CN105957926A - Method for regulating and controlling band offset of copper zinc tin sulfide/indium sulfide heterojunction - Google Patents
Method for regulating and controlling band offset of copper zinc tin sulfide/indium sulfide heterojunction Download PDFInfo
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- CN105957926A CN105957926A CN201610571895.3A CN201610571895A CN105957926A CN 105957926 A CN105957926 A CN 105957926A CN 201610571895 A CN201610571895 A CN 201610571895A CN 105957926 A CN105957926 A CN 105957926A
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- China
- Prior art keywords
- zinc
- copper
- sulfur
- tin
- indium sulfide
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 30
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 26
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 230000001276 controlling effect Effects 0.000 title claims abstract 3
- 230000001105 regulatory effect Effects 0.000 title claims abstract 3
- 239000010409 thin film Substances 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 23
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001704 evaporation Methods 0.000 claims description 80
- 230000008020 evaporation Effects 0.000 claims description 80
- 239000010408 film Substances 0.000 claims description 34
- 239000011521 glass Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- ZOMNDSJRWSNDFL-UHFFFAOYSA-N sulfanylidene(sulfanylideneindiganylsulfanyl)indigane Chemical compound S=[In]S[In]=S ZOMNDSJRWSNDFL-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 210000003041 ligament Anatomy 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 12
- 239000005357 flat glass Substances 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000007738 vacuum evaporation Methods 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 238000002207 thermal evaporation Methods 0.000 abstract 1
- 230000012010 growth Effects 0.000 description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 20
- 239000010949 copper Substances 0.000 description 14
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000001119 stannous chloride Substances 0.000 description 5
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000013213 extrapolation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000002061 vacuum sublimation Methods 0.000 description 2
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- SIXIBASSFIFHDK-UHFFFAOYSA-N indium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[In+3].[In+3] SIXIBASSFIFHDK-UHFFFAOYSA-N 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0623—Sulfides, selenides or tellurides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- 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
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
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- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
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Abstract
The invention discloses a method for regulating and controlling a band offset of a copper zinc tin sulfide/indium sulfide heterojunction. A copper zinc tin sulfide thin film is prepared by a sol-gel method, and an indium sulfide thin film grows on the copper zinc tin sulfide thin film by a vacuum thermal evaporation method at different substrate temperatures to obtain the copper zinc tin sulfide/indium sulfide heterojunction and to regulate and control the band offset of the copper zinc tin sulfide/indium sulfide heterojunction, so that the target of optimizing the band offset of the copper zinc tin sulfide/indium sulfide heterojunction is achieved. In addition, the used method is simple; the operability is high; the regulation effect is significant; and the method is easy to implement and can be applied to preparation of a copper zinc tin sulfide thin film solar cell buffer layer.
Description
Technical field
The invention belongs to technical field of material, be specifically related to a kind of regulation and control copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank
Method.
Background technology
General copper-zinc-tin-sulfur (Cu2ZnSnS4, it being called for short CZTS) and film solar battery structure is: medium/hearth electrode/absorption
Layer (CZTS)/cushion/transparency conducting layer/upper electrode, wherein cushion be mainly used to reduce transparency conducting layer and absorbed layer it
Between can band non-continuous event, typically can use high transmission rate, resistivity is at the material of 5.0 ~ 120 Ω cm.Present solar energy
Battery mainly use CdS is as cushion, but CdS is a kind of virose material, is not suitable for sustainable development, therefore needs development
A kind of material nontoxic, environmental protection replaces.Indium sulfide (In2S3) it is a kind of nontoxic, energy gap quasiconductor at 1.9 ~ 3.7eV
Material, is a kind of ideal replacement CdS new material as CZTS thin-film solar cells cushion.
But due to CZTS/In2S3Conduction band band rank (CBO) be (0.41 ± 0.10eV) than optimum scope (0 ~ 0.3eV)
Height, this can make light induced electron hindering by high potential barrier, thus hinder photogenerated current, make short-circuit current density and filling
The factor reduces, and reduces the performance of battery.For this problem, the present invention regulates and controls copper zinc-tin by controlling substrate temperature
Sulfur/indium sulfide heterogeneous ligament rank, thus reach to optimize the purpose on copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank.And by controlling base
Sheet temperature regulates and controls copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank, there is presently no relevant report.
Summary of the invention
It is an object of the invention to provide a kind of regulate and control copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank method, at copper zinc-tin
Under different substrate temperatures, grown indium sulfide thin film with Vacuum sublimation above sulfur thin film, reach regulate and control copper-zinc-tin-sulfur/
The purpose on indium sulfide heterogeneous ligament rank.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of regulate and control copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank method, it specifically includes following steps:
Step 1): be cleaned transparent glass sheet processing, will carry out in deionized water, acetone and ethanol successively by sheet glass
Supersound process, then takes out, dries；
Step 2): by copper acetate monohydrate (Cu (CH3COOH)2•H2O), Zinc diacetate dihydrate (Zn (CH3COOH)2•2H2O) and
Two hydrated stannous chloride (SnCl2•2H2O), after mixing, add thiourea and be dissolved in ethylene glycol monomethyl ether, and add stabilizer, 50 DEG C
Heating in water bath stirring 1h, obtains colloid；
Step 3): utilize spin-coating method by step 2) colloid prepared is coated on the drying sheet glass of step 1) gained, through 280 DEG C
Baking becomes copper-zinc-tin-sulfur preformed layer thin film；It is repeated several times to reach required film thickness, thickness 800nm；
Step 4): the copper-zinc-tin-sulfur preformed layer film sample that step 3) is prepared puts into quartz boat, then puts the stone in vulcanizing oven into
In English glass tubing, with mechanical pump to quartz glass tube evacuation, after below 5pa, close mechanical pump；Then toward the quartz in stove
Glass tubing is passed through N2Gas, flow is 180sccm, keeps being passed through N after logical 10min2Gas, then it is passed through H2S gas, flow is
20sccm；After ten minutes, start to allow vulcanizing oven heat up, after 1h, be raised to 580 DEG C, keep temperature 1h, subsequently by cooling water cooling
4h, to room temperature, prepares solar cell absorbed layer material copper zinc-tin-sulfur film；
Step 5): the copper-zinc-tin-sulfur film (load is on a glass substrate) step 4) prepared is placed in the evaporation cavity of vacuum evaporation stove
In；Indium sulfide powder is placed in evaporation boat, then puts in evaporation cavity；After evaporation cavity evacuation, to being loaded with copper-zinc-tin-sulfur
The glass substrate of thin film carries out being heated or not heated process, if carrying out heat treated, substrate temperature is heated to 100 ~ 200 DEG C；
Evaporation boat is heated by subsequent power-up stream, and the indium sulfide powder to evaporation boat evaporates completely, and now electric current is 100A, then
Stop evaporation, obtain copper-zinc-tin-sulfur/indium sulfide hetero-junctions.
The time of supersound process described in step 1) is 15 minutes；The temperature of described drying is 100 DEG C, and drying time is
25-40 minute.
In step 5), adding the speed that evaporation boat heats by electric current is 10A/ minute.
In step 5), in copper-zinc-tin-sulfur/indium sulfide hetero-junctions that evaporation obtains, indium sulfide thin film thickness is 3-5nm.
In step 5), the quality of the indium sulfide powder being placed in evaporation boat is 5mg.
Evaporation boat described in step 5) is molybdenum boat；During evacuation, it is 1.0 × 10 by being evacuated to vacuum in evaporation cavity-3Handkerchief.
The beneficial effects of the present invention is: the present invention provide a kind of regulate and control copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank side
Method, grown indium sulfide thin film with Vacuum sublimation under different substrate temperatures on copper-zinc-tin-sulfur film, obtains copper
Zinc-tin sulfur/indium sulfide hetero-junctions, reaches the purpose on copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank.Additionally, used by the present invention
Method is simple, workable, easily realizes, can be used for the preparation of copper-zinc-tin-sulfur film solar cell cushion.
Accompanying drawing explanation
Fig. 1 is the top of valence band position view of normalized indium sulfide (a), copper-zinc-tin-sulfur (b)；
Fig. 2 is the energy gap of copper-zinc-tin-sulfur body material；
Fig. 3 is the energy gap of indium sulfide body material, and (a) is without heating, (b) 100 DEG C, (c) 150 DEG C and (d) 200 DEG C；
Fig. 4 is the energy band diagram of the hetero-junctions of four kinds of different growth temperatures.
Detailed description of the invention
In order to make content of the present invention easily facilitate understanding, below in conjunction with detailed description of the invention to of the present invention
Technical scheme is described further, but the present invention is not limited only to this.
Embodiment 1
A kind of regulate and control copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank method, it specifically includes following steps:
Step 1): be cleaned transparent glass sheet processing, will sheet glass each super in deionized water, acetone and ethanol successively
Sonication 15 minutes, then takes out, and is placed in 100 DEG C of high temperature drying casees drying 30 minutes；
Step 2): by copper acetate monohydrate (Cu (CH3COOH)2•H2O), Zinc diacetate dihydrate (Zn (CH3COOH)2•2H2O) and
Two hydrated stannous chloride (SnCl2•2H2O), after mixing, add thiourea and be dissolved in ethylene glycol monomethyl ether, and add stabilizer, 50 DEG C
Heating in water bath stirring 1h, obtains colloid；
Step 3): utilize spin-coating method by step 2) colloid prepared is coated on the drying sheet glass of step 1) gained, through 280
Copper-zinc-tin-sulfur preformed layer thin film is made in DEG C baking；Being repeated several times to reach required film thickness, thickness is about 800nm.
Step 4): the copper-zinc-tin-sulfur preformed layer film sample that step 3) is prepared puts into quartz boat, then puts in vulcanizing oven
Quartz glass tube in, with mechanical pump to quartz glass tube evacuation, after below 5pa, close mechanical pump；Then toward in stove
Quartz glass tube is passed through N2Gas, flow is 180sccm, keeps being passed through N after logical 10min2Gas, then it is passed through H2S gas, flow
For 20sccm；After ten minutes, start to allow vulcanizing oven heat up, after 1h, be raised to 580 DEG C, keep temperature 1h, subsequently by cooling water-cooled
But 4h is to room temperature, prepares solar cell absorbed layer material copper zinc-tin-sulfur film；
Step 5): step 4) gained copper-zinc-tin-sulfur film is placed in the evaporation cavity of vacuum evaporation stove；By the indium sulfide powder of 5mg
It is placed in evaporation boat, then puts in evaporation cavity；By evaporation cavity evacuation, it is extracted into 1 × 10-3After Pa, thin to being loaded with copper-zinc-tin-sulfur
The glass substrate of film heats, and after substrate temperature is increased to 150 DEG C, slowly adds electric current pair with the rate of heat addition of 10A/min
Evaporation boat heats, and the indium sulfide powder to evaporation boat evaporates completely, and now electric current is 100A, then stops evaporation, institute
The indium sulfide thin film obtained is at 3 ~ 5nm.
Wear the needs of rank test under in order to, increase the preparation of indium sulfide thin film: by above-mentioned steps 1) the drying glass of gained
Glass is placed in the evaporation cavity of vacuum evaporation stove；The indium sulfide powder of 100mg is placed in evaporation boat, then puts in evaporation cavity；Will
Evaporation cavity evacuation, is extracted into 1 × 10-3After Pa, substrate is heated, after substrate temperature is increased to 150 DEG C, with 10A/min
The rate of heat addition slowly add electric current evaporation boat heated, the indium sulfide powder to evaporation boat evaporates completely, now electric current
For 100A, then stopping evaporation, the indium sulfide thin film of gained is about 50nm.
Embodiment 2
Step 1): be cleaned transparent glass sheet processing, will sheet glass each super in deionized water, acetone and ethanol successively
Sonication 15 minutes, then takes out, and is placed in 100 DEG C of high temperature drying casees drying 30 minutes；
Step 2): by copper acetate monohydrate (Cu (CH3COOH)2•H2O), Zinc diacetate dihydrate (Zn (CH3COOH)2•2H2O) and
Two hydrated stannous chloride (SnCl2•2H2O), after mixing, add thiourea and be dissolved in ethylene glycol monomethyl ether, and add stabilizer, 50 DEG C
Heating in water bath stirring 1h, obtains colloid；
Step 3): utilize spin-coating method by step 2) colloid prepared is coated on the drying sheet glass of step 1) gained, through 280 DEG C
Copper-zinc-tin-sulfur preformed layer thin film is made in baking；Being repeated several times to reach required film thickness, thickness is 800nm；
Step 4): the copper-zinc-tin-sulfur preformed layer film sample that step 3) is prepared puts into quartz boat, then puts the stone in vulcanizing oven into
In English glass tubing, with mechanical pump to quartz glass tube evacuation, after below 5pa, close mechanical pump；Then toward the quartz in stove
Glass tubing is passed through N2Gas, flow is 180sccm, keeps being passed through N after logical 10min2Gas, then it is passed through H2S gas, flow is
20sccm；After ten minutes, start to allow vulcanizing oven heat up, after 1h, be raised to 580 DEG C, keep temperature 1h, subsequently by cooling water cooling
4h, to room temperature, prepares solar cell absorbed layer material copper zinc-tin-sulfur film；
Step 5): step 4) gained copper-zinc-tin-sulfur film is placed in the evaporation cavity of vacuum evaporation stove；By the indium sulfide powder of 5mg
It is placed in evaporation boat, then puts in evaporation cavity；By evaporation cavity evacuation, it is extracted into 1 × 10-3After Pa, not to being loaded with copper-zinc-tin-sulfur
The glass substrate of thin film carries out heating (30 DEG C), slowly adds electric current with the rate of heat addition of 10A/min and heats evaporation boat, extremely
Indium sulfide powder in evaporation boat evaporates completely, and now electric current is 100A, then stops evaporation, the indium sulfide thin film of gained 3 ~
5nm。
Wear the needs of rank test under in order to, increase the preparation of indium sulfide thin film: by above-mentioned steps 1) the drying glass of gained
Glass is placed in the evaporation cavity of vacuum evaporation stove；The indium sulfide powder of 100mg is placed in evaporation boat, then puts in evaporation cavity；Will
Evaporation cavity evacuation, is extracted into 1 × 10-3After Pa, substrate is not heated, slowly add electric current pair with the rate of heat addition of 10A/min
Evaporation boat heats, and the indium sulfide powder to evaporation boat evaporates completely, and now electric current is 100A, then stops evaporation, institute
The indium sulfide thin film obtained is about 50nm.
Embodiment 3
Step 1): be cleaned transparent glass sheet processing, will sheet glass each super in deionized water, acetone and ethanol successively
Sonication 15 minutes, then takes out, and is placed in 100 DEG C of high temperature drying casees drying 25-40 minute；
Step 2): by copper acetate monohydrate (Cu (CH3COOH)2•H2O), Zinc diacetate dihydrate (Zn (CH3COOH)2•2H2O) and
Two hydrated stannous chloride (SnCl2•2H2O), after mixing, add thiourea and be dissolved in ethylene glycol monomethyl ether, and add stabilizer, 50 DEG C
Heating in water bath stirring 1h, obtains colloid；
Step 3): utilize spin-coating method by step 2) colloid prepared is coated on the drying sheet glass of step 1) gained, through 280
Copper-zinc-tin-sulfur preformed layer thin film is made in DEG C baking；Being repeated several times to reach required film thickness, thickness is about 800nm.
Step 4): the copper-zinc-tin-sulfur preformed layer film sample that step 3) is prepared puts into quartz boat, then puts in vulcanizing oven
Quartz glass tube in, with mechanical pump to quartz glass tube evacuation, after below 5pa, close mechanical pump；Then toward in stove
Quartz glass tube is passed through N2Gas, flow is 180sccm, keeps being passed through N after logical 10min2Gas, then it is passed through H2S gas, flow
For 20sccm；After ten minutes, start to allow vulcanizing oven heat up, after 1h, be raised to 580 DEG C, keep temperature 1h, subsequently by cooling water-cooled
But 4h is to room temperature, prepares solar cell absorbed layer material copper zinc-tin-sulfur film；
Step 5): step 4) gained copper-zinc-tin-sulfur film is placed in the evaporation cavity of vacuum evaporation stove；By the indium sulfide powder of 5mg
It is placed in evaporation boat, then puts in evaporation cavity；By evaporation cavity evacuation, it is extracted into 1 × 10-3After Pa, thin to being loaded with copper-zinc-tin-sulfur
The glass substrate of film heats, and after substrate temperature is increased to 100 DEG C, slowly adds electric current pair with the rate of heat addition of 10A/min
Evaporation boat heats, and the indium sulfide powder to evaporation boat evaporates completely, and now electric current is 100A, then stops evaporation, institute
The indium sulfide thin film obtained is at 3 ~ 5nm.
Wear the needs of rank test under in order to, increase the preparation of indium sulfide thin film: by above-mentioned steps 1) the drying glass of gained
Glass is placed in the evaporation cavity of vacuum evaporation stove；The indium sulfide powder of 100mg is placed in evaporation boat, then puts in evaporation cavity；Will
Evaporation cavity evacuation, is extracted into 1 × 10-3After Pa, substrate is heated, after substrate temperature is increased to 100 DEG C, with 10A/min
The rate of heat addition slowly add electric current evaporation boat heated, the indium sulfide powder to evaporation boat evaporates completely, now electric current
For 100A, then stopping evaporation, the indium sulfide thin film of gained is about 50nm；
Embodiment 4
Step 1): be cleaned transparent glass sheet processing, will sheet glass each super in deionized water, acetone and ethanol successively
Sonication 15 minutes, then takes out, and is placed in 100 DEG C of high temperature drying casees drying 25-40 minute；
Step 2): by copper acetate monohydrate (Cu (CH3COOH)2•H2O), Zinc diacetate dihydrate (Zn (CH3COOH)2•2H2O) and
Two hydrated stannous chloride (SnCl2•2H2O), after mixing, add thiourea and be dissolved in ethylene glycol monomethyl ether, and add stabilizer, 50 DEG C
Heating in water bath stirring 1h, obtains colloid；
Step 3): utilize spin-coating method by step 2) colloid prepared is coated on the drying sheet glass of step 1) gained, through 280
Copper-zinc-tin-sulfur preformed layer thin film is made in DEG C baking；Being repeated several times to reach required film thickness, thickness is about 800nm.
Step 4): the copper-zinc-tin-sulfur preformed layer film sample that step 3) is prepared puts into quartz boat, then puts in vulcanizing oven
Quartz glass tube in, with mechanical pump to quartz glass tube evacuation, after below 5pa, close mechanical pump；Then toward in stove
Quartz glass tube is passed through N2Gas, flow is 180sccm, keeps being passed through N after logical 10min2Gas, then it is passed through H2S gas, flow
For 20sccm；After ten minutes, start to allow vulcanizing oven heat up, after 1h, be raised to 580 DEG C, keep temperature 1h, subsequently by cooling water-cooled
But 4h is to room temperature, prepares solar cell absorbed layer material copper zinc-tin-sulfur film；
Step 5): step 4) gained copper-zinc-tin-sulfur film is placed in the evaporation cavity of vacuum evaporation stove；By the indium sulfide powder of 5mg
It is placed in evaporation boat, then puts in evaporation cavity；By evaporation cavity evacuation, it is extracted into 1 × 10-3After Pa, thin to being loaded with copper-zinc-tin-sulfur
The glass substrate of film heats, and after substrate temperature is increased to 200 DEG C, slowly adds electric current pair with the rate of heat addition of 10A/min
Evaporation boat heats, and the indium sulfide powder to evaporation boat evaporates completely, and now electric current is 100A, then stops evaporation, institute
The indium sulfide thin film obtained is at 3 ~ nm.
Wear the needs of rank test under in order to, increase the preparation of indium sulfide thin film: by above-mentioned steps 1) the drying glass of gained
Glass is placed in the evaporation cavity of vacuum evaporation stove；The indium sulfide powder of 100mg is placed in evaporation boat, then puts in evaporation cavity；Will
Evaporation cavity evacuation, is extracted into 1 × 10-3After Pa, substrate is heated, after substrate temperature is increased to 200 DEG C, with 10A/min
The rate of heat addition slowly add electric current evaporation boat heated, the indium sulfide powder to evaporation boat evaporates completely, now electric current
For 100A, then stopping evaporation, the indium sulfide thin film of gained is about 50nm.
The test on the band rank under different growth temperatures
Record one group of band exponent number evidence, i.e. valence band rank and conduction band rank, need three kinds of samples: heterojunction material, composition hetero-junctions
Two semi-conducting materials.To measure one group of CZTS/ In2S3The band exponent number of hetero-junctions is according to illustrating.
The implication representated by symbol will used in regulation this patent:
VBO: valence band rank (Valence band offset)
CBO: conduction band rank (Conduction band offset)
E VBM : top of valence band (Valence band maximum)
E CL : core energy level (Core level)
V bb : band curvature (Band bending)
i: at heterojunction boundary (Interface)
E g : energy gap
WhereinVBO、V bb WithCBOThere is following relation
I.e. measure the sum of two kinds of samples band curvature at heterojunction boundaryV bb , also the value of the top of valence band of two kinds of samples is just
Valence band rank can be drawnVBO.Value further according to the energy gap of two kinds of samples just can draw conduction band rank afterwardsCBO.WhenVBOValue be
Timing, illustrates In2S3Valence-band edge at below CZTS；And forCBO, now symbol is canonical explanation, In2S3Conduction band limit
At more than CZTS.
Fig. 1 is normalized In2S3(a) and CZTS(b) top of valence band position view, obtained by linear extrapolation, point
It is not 0.43 ± 0.1eV(In2S3) and-0.07 ± 0.1eV(CZTS), the method for this linear extrapolation has the uncertain of 0.1eV
Degree, the XPS data of this section all use the peak position (284.64eV) of C1s to calibrate.
List core level and the body of each element in the hetero-junctions sample of pure body material and different temperatures growth in Table 1
Material energy gap.Wherein energy gap be by~The method of curve negotiating linear extrapolation obtains, Fig. 2 and Fig. 3 is CZTS
And In2S3's~Curve, for CZTS, n=2；For In2S3, n=1/2.
Fig. 3 depicts In2S3Energy gap under different growth temperatures, it can be seen that In2S3Energy gap meeting
Change along with the change of growth temperature: when not heating, for 2.03eV；Maximum is reached when growth temperature is 100 DEG C
2.14eV；When growth temperature reaches 150 DEG C, for 2.01eV；1.92eV is then dropped to when growth temperature is increased to 200 DEG C.Different
At a temperature of growth In2S3Energy gap be shown in Table 1.
The core level of each element and body material forbidden band width in the hetero-junctions sample of table 1 body material and different temperatures growth
Degree
The corresponding core level of each element is substituted into formula (1) and obtains band curvature under different temperaturesV bb , due to different units
The band curvature value that element obtains is different, the band curvature value that each element under same temperature obtains is averaged for this, obtains
When band curvature total amount at a temperature of each is respectively as follows: non-heat growth,V bb =-0.22±0.1 eV；During 100 DEG C of growths,V bb =-0.22 ± 0.1 eV, during 150 DEG C of growths,V bb = -0.16±0.1 eV；During 200 DEG C of growths,V bb = -0.08±0.1eV
Afterwards the band curvature total amount at a temperature of the value of the top of valence band of body material and each is substituted into formula (2) and just can obtain valence band rankVBO, when being respectively as follows: non-heat growth,VBO=0.28±0.1 eV；During 100 DEG C of growths,VBO=0.28 ± 0.1 eV, 150 DEG C
During growth,VBO= 0.34±0.1 eV；During 200 DEG C of growths,VBO= 0.42±0.1 eV。
Finally calculateCBO, formula (3) obtain:CBO= 0.30±0.1 eV；During 100 DEG C of growths,CBO= 0.41±0.1
EV, during 150 DEG C of growths,CBO= 0.22±0.1 eV；During 200 DEG C of growths,CBO= 0.01±0.1 eV.Afterwards, by gained
Band exponent number value and band curvature are listed in table 2.
The heterostructure band figure under different growth temperature can be drawn by table 2.As shown in Figure 4, it is four kinds of different growth temperature
The energy band diagram of the hetero-junctions of degree.As seen from the figure, all samples is all the heterojunction semiconductor of I type.Along with the rising of growth temperature,
Valence band rank are gradually increased, and conduction band rank are gradually reduced.Here band curvature and the interface normal attribute one of semi-conducting material
Causing, namely at interface, the semiconductor energy gap of N-shaped can be bent upwards in interface, and the semiconductor energy gap of p-type can be at hetero-junctions
Interface is bent downwardly.It should be noted that the hetero-junctions sample for 200 DEG C of growths, In2S3The band curvature of side be to
Under, this imply that, at the In of 200 DEG C of growths2S3Become p-type material in interface, cause the reason of this change to be likely to be
Under the influence of CZTS, In2S3Rotten in interface, generate the material of a kind of p-type electric-conducting, and this p-type electric-conducting material pole
It is likely to be CuInS2(analysis will be given below).
The hetero-junctions sample belt rank of table 2 different temperatures growth and band curvature numerical value
In order to find out the composition at the hetero-junctions example interface of 200 DEG C of growths, we analyze the metal unit at heterojunction boundary
Element ratio.The information depth of XPS is 3 ~ 5nm, and we are at the In of hetero-junctions growth2S3Film thickness is at below 5nm, so from XPS
The elemental composition information obtained is to contain the CZTS thin film of part.The elemental constituent atomic ratio of XPS detection is as shown in table 3.
As can be seen from Table 3, the atomic ratio of metal In constantly reduces along with the raising of growth temperature, from 13.8 at. %
It is reduced to 6.3 at. % and decreases nearly 1 times, and the ratio of Cu element constantly increases and increases to 25.4 from 5.8 at. %
At. % adds nearly 4 times.This explanation is at CZTS/In2S3There is counterdiffusion at heterojunction boundary, and this counterdiffusion along with
The rising of growth temperature and constantly strengthen.The atomic ratio change of Zn and Sn element is little, illustrates that the element of diffusion is with In and Cu
Being main, the most substantial amounts of Cu element is from CZTS film diffusion to In2S3Thin film, and In element is from In2S3Film diffusion is to CZTS
Thin film.The ratio of the atomic ratio of In and Cu at assay surface again, finds the ratio nearly 4:1 of the atomic number of Cu and In, this explanation
In2S3Substantial amounts of Cu element, In is there is in thin film2S3Containing substantial amounts of cation vacancy, be a kind of easy doping material and
And, just can be had when the amount of Cu element of diffusion reaches 1:5:8 with the composition ratio of In and S element by Cu element doping
CuIn may be produced5S8, after the amount of diffusion Cu continues to increase, it is possible to further generate CuInS2。CuIn5S8It is a kind of narrow
The n-type semiconductor of band gap, and CuInS2It is then a kind of p-type semiconductor, in conjunction with energy band diagram analysis, the hetero-junctions sample of 200 DEG C of growths
Product generate the CuInS of p-type in interface2, so that In2S3Being bent downwardly by band of side.
The atomic ratio of each metallic element near table 3 heterojunction boundary
As seen from the above analysis, along with the raising of growth temperature, valence band rank are gradually increased, but due to indium sulfide
Energy gap also can change, so, the change on conduction band rank is that the two change is caused.But it can be seen that 150 DEG C of growths
Sample conduction band rank be 0.22 ± 0.1eV, within optimum 0.3eV.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (6)
1. the method regulating and controlling copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank, it is characterised in that: comprise the following steps:
Step 1): be cleaned transparent glass sheet processing, will carry out in deionized water, acetone and ethanol successively by sheet glass
Supersound process, then takes out, dries；
Step 2): after copper acetate monohydrate, Zinc diacetate dihydrate and two hydrated stannous chlorides are mixed, add thiourea and be dissolved into
In ethylene glycol monomethyl ether, and add stabilizer, 50 DEG C of heating in water bath stirring 1h, obtain colloid；
Step 3): utilize spin-coating method by step 2) colloid prepared is coated on the drying sheet glass of step 1) gained, through 280 DEG C
Baking becomes copper-zinc-tin-sulfur preformed layer thin film；It is repeated several times to reach required film thickness, thickness 800nm；
Step 4): the copper-zinc-tin-sulfur preformed layer film sample that step 3) is prepared puts into quartz boat, then puts the stone in vulcanizing oven into
In English glass tubing, with mechanical pump to quartz glass tube evacuation, after below 5pa, close mechanical pump；Then toward the quartz in stove
Glass tubing is passed through N2Gas, flow is 180sccm, keeps being passed through N after logical 10min2Gas, then it is passed through H2S gas, flow is
20sccm；After ten minutes, start to allow vulcanizing oven heat up, after 1h, be raised to 580 DEG C, keep temperature 1h, subsequently by cooling water cooling
4h, to room temperature, prepares solar cell absorbed layer material copper zinc-tin-sulfur film；
Step 5): the copper-zinc-tin-sulfur film that step 4) prepares is placed in the evaporation cavity of vacuum evaporation stove；Indium sulfide powder is put
In evaporation boat, then put in evaporation cavity；After evaporation cavity evacuation, the glass substrate being loaded with copper-zinc-tin-sulfur film is carried out
Being heated or not heated process, if carrying out heat treated, substrate temperature being heated to 100 ~ 200 DEG C；Subsequent power-up stream is to evaporation boat
Heating, the indium sulfide powder to evaporation boat evaporates completely, and now electric current is 100A, then stops evaporation, obtains copper zinc
Stannum sulfur/indium sulfide hetero-junctions.
A kind of regulate and control copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank method, it is characterised in that: step
Rapid 1) time of described supersound process is 15 minutes；The temperature of described drying is 100 DEG C, and drying time is 25-40 minute.
A kind of regulate and control copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank method, it is characterised in that: step
Rapid 5), in, adding the speed that evaporation boat heats by electric current is 10A/ minute.
A kind of regulate and control copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank method, it is characterised in that: step
Rapid 5), in, in copper-zinc-tin-sulfur/indium sulfide hetero-junctions that evaporation obtains, indium sulfide thin film thickness is 3-5nm.
A kind of regulate and control copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank method, it is characterised in that: step
Rapid 5), in, the quality of the indium sulfide powder being placed in evaporation boat is 5mg.
A kind of regulate and control copper-zinc-tin-sulfur/indium sulfide heterogeneous ligament rank method, it is characterised in that: step
Rapid 5) evaporation boat described in is molybdenum boat；During evacuation, it is 1.0 × 10 by being evacuated to vacuum in evaporation cavity-3Handkerchief.
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| CN103606591A (en) * | 2013-11-13 | 2014-02-26 | 福州大学 | A preparation method for a copper zinc tin sulfur film of solar battery absorbing layer materials |
| WO2014184661A2 (en) * | 2013-03-14 | 2014-11-20 | First Solar Malaysia Sdn.Bhd. | Photovoltaic devices and method of making |
| CN105428217A (en) * | 2015-11-23 | 2016-03-23 | 福州大学 | Cu-doped indium sulfide film preparation method |
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| CN103606591A (en) * | 2013-11-13 | 2014-02-26 | 福州大学 | A preparation method for a copper zinc tin sulfur film of solar battery absorbing layer materials |
| CN105428217A (en) * | 2015-11-23 | 2016-03-23 | 福州大学 | Cu-doped indium sulfide film preparation method |
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| CN109346613A (en) * | 2018-10-11 | 2019-02-15 | 电子科技大学 | Differential temperature preheats spin coating proceeding and the organic photodetector based on technique preparation |
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