfide optoelectronic film.

Background technology

Along with society and expanding economy; China's total energy consumption increases severely; the pollution that energy scarcity and consuming energy bring has become the outstanding problem in domestic social development, therefore develops clean energy resource to protection of the environment, sustainable economic development with construct harmonious society and have important meaning.In order to utilize the renewable resource of this clean, safety of solar energy and environmental protection more fully, 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), there is custerite structure, and the rich content of each element in the earth's crust, preparation cost is low, and CZTS is direct band gap material, and its absorption coefficient of light is higher than 10 ⁴cm ^-1, in battery, material requested thickness is less, and energy gap is 1.05 ~ 1.50eV about, mated with the best energy gap 1.50eV required for solar cell, so it is the ideal material of solar cell.Can become following main flow battery according to the battery CZTS hull cell that abundance, unit cells materials'use amount, battery conversion efficiency etc. dope economic environmental protection of originally originating, the photovoltaic art is from now on rapidly developed.

At present, copper-zinc-tin-sulfur polycrystal manufacture technology is a lot, comprise vacuum method and antivacuum method, vacuum method comprises evaporation, sputtering method, pulsed laser deposition etc., and antivacuum method comprises electro-deposition, spray pyrolysis method, Sol-gel method, chemical deposition, silk screen print method etc.This experiment adopts spin coating-chemical method to prepare copper zinc tin sulfide 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]AbermannS.Non-vacuumprocessednextgenerationthinfilmphotovoltaics：TowardsmarketableefficiencyandproductionofCZTSbasedsolarcells.SolarEnergy，2013，94：37-70.

Article essentially describes prepares photovoltaic generation film of future generation under antivacuum condition, mainly teaches the effect in the market producing CZTS solar cell, outlines the premium properties of CZTS solar cell.

[2]MoholkarAV，ShindeSS，BabarAR，etal.DevelopmentofCZTSthinfilmssolarcellsbypulsedlaserdeposition：Influenceofpulserepetitionrate.SolarEnergy，2011，85(7)：1354-1363.

Mainly report with pulsed laser deposition solar cell CZTS film, and the change that have studied the repetition rate of pulse changes the crystal type of film and the impact of photoelectric properties, is that the structure type of CZTS film under the condition of 10Hz improves 2% by unformed to crystalline transformation efficiency in repetition rate.

[3]A.IInamdar，SeulgiLee，Ki-YoungJeon，ChongHaLee，S.M.Pawar，OptimizedfabricationofsputterdepositedCu ₂ZnSnS ₄(CZTS)thinfilms，SolarEnergy91(2013)196-203.

Article reports prepares CZTS solar energy film by the method for rf magnetron sputtering, and have studied the impact of annealing temperature on film the Nomenclature Composition and Structure of Complexes, mainly have 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，PulsedelectrodepositedCZTSthinFilms：effectofdutycycle，S0167-577X(13)00873-2.

There is primarily described herein and prepare CZTS film by impulse electrodeposition technology, mainly research is that the duration of change pulse voltage is on the impact of the stoichiometric number that film forms.

[5]ShindeNM，DubalDP，DhawaleDS，etal.RoomtemperaturenovelchemicalsynthesisofCu ₂ZnSnS ₄(CZTS)absorbinglayerforphotovoltaicapplication[J].MaterialsResearchBulletin，2012，47(2)：302-307.

Prepare CZTS absorbed layer film with novel chemical synthesis process and SILAR method (SILAR) in paper, and describe the film prepared under annealing temperature 673K there is higher absorptivity (10 ⁴cm ^-1), p-type battery, energy gap is 1.55eV.

Summary of the invention

The present invention in order to solve the deficiencies in the prior art, and invents a kind of diverse with the preparation method of prior art, the preparation technology of copper-zinc-tin-sulfur solar cell thin-film material.

The present invention adopts spin coating-chemical co-reducing process to prepare copper-zinc-tin-sulfur film material, adopts soda-lime glass sheet or silicon chip to be substrate, with CuCl ₂2H ₂o, SnCl ₂2H ₂o and ZnCl ₂2H ₂o is raw material, one or more mixture in deionized water, ethanol, ethylene glycol, hydrochloric acid is solvent, the precursor thin-film of certain thickness copper zinc-tin is first prepared with spin-coating method, take hydrazine hydrate as reducing agent, heat at a lower temperature in closed container, make precursor thin-film and sublimed sulfur reduce concurrent GCMS computer and be obtained by reacting 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 chip put into chloroform by volume: ethanol=5: the solution of 1, Ultrasonic Cleaning 30min by size; Again substrate is put into acetone: distilled water=5: the solution of 1, Ultrasonic Cleaning 30min; Again in distilled water by substrate supersonic oscillations 30min; Substrate obtained above is emitted in glass dish send in baking oven and dries for masking.

B. by CuCl ₂2H ₂o, SnCl ₂2H ₂o and ZnCl ₂2H ₂o puts into solvent, makes the material Homogeneous phase mixing in solution.Specifically, can by 2.0 ~ 4.0 parts of CuCl ₂2H ₂o, 1.0 ~ 2.0 parts of ZnCl ₂2H ₂o and 1.3 ~ 2.6 part SnCl ₂2H ₂o puts into the solvent of 30 ~ 120 parts, makes the material Homogeneous phase mixing in solution, and wherein solvent is one or more the mixture in deionized water, ethanol, ethylene glycol, hydrochloric acid.

C. make the substrate of solution described in outside uniform application step b, and dry, obtain precursor thin-film sample.Above-mentioned solution can be dripped on the substrate that is placed on sol evenning machine, restart sol evenning machine and rotate certain hour with 200 ~ 3500 revs/min, after making the solution coat on dripping even, and after substrate is dried, dry again after again repeating to drip upper previous solu and spin coating, repetition like this 2 ~ 15 times, so obtain certain thickness precursor thin-film sample on substrate.

What d. the sublimed sulfur of 0.782 ~ 1.564 part is placed with hydrazine hydrate can closed container, and sublimed sulfur is mixed with hydrazine hydrate.

E. be placed on support by step c gained precursor thin-film sample, what be placed with Step d gained hydrazine hydrate and sublimed sulfur can closed container, and precursor thin-film sample is not contacted with sublimed sulfur with hydrazine.The hydrazine hydrate amount of putting into is 40.0 ~ 90.0 parts.The above-mentioned closed container that precursor thin-film sample is housed is put into baking oven, is heated between 160 ~ 220 DEG C, temperature retention time 10 ~ 60 hours, then cool to room temperature takes out.

F. by step e products therefrom, after carrying out natural drying, namely copper zinc tin sulfide optoelectronic film is obtained;

The present invention does not need high temperature 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 zinc tin sulfide optoelectronic film has good continuity and uniformity, the composition and structure of the easy control objectives product of this new technology, providing a kind of low cost for preparing high performance copper zinc tin sulfide optoelectronic film, can realize the method for large-scale industrial production.

Embodiment

Embodiment 1

A. the cleaning of substrate: carry out cleaning silicon chip (size is 2mm × 2mm) as previously mentioned.

B. by part 1.97 parts of CuCl ₂2H ₂o, 1.0 parts of ZnCl ₂2H ₂o and 1.31 part SnCl ₂2H ₂o puts into vial, adds 37.037 parts of ethanol, utilizes more than ultrasonic vibration 30min, makes the material Homogeneous phase mixing in solution.

C. above-mentioned solution is dripped on the silicon chip be placed on sol evenning machine, restart sol evenning machine, sol evenning machine rotates 5 seconds with 200 revs/min, rotate 15 seconds with 3000 revs/min, after making the solution coat on dripping even, after substrate is dried, dry again after again repeating to drip upper previous solu and spin coating, repetition like this 12 times, so obtain 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 the sublimed sulfur of 58.03. part hydrazine hydrate and 0.791 part, precursor thin-film sample is placed on support and makes it not contact with sublimed sulfur with hydrazine, the closed container that precursor thin-film sample is housed is put into baking oven, be heated to 200 DEG C, temperature retention time 20 hours, then cool to room temperature takes out.

E. by above-mentioned steps d product, after carrying out natural drying, namely obtain copper zinc tin sulfide optoelectronic film;

Embodiment 2

A. the cleaning of substrate: carry out cleaning glass substrate (size is 2mm × 2mm) as previously mentioned.

B. by 3.41 parts of CuCl ₂2H ₂o, 1.72 parts of ZnCl ₂2H ₂o and 2.26 part SnCl ₂2H ₂o puts into vial, adds 74.074 parts of ethylene glycol, utilizes more than ultrasonic vibration 30min, makes the material Homogeneous phase mixing in solution.

C. above-mentioned solution is dripped on the glass substrate be placed on sol evenning machine, restart sol evenning machine, sol evenning machine rotates 9 seconds with 500 revs/min, after making the solution coat on dripping even, after substrate is dried, dry again after again repeating to drip upper previous solu and spin coating, so repeat 4 times, so obtain certain thickness precursor thin-film sample on a glass substrate.

D. the precursor thin-film sample of above-mentioned technique gained is put into sealable container, and put into the sublimed sulfur of 89.76 parts of hydrazine hydrates and 1.36 parts, precursor thin-film sample is placed on support and makes it not contact with hydrazine, the closed container that precursor thin-film sample is housed is put into baking oven, be heated to 180 DEG C, temperature retention time 60 hours, then cool to room temperature takes out.

E. by steps d products therefrom, after carrying out natural drying, namely copper zinc tin sulfide optoelectronic film is obtained.

Claims (1)

1. prepare a method for copper zinc tin sulfide optoelectronic film, comprise the step of following order:

A. the cleaning of substrate: be that 2mm × 2mm glass substrate puts into volume ratio chloroform: ethanol=5: the solution of 1, Ultrasonic Cleaning 30min by size; Again substrate is put into volume ratio acetone: distilled water=5: the solution of 1, Ultrasonic Cleaning 30min; Again in distilled water by substrate supersonic oscillations 30min; Substrate obtained above is emitted in glass dish send in baking oven and dries for masking;

B. by 3.41 parts of CuCl ₂2H ₂o, 1.72 parts of ZnCl ₂2H ₂o and 2.26 part SnCl ₂2H ₂o puts into vial, adds 74.074 parts of ethylene glycol, utilizes more than supersonic oscillations 30min, makes the material Homogeneous phase mixing in solution;

C. above-mentioned solution is dripped on the glass substrate be placed on sol evenning machine, restart sol evenning machine, sol evenning machine rotates 9 seconds with 500 revs/min, after making the solution coat on dripping even, after substrate is dried, dry again after again repeating to drip upper previous solu and spin coating, so repeat 4 times, so obtain certain thickness precursor thin-film sample on a glass substrate;

D. the precursor thin-film sample of above-mentioned technique gained is put into sealable container, and put into the sublimed sulfur of 89.76 parts of hydrazine hydrates and 1.36 parts, precursor thin-film sample is placed on support and makes it not contact with hydrazine, the closed container that precursor thin-film sample is housed is put into baking oven, be heated to 180 DEG C, temperature retention time 60 hours, then cool to room temperature takes out;

E. by steps d products therefrom, after carrying out natural drying, namely copper zinc tin sulfide optoelectronic film is obtained.