CN106449862A - Preparation method of CZTS thin film - Google Patents
Preparation method of CZTS thin film Download PDFInfo
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- CN106449862A CN106449862A CN201610573931.XA CN201610573931A CN106449862A CN 106449862 A CN106449862 A CN 106449862A CN 201610573931 A CN201610573931 A CN 201610573931A CN 106449862 A CN106449862 A CN 106449862A
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- zinc
- copper
- tin
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- sulfur
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- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000010409 thin film Substances 0.000 title claims abstract description 17
- 239000010408 film Substances 0.000 claims abstract description 65
- 238000000137 annealing Methods 0.000 claims abstract description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 150000003751 zinc Chemical class 0.000 claims abstract description 4
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000010439 graphite Substances 0.000 claims description 21
- 229910002804 graphite Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- YGSCHSPBVNFNTD-UHFFFAOYSA-N [S].[Sn].[Zn] Chemical compound [S].[Sn].[Zn] YGSCHSPBVNFNTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011160 research Methods 0.000 abstract description 4
- 238000004528 spin coating Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 150000001879 copper Chemical class 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- ALRFTTOJSPMYSY-UHFFFAOYSA-N tin disulfide Chemical compound S=[Sn]=S ALRFTTOJSPMYSY-UHFFFAOYSA-N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 229910005641 SnSx Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared 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
- H01L31/0248—Semiconductor devices sensitive to infrared 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
- H01L31/0256—Semiconductor devices sensitive to infrared 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
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic 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
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a preparation method of a CZTS thin film. The preparation method comprises the steps of 1) dissolving four compounds of a copper salt, a zinc salt, a tin salt and thiourea which are taken as raw materials in an organic solvent to form a CZTS solution according to a proportion of atomic ratio being Cu/(Zn+Sn)=0.7-1 and Zn/Sn=1-1.2; 2) spin-coating the CZTS solution on a substrate; 3) performing pre-annealing under 200-300 DEG C to prepare the CZTS thin film; and 4) placing the CZTS thin film in an annealing chamber, and performing post-annealing under 500-600 DEG C. By the preparation method, the problem of high-temperature decomposition of CZTS can be effectively solved, the metal proportion after film forming is consistent with the precursor solution proportion, and an ideal copper-poor zinc-rich metal proportion can be easily acquired. By the preparation method, the crystallinity of the thin film can be improved, and the efficiency of a CZTS solar cell is favorably improved; the pollution problem can be effectively avoided, the production cost is reduced, and the preparation method had practical value; and since the initial pressure of inflatable nitrogen is controllable, the research of the influence of different pressures on the film forming can be achieved, and the preparation method has important significance.
Description
Technical field
The invention belongs to photovoltaic material technical field of new energies is and in particular to a kind of copper zinc-tin based on high-temperature processing technology
The preparation method of sulfur thin film.
Background technology
Purdue Univ-West Lafayette USA scientist is in a nearest phase《American Chemical Society can will》On write articles and point out, they using a kind of with
Film forming method based on solution, is made for this using the very abundant copper zincium tin sulfur compound of reserves on the earth (CZTSSe)
Plant solaode.This opinion the article pointed out, it have devised the solar-electricity that a kind of material by low cost, abundance is made
Pond, this battery is easy to large-scale production and performance is highly stable, and its universe transformation efficiency is up to 7.2%, same higher than current
Class solaode, its transformation efficiency is in following also very big room for promotion.
Research before has shown that, can produce solaode using copper-zinc-tin-sulfur (CZTS) nanocrystal.Australia
CZTS is referred to as the candidate technology of the 3rd generation thin-film solar cells by NSW university Martin professor Green, and it possesses no
The characteristic that poison, mineral resources are enriched, is expected to replace cadmium telluride (CdTe) and CIGS (CIGS) thin film solar technology, thus reducing
Cost for solar power generation, makes regenerative resource really realize substitute fossil fuels in life.In 2 months this year, IBM announces to use
CZTS has produced this solaode, and but, its transformation efficiency is less than 1%.
Although CZTS or CZTSSe solaode does not also occur in the market, copper-zinc-tin-sulfur solaode with
The solaode of additive method manufacture is compared and is rich in competitive advantage.
In the preparation method of existing copper-zinc-tin-sulfur, there is following defect：
First, using Low Temperature Heat Treatment, the generation of SnSx and S gas can be avoided so that Sn loss reduces, but copper zinc-tin
The degree of crystallinity of sulfur is low, and crystal grain is little.
Second, using high-temperature heat treatment, the degree of crystallinity of copper-zinc-tin-sulfur can be improved, but compound can be caused to decompose, produce
Raw Binary-phase, component is not single, is unfavorable for that photoelectric transformation efficiency is lifted；In addition, high-temperature decomposition product SnSx and S is gas, Sn
Loss causes metal ratio in thin film uncontrollable it is impossible to reach the metal ratio needed for device level absorbed layer；
3rd, add sulphur powder in annealing, compound decomposition and the generation of SnSx and S gas can be reduced, but sulfur
Powder can cause larger pollution.
Based on the above, provide that a kind of metal component is single, ratio is controlled, the copper-zinc-tin-sulfur film of inexpensive and environmental protection
Preparation method be necessary.
Content of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of preparation of copper-zinc-tin-sulfur film
Method, be difficult to control to for solving copper-zinc-tin-sulfur film metal component in prior art, preparation cost higher and to easily right
The problem of environment.In particular for occur when the existing copper-zinc-tin-sulfur film high-temperature heat treatment decomposing phenomenon (>450
DEG C will occur), Sn element loss serious it is impossible to obtain a difficult problem for preferably lean copper zinc-rich metal ratio, a kind of sealing is provided
Graphite method for annealing, in the acquisition thin film consistent with presoma metal ratio after (500 DEG C～600 DEG C) annealing of high temperature,
Composition is mutually single quaternary phase, and crystallite dimension is larger, and crystallinity improves.
For achieving the above object and other related purposes, the present invention provides a kind of preparation method of copper-zinc-tin-sulfur film, bag
Include step：Step 1), with mantoquita, zinc salt, pink salt, four kinds of compounds of thiourea as raw material, by atomic ratio Cu/ (Zn+Sn)=0.7～
1, Zn/Sn=1～1.2 ratio is dissolved in formation copper-zinc-tin-sulfur solution in organic solvent；Step 2), will be molten for described copper-zinc-tin-sulfur
Liquid is spun on substrate；And step 3), carry out preannealing at 200 DEG C～300 DEG C and make copper-zinc-tin-sulfur film.
As a kind of preferred version of the preparation method of the copper-zinc-tin-sulfur film of the present invention, step 3) in, preannealing when
Between scope be 5min～30min.
As a kind of preferred version of the preparation method of the copper-zinc-tin-sulfur film of the present invention, also include step：Step 4), will
Described copper-zinc-tin-sulfur film puts into annealing chamber, carries out after annealing at 500 DEG C～600 DEG C.
As a kind of preferred version of the preparation method of the copper-zinc-tin-sulfur film of the present invention, the time range of described after annealing
For 60～200min.
As a kind of preferred version of the preparation method of the copper-zinc-tin-sulfur film of the present invention, step 4) in, first by described copper
Zinc-tin-sulfur film is put in the graphite of closing, then puts into annealing chamber together with graphite, enters at 500 DEG C～600 DEG C
Row after annealing, the lean copper zinc-rich metal ratio needed for acquisition copper-zinc-tin-sulfur solar cell, the copper-zinc-tin-sulfur of single quaternary phase component
Thin film semiconductor.
Further, each metal ratio in the copper-zinc-tin-sulfur film before and after described after annealing is consistent.
As a kind of preferred version of the preparation method of the copper-zinc-tin-sulfur film of the present invention, described graphite include cassette bottom,
Box wall and lid, described cassette bottom and box wall are to be fixedly connected, described lid and described box wall for movable open or close be connected.
As a kind of preferred version of the preparation method of the copper-zinc-tin-sulfur film of the present invention, step 4) in, by described copper zinc
After stannum sulfur thin film puts into annealing chamber, evacuation process is carried out to described annealing chamber, is then filled with nitrogen within the chamber laggard
Row after annealing.
As a kind of preferred version of the preparation method of the copper-zinc-tin-sulfur film of the present invention, after being filled with nitrogen, described annealing
The pressure range of chamber is 20kPa～30kPa.
As a kind of preferred version of the preparation method of the copper-zinc-tin-sulfur film of the present invention, described organic solvent includes second two
Alcohol methyl ether solution.
As described above, the preparation method of the copper-zinc-tin-sulfur film of the present invention, have the advantages that：
1) with existing prepare copper-zinc-tin-sulfur film method compared with, the present invention provide preparation method can achieve copper-zinc-tin-sulfur
The control of film metal ratio, can obtain preferable metal ratio easily：Cu/ (Zn+Sn)=0.7～1, Zn/Sn=1～1.2.
2) existing technology needs to add the catabolite such as sulphur powder, selenium powder or Tin disulfide to suppress point in high annealing
Solution, the preparation method that the present invention provides need not add sulphur powder, selenium powder or Tin disulfide, only need to be filled with a certain amount of nitrogen within the chamber
Gas, decreases pollution, has saved cost；And can control initial nitrogen pressure, can achieve the difference research to effect of film formation for the pressure.
3) to need the opening of sintered quartz pipe to carry out melting sealed for prior art, and the present invention is provided and carried out using graphite
Sealing, this graphite is made up of cassette bottom, box wall and lid, need not complicated encapsulation process, only can need to facilitate on lid lid
Pick and place sample, recycling, simple to operate, time-consuming and cost.
Brief description
Fig. 1 is shown as the steps flow chart schematic diagram of the preparation method of the copper-zinc-tin-sulfur film in embodiments of the invention 1.
Fig. 2 is shown as the steps flow chart schematic diagram of the preparation method of the copper-zinc-tin-sulfur film in embodiments of the invention 2.
The post growth annealing of the preparation method of the copper-zinc-tin-sulfur film that Fig. 3 is shown as in embodiments of the invention 2 is adopted
Graphite and annealing chamber structural representation.
The graphite that the preparation method of the copper-zinc-tin-sulfur film that Fig. 4～Fig. 5 is shown as in embodiments of the invention 2 is adopted
Structural representation.
The preparation method of the copper-zinc-tin-sulfur film that Fig. 6 is shown as in embodiments of the invention 1 does not carry out post growth annealing
Copper-zinc-tin-sulfur film surface SEM picture.
The preparation method of the copper-zinc-tin-sulfur film that Fig. 7 is shown as in embodiments of the invention 1 does not carry out post growth annealing
The XRD spectra of copper-zinc-tin-sulfur film.
Fig. 8 is shown as the copper zinc through post growth annealing for the preparation method of the copper-zinc-tin-sulfur film in embodiments of the invention 2
Stannum sulfur film surface SEM picture.
Fig. 9 is shown as the copper zinc through post growth annealing for the preparation method of the copper-zinc-tin-sulfur film in embodiments of the invention 2
The XRD spectra of stannum sulfur thin film.
Component label instructions
101 box wall
102 cassette bottom
103 lids
S11～S13 step
S24 step
Specific embodiment
Below by way of specific instantiation, embodiments of the present invention are described, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also be by addition different concrete realities
The mode of applying is carried out or applies, and the every details in this specification can also be based on different viewpoints and application, without departing from
Carry out various modifications and changes under the spirit of the present invention.
Refer to Fig. 1～Fig. 9.It should be noted that the diagram provided in the present embodiment only illustrates this in a schematic way
The basic conception of invention, only shows the assembly relevant with the present invention rather than according to package count during actual enforcement in then illustrating
Mesh, shape and size are drawn, and during its actual enforcement, the kenel of each assembly, quantity and ratio can be a kind of random change, and its
Assembly layout kenel is likely to increasingly complex.
As shown in Fig. 1, Fig. 6 and Fig. 7, the present embodiment provides a kind of preparation method of copper-zinc-tin-sulfur film, including step：
As shown in figure 1, carrying out step 1 first) S11, with mantoquita, zinc salt, pink salt, four kinds of compounds of thiourea as raw material, presses
The ratio of atomic ratio Cu/ (Zn+Sn)=0.7～1, Zn/Sn=1～1.2 is dissolved in formation copper-zinc-tin-sulfur solution in organic solvent.
For example, described atomic ratio can for Cu/ (Zn+Sn)=0.7, Zn/Sn=1 or Cu/ (Zn+Sn)=
0.8, Zn/Sn=1.1 or Cu/ (Zn+Sn)=1, Zn/Sn=1.2 etc., to meet the copper needed for different solar cells
The metal ratio of zinc-tin sulfur, and it is not limited to example recited herein.
As an example, described organic solvent includes ethylene glycol monomethyl ether solution.
As shown in figure 1, and then carrying out step 2) S12, described copper-zinc-tin-sulfur solution is spun on substrate；
As shown in figure 1, finally carrying out step 3) S13, carrying out preannealing at 200 DEG C～300 DEG C, to make copper-zinc-tin-sulfur thin
Film.
As an example, step 3) in, the time range of preannealing is 5min～30min.
In a specific implementation process, take 300mg CuCl respectively2With 300mg SnCl2·H2O is dissolved in 10ml second
In glycol methyl ether solution, treat that solution colour is changed into milky, weigh 200mg ZnCl2Add in above-mentioned solution with 760mg thiourea,
It is stirred at room temperature, stir about 72 hours is to being completely dissolved.Take this solution appropriate to drip on clean soda-lime glass, carry out spin coating,
First under 500rpm obtains rotating speed, rotate 10s, after rotate 30s under the rotating speed of 1500RPM, spin coating terminates, and sample is placed on 300
DEG C warm table on heat 5min, formed copper-zinc-tin-sulfur (CZTS) quaternary compound.After cooling, repeat above procedure.Repeat
Above procedure 14 times is up to ideal thickness.Fig. 6 is the buffer-layer surface SEM picture not carrying out post growth annealing, and Fig. 7 is not carry out
The cushion XRD spectra of post growth annealing is it is seen that copper-zinc-tin-sulfur film component is extremely complex, not merely.
Certainly, the temperature of described preannealing can be 200 DEG C, 250 DEG C etc., its corresponding heat time heating time can for 30min,
15min etc..
Embodiment 2
As shown in Fig. 2～Fig. 5 and Fig. 8～Fig. 9, the present embodiment provides a kind of preparation method of copper-zinc-tin-sulfur film, its base
This step is substantially the same manner as Example 1, wherein, is with the difference of embodiment 1：The preparation side of described copper-zinc-tin-sulfur film
Method also includes step：Step 4) S24, described copper-zinc-tin-sulfur film is put into annealing chamber, after carrying out at 500 DEG C～600 DEG C
Annealing.
As an example, the time range of described after annealing is 60～200min.
As an example, step 4) in, first described copper-zinc-tin-sulfur film is put in the graphite of closing, then together with graphite
Put into annealing chamber together, carry out after annealing at 500 DEG C～600 DEG C, the lean copper obtaining needed for copper-zinc-tin-sulfur solar cell is rich
Zinc metal ratio, the copper-zinc-tin-sulfur film quasiconductor of single quaternary phase component.Further, the copper zinc-tin before and after described after annealing
Each metal ratio in sulfur thin film is consistent.
As an example, described graphite includes cassette bottom 102, box wall 101 and lid 103, described cassette bottom 102 and box wall 101
For being fixedly connected, described lid 103 and described box wall 101 be movable open or close be connected.
As an example, step 4) in, described copper-zinc-tin-sulfur film is put into after annealing chamber, described annealing chamber is carried out
Evacuation is processed, and is then filled with after nitrogen within the chamber and carries out after annealing.
As an example, after being filled with nitrogen, the pressure range of described annealing chamber is 20kPa～30kPa.
Specifically, in the present embodiment, spin coating and pre-warmed copper-zinc-tin-sulfur film are placed in the graphite of customization,
Described graphite includes cassette bottom 102, box wall 101 and lid 103, and described cassette bottom 102 and box wall 101 are to be fixedly connected, described box
Lid 103 with described box wall 101 be movable open or close be connected, described graphite be cylinder barrel assembling structure, its apparent size
For(diameter) * 90mm (length), box wall 101 is thick to be 6.5mm, as shown in Fig. 4～Fig. 5, as 5 are shown as graphite
The cross section structure schematic diagram of lid 103, it is set to inclined-plane with the joint portion of box wall 101, and the angle of inclination on described inclined-plane is 45
Degree, described inclined-plane can greatly improve the convenience that lid 103 is opened or closed with box wall 101.The table top that described inclined-plane is formed
On there is sealing, to strengthen the air-tightness of lid 103 and box wall 101.As shown in figure 3, graphite is placed in annealing chamber,
Again annealing chamber is evacuated to<10Pa, then passes to N2So that the air pressure level of annealing within the chamber is 20kPa～30kPa,
It is warming up to 550 DEG C, then constant temperature processes 2h, after cooling, take out sample, carry out test analysis.Table 1 below is that the present invention is annealed
The cushion EDS spectrogram of technique and element ratio table, from table 1, constituent content (percentage by weight before and after after annealing
Weight% and atomic percent Atomic%) close with content in precursor solution (Ratio), element ratio is close to ideal
CZTS device required ratio.Fig. 8 is shown as carrying out the buffer-layer surface SEM picture of annealing process it is seen that crystal grain through the present invention
Substantially, film forming is fine and close for dimensional growth.Fig. 9 carries out the cushion XRD spectra of annealing process it is seen that thin film component is single for the present invention
One quaternary CZTS phase.
Certainly, the temperature of described after annealing can be chosen as 500 DEG C or 600 DEG C etc., and its corresponding heat time heating time can be
180min and 60min.
Table 1
As described above, the preparation method of the copper-zinc-tin-sulfur film of the present invention, have the advantages that：
1) with existing prepare copper-zinc-tin-sulfur film method compared with, the present invention provide preparation method can achieve copper-zinc-tin-sulfur
The control of film metal ratio, can obtain preferable metal ratio easily：Cu/ (Zn+Sn)=0.7～1, Zn/Sn=1～1.2.
2) existing technology needs to add the catabolite such as sulphur powder, selenium powder or Tin disulfide to suppress point in high annealing
Solution, the preparation method that the present invention provides need not add sulphur powder, selenium powder or Tin disulfide, only need to be filled with a certain amount of nitrogen within the chamber
Gas, decreases pollution, has saved cost；And can control initial nitrogen pressure, can achieve the difference research to effect of film formation for the pressure.
3) to need the opening of sintered quartz pipe to carry out melting sealed for prior art, and the present invention is provided and carried out using graphite
Sealing, this graphite is made up of cassette bottom 102, box wall 101 and lid 103, need not complicated encapsulation process, only lid 103 need to be covered
Upper, can conveniently pick and place sample, recycling, simple to operate, time-consuming and cost.
So, the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
Above-described embodiment only principle of the illustrative present invention and its effect, not for the restriction present invention.Any ripe
The personage knowing this technology all can carry out modifications and changes without prejudice under the spirit and the scope of the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as
All equivalent modifications becoming or change, must be covered by the claim of the present invention.
Claims (10)
1. a kind of preparation method of copper-zinc-tin-sulfur film is it is characterised in that include step：
Step 1), with mantoquita, zinc salt, pink salt, four kinds of compounds of thiourea as raw material, by atomic ratio Cu/ (Zn+Sn)=0.7～1,
The ratio of Zn/Sn=1～1.2 is dissolved in formation copper-zinc-tin-sulfur solution in organic solvent；
Step 2), described copper-zinc-tin-sulfur solution is spun on substrate；
Step 3), carry out preannealing at 200 DEG C～300 DEG C and make copper-zinc-tin-sulfur film.
2. copper-zinc-tin-sulfur film according to claim 1 preparation method it is characterised in that：Step 3) in, preannealing
Time range is 5min～30min.
3. the preparation method of copper-zinc-tin-sulfur film according to claim 1 is it is characterised in that also include step：
Step 4), described copper-zinc-tin-sulfur film is put into annealing chamber, at 500 DEG C～600 DEG C, carries out after annealing.
4. the preparation method of copper-zinc-tin-sulfur film according to claim 2 is it is characterised in that the time model of described after annealing
Enclose for 60～200min.
5. copper-zinc-tin-sulfur film according to claim 2 preparation method it is characterised in that：Step 4) in, first will be described
Copper-zinc-tin-sulfur film is put in the graphite of closing, then puts into annealing chamber together with graphite, at 500 DEG C～600 DEG C
Carry out after annealing, the lean copper zinc-rich metal ratio needed for acquisition copper-zinc-tin-sulfur solar cell, the copper zinc-tin of single quaternary phase component
Sulfur thin film semiconductor.
6. copper-zinc-tin-sulfur film according to claim 4 preparation method it is characterised in that：Copper before and after described after annealing
Each metal ratio in zinc-tin-sulfur film is consistent.
7. copper-zinc-tin-sulfur film according to claim 4 preparation method it is characterised in that：Described graphite includes box
Bottom, box wall and lid, described cassette bottom and box wall are to be fixedly connected, and described lid and described box wall are movable opening or the company of closure
Connect.
8. the copper-zinc-tin-sulfur film according to claim 2～7 any one preparation method it is characterised in that：Step 4)
In, described copper-zinc-tin-sulfur film is put into after annealing chamber, evacuation process is carried out to described annealing chamber, then within the chamber
Carry out after annealing after being filled with nitrogen.
9. copper-zinc-tin-sulfur film according to claim 8 preparation method it is characterised in that：After being filled with nitrogen, described move back
The pressure range of fiery chamber is 20kPa～30kPa.
10. copper-zinc-tin-sulfur film according to claim 1 preparation method it is characterised in that：Described organic solvent includes
Ethylene glycol monomethyl ether solution.
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| CN107968041A (en) * | 2017-11-22 | 2018-04-27 | 杨晓艳 | A kind of preparation method of copper-zinc-tin-sulfur film |
| CN108328667A (en) * | 2018-03-09 | 2018-07-27 | 三峡大学 | A kind of method that solid phase reaction in-situ prepares flower-shaped cobalt sulfide nickel nanosphere |
| CN108611661A (en) * | 2018-05-16 | 2018-10-02 | 东北师范大学 | A method of it improving optical electro-chemistry and decomposes water photocathode copper-zinc-tin-sulfur film quality |
| CN111916527A (en) * | 2019-05-10 | 2020-11-10 | 东泰高科装备科技有限公司 | Semiconductor material vulcanization method |
| CN113380924A (en) * | 2021-06-04 | 2021-09-10 | 南开大学 | Method for regulating and controlling components of absorption layer of copper-based thin film solar cell and solar cell prepared by method |
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| CN105161572A (en) * | 2015-08-31 | 2015-12-16 | 南京航空航天大学 | Ink multi-layer coating preparation method of Cu2ZnSnS4 solar cell absorption layer |
| CN105185847A (en) * | 2015-08-24 | 2015-12-23 | 扬州大学 | Method for preparing copper-zinc-tin-sulfur film |
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| CN103560165A (en) * | 2013-09-12 | 2014-02-05 | 北京工业大学 | A method for preparing absorption layer film of Cu2ZnSn (S, se)4solar cell by using thiol group ink |
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| CN107968041A (en) * | 2017-11-22 | 2018-04-27 | 杨晓艳 | A kind of preparation method of copper-zinc-tin-sulfur film |
| CN108328667A (en) * | 2018-03-09 | 2018-07-27 | 三峡大学 | A kind of method that solid phase reaction in-situ prepares flower-shaped cobalt sulfide nickel nanosphere |
| CN108611661A (en) * | 2018-05-16 | 2018-10-02 | 东北师范大学 | A method of it improving optical electro-chemistry and decomposes water photocathode copper-zinc-tin-sulfur film quality |
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| CN113380924A (en) * | 2021-06-04 | 2021-09-10 | 南开大学 | Method for regulating and controlling components of absorption layer of copper-based thin film solar cell and solar cell prepared by method |
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