CN104201236A - Copper-zinc-tin sulfide thin film preparation method - Google Patents
Copper-zinc-tin sulfide thin film preparation method Download PDFInfo
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- CN104201236A CN104201236A CN201410391367.0A CN201410391367A CN104201236A CN 104201236 A CN104201236 A CN 104201236A CN 201410391367 A CN201410391367 A CN 201410391367A CN 104201236 A CN104201236 A CN 104201236A
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- zinc
- copper
- ion
- tin
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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 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010409 thin film Substances 0.000 title abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 51
- 229910001432 tin ion Inorganic materials 0.000 claims abstract description 34
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 33
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000002500 ions Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000001179 sorption measurement Methods 0.000 claims abstract description 20
- 125000002091 cationic group Chemical group 0.000 claims description 28
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 27
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052737 gold Inorganic materials 0.000 claims description 26
- 239000010931 gold Substances 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- -1 zinc sulphide compound Chemical class 0.000 claims description 20
- 239000005083 Zinc sulfide Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 150000001450 anions Chemical class 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 16
- 239000005361 soda-lime glass Substances 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 230000000536 complexating effect Effects 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical group [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 82
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000005987 sulfurization reaction Methods 0.000 abstract description 2
- YGSCHSPBVNFNTD-UHFFFAOYSA-N [S].[Sn].[Zn] Chemical compound [S].[Sn].[Zn] YGSCHSPBVNFNTD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 49
- 239000000203 mixture Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
- H01L31/036—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 their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03923—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
-
- 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
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- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
The invention relates to a copper-zinc-tin sulfide thin film preparation method. The preparation method includes the deposition of a copper ion and tin ion thin film compound on the surface of a substrate through a successive ion layer adsorption reaction method, the deposition of a zinc ion thin film compound and final high temperature sulfuration treatment for obtaining a zinc tin sulfide thin film. According to the preparation method, the problem of uneven film components due to ion competition in a copper ion, tin ion and zinc ion co-adsorption process can be solved, and the proportion of every component in the copper-zinc-tin sulfide thin film can be effectively controlled for the preparation of the single-phase copper-zinc-tin sulfide thin film.
Description
Technical field
The preparation method who the present invention relates to a kind of semiconductor copper zinc-tin-sulfur film, belongs to field of thin film solar cells.
Background technology
Photovoltaic generation new forms of energy development in recent years is rapid, enjoys the world to attract attention, and is expected to become the effective way that solves energy crisis and environmental crisis.Current solar cell is mainly silicon solar cell.But the light absorbing zone that silicon solar cell relies on is monocrystalline silicon or microcrystal silicon, it belongs to indirect gap semiconductor material, need thicker film thickness to go to absorb broad solar spectral, and monocrystalline silicon is with high costs.
Quaternary compound copper-zinc-tin-sulfur (Cu
2znSnS
4, be called for short CZTS) and belong to direct band gap P type semiconductor material, energy gap is mated with best energy gap (1.5eV) value of solar cell, and the absorption coefficient of light is greater than 10
4cm
-1, component earth's surface is abundant, nontoxic environmental friendliness, low cost.Therefore, copper-zinc-tin-sulfur material has very high photoelectric conversion efficiency, and the most potential substituted for silicon is as the light absorption layer material of novel solar battery.
A kind of method of continuous ionic layer adsorption reaction method (Successive Ion Layer Adsorption and Reaction) legal system for copper-zinc-tin-sulfur film that adopt of U.S. Patent Application Publication that on November 14th, 2013, disclosed publication number was US2013/0302597Al.The method comprises copper sulphate (CuSO
4), STANNOUS SULPHATE CRYSTALLINE (SnSO
4), zinc sulfate (ZnSO
4) be mixed to get a cationic solution (cationic solution); One substrate is immersed to this cationic solution and make substrate surface absorbing copper ion (Cu
2+), tin ion (Sn
2+), zinc ion (Zn
2+) cation; The substrate of this Liquidity limit of washed with de-ionized water; Substrate after this cleaning is immersed to a vulcanized sodium (Na
2s) anion solutions (anionic solution) makes substrate surface absorption sulphion (S
2-) anion; And annealing in process.But, in the method, be total in Liquidity limit process, due to Cu at substrate surface
2+, Sn
2+, Zn
2+ion competition, easily causes the bad control of the each component ratio of copper-zinc-tin-sulfur film, occurs dephasign in copper-zinc-tin-sulfur film.For example, from US2013/0302597Al accompanying drawing, 4-6 can find out, has obvious evil ZnO, SnO in its copper-zinc-tin-sulfur film of preparing
2dephasign.
Summary of the invention
In view of this, necessaryly provide a kind of and can effectively control the ratio of each composition in copper-zinc-tin-sulfur film, and prepare the method for single-phase copper zinc-tin-sulfur film.
A preparation method for copper-zinc-tin-sulfur film, the method comprises the following steps:
S10, takes out after a substrate is flooded in one first cationic solution, makes adsorption one copper ion of this substrate and the hybrid ionic layer of tin ion;
S11, cleans the hybrid ionic layer of this copper ion and tin ion;
S12, the substrate of the hybrid ionic layer that is formed with copper ion and tin ion is flooded to rear taking-up in one first anion solutions, make multiple first sulphions of adsorption of the hybrid ionic layer of this copper ion and tin ion, and the hybrid ionic layer of the plurality of the first sulphion and this copper ion and tin ion reacts and forms a copper sulfide and artificial gold mixing cpd film;
S13, cleans this copper sulfide and artificial gold mixing cpd film;
S14, takes out after the substrate that is formed with copper sulfide and artificial gold mixing cpd film is flooded in one second cationic solution, makes the adsorption one zinc ion layer of this copper sulfide and artificial gold mixing cpd film;
S15, cleans this zinc ion layer;
S16, after being flooded in one second anion solutions, the substrate that is formed with zinc ion layer takes out, make multiple second sulphions of adsorption of this second cationic layer, and the plurality of the second sulphion and this zinc ion layer react and form a zinc sulphide compound film;
S17, obtains an absorption and has the substrate of copper-zinc-tin-sulfur film presoma thereby clean this zinc sulphide compound film; And
S18, has the substrate of copper-zinc-tin-sulfur film presoma to carry out vulcanizing treatment to this absorption.
Compared with prior art, the preparation method of copper-zinc-tin-sulfur film provided by the invention, the filming compound of first deposited copper ion and tin ion, the filming compound of deposition zinc ion again, can solve copper ion, tin ion and zinc ion is total in adsorption process because ion competition causes the inhomogeneous of thin film composition, effectively control the ratio of each composition in copper-zinc-tin-sulfur film, preparation single-phase copper zinc-tin-sulfur film.
Brief description of the drawings
Fig. 1 is the preparation method's of copper-zinc-tin-sulfur film provided by the invention process chart.
Fig. 2 is ESEM (SEM) photo of the copper-zinc-tin-sulfur film prepared of the embodiment of the present invention.
Fig. 3 is the EDS EDAX results of the copper-zinc-tin-sulfur film prepared of the embodiment of the present invention.
Fig. 4 is the XRD x ray diffraction result of the copper-zinc-tin-sulfur film prepared of the embodiment of the present invention.
Fig. 5 is Raman (Raman) spectrum of the copper-zinc-tin-sulfur film prepared of the embodiment of the present invention.
Main element symbol description
| Substrate | 100 |
| Copper ion | 110 |
| Tin ion | 112 |
| The hybrid ionic layer of copper ion and tin ion | 114 |
| The first sulphion | 120 |
| Copper sulfide and artificial gold mixing cpd film | 122 |
| Zinc ion | 130 |
| Zinc ion layer | 132 |
| The second sulphion | 140 |
| Zinc sulphide compound film | 142 |
| Copper-zinc-tin-sulfur film presoma | 150 |
| Copper-zinc-tin-sulfur film | 152 |
Following embodiment further illustrates the present invention in connection with above-mentioned accompanying drawing.
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments, the preparation method of copper-zinc-tin-sulfur film provided by the invention is described in further detail.
Referring to Fig. 1, the preparation method of copper-zinc-tin-sulfur film 152 provided by the invention comprises the following steps:
S10, takes out after a substrate 100 is flooded in one first cationic solution, makes adsorption one copper ion of this substrate 100 and the hybrid ionic layer 114 of tin ion;
S11, cleans the hybrid ionic layer 114 of this copper ion and tin ion;
S12, the substrate 100 of the hybrid ionic layer 114 that is formed with copper ion and tin ion is flooded to rear taking-up in one first anion solutions, make multiple first sulphions 120 of adsorption of the hybrid ionic layer 114 of this copper ion and tin ion, and the plurality of the first sulphion 120 reacts and forms a copper sulfide and artificial gold mixing cpd film 122 with the hybrid ionic layer 114 of this copper ion and tin ion;
S13, cleans this copper sulfide and artificial gold mixing cpd film 122;
S14, takes out after the substrate 100 that forms copper sulfide and artificial gold mixing cpd film 122 is flooded in one second cationic solution, makes the adsorption one zinc ion layer 132 of this copper sulfide and artificial gold mixing cpd film 122;
S15, cleans this zinc ion layer 132;
S16, after being flooded in one second anion solutions, the substrate 100 that is formed with zinc ion layer 132 takes out, make multiple second sulphions 140 of adsorption of this zinc ion layer 132 2, and the plurality of the second sulphion 140 reacts and forms a zinc sulphide compound film 142 with this zinc ion layer 132;
S17, obtains an absorption and has the substrate 100 of copper-zinc-tin-sulfur film presoma 150 thereby clean this zinc sulphide compound film 142; And
S18, has the substrate 100 of copper-zinc-tin-sulfur film presoma 150 to carry out vulcanizing treatment to this absorption.
In step S10, described method of substrate 100 being flooded in the first cationic solution to rear taking-up specifically comprises: substrate 100 is immersed in the first cationic solution, keeps 20 seconds ~ 30 seconds, then slowly lift taking-up, wherein, pull rate is 100 mm/min ~ 300 mm/min.Described the first cationic solution is made up of deionized water, mantoquita, pink salt and complexing additive.Described mantoquita is CuSO
4or CuCl
2.Described pink salt is SnSO
4or SnCl
2.Described complexing additive is trisodium citrate or ammonium fluoride or triethanolamine.The purity of described mantoquita and pink salt is more than or equal to 99.99%.In described the first cationic solution, Cu
2+ion concentration be 0.005 mol/L ~ 0.02 mol/L, Sn
2+ion concentration be 0.01 mol/L ~ 0.05 mol/L.Further, can adopt watery hydrochloric acid and diluted sodium hydroxide solution to regulate the pH of the first cationic solution is 4.5 ~ 6.0.
The hybrid ionic layer 114 of described copper ion and tin ion comprises multiple copper ions 110 and multiple tin ion 112.The plurality of copper ion 110 and multiple tin ion 112 continuous arrangements form the stratiform mixed-cation layer of a densification.The surface that is appreciated that the hybrid ionic layer 114 of described copper ion and tin ion also can hang some discontinuous copper ion 110 and tin ions 112, is below called unnecessary copper ion 110 and tin ion 112.
Described substrate 100 can be soda-lime glass, tin indium oxide (ITO) electro-conductive glass, fluorine doped tin oxide (FTO) electro-conductive glass, sheet metal or metal coating glass.Before described substrate 100 is used, adopt successively alkaline cleaning fluid, acetone, isopropyl alcohol and high purity deionized water ultrasonic cleaning, nitrogen dries up.Then, use ultraviolet light (UV) cleaning machine to the surperficial ozone clean of substrate 100.
In step S11, the method for the hybrid ionic layer 114 of this copper ion of described cleaning and tin ion specifically comprises: substrate 100 is immersed in high purity deionized water, keeps 10 seconds ~ 30 seconds, then take out.The resistivity of high purity deionized water purity is 18 M Ω cm.In this cleaning step, hybrid ionic layer 114 unnecessary copper ion 110 and the tin ion 112 in surface of described copper ion and tin ion are removed.
In step S12, described method of taking out after the substrate 100 of hybrid ionic layer 114 that is formed with copper ion and tin ion is flooded in the first anion solutions specifically comprises: substrate 100 is immersed in the first anion solutions, keep 10 seconds ~ 30 seconds, then slowly lift taking-up, wherein, pull rate is 100 mm/min ~ 300 mm/min.Described the first anion solutions is N
2s salt or H
3cCSNH
2deionized water solution, and S
2-ion concentration be 0.01 mol/L ~ 0.08 mol/L.
Be appreciated that in this step S12, the copper ion 110 on the sulphion in described the first anion solutions and substrate 100 surfaces and tin ion 112 react and form this copper sulfide and artificial gold mixing cpd film 122.The surface that is appreciated that described copper sulfide and artificial gold mixing cpd film 122 also can hang some discontinuous first sulphions 120, is below called the first unnecessary sulphion 120.
In step S13, the method for this copper sulfide of described cleaning and artificial gold mixing cpd film 122 specifically comprises: substrate 100 is immersed in high purity deionized water, keeps 10 seconds ~ 30 seconds, then take out.In this cleaning step, described copper sulfide and artificial gold mixing cpd film 122 the first unnecessary sulphions 120 of surface are removed.
Further, all right repeating step S10 to S13 of the present invention, obtains certain thickness copper sulfide and artificial gold mixing cpd film 122.Preferably, number of repetition can be 60 ~ 100 times, to obtain copper sulfide and the artificial gold mixing cpd film 122 of thickness as 300 nanometer ~ 400 nanometers.
In step S14, described by the substrate 100 that is formed with copper sulfide and artificial gold mixing cpd film 122 in the second cationic solution, flood after take out method specifically comprise: substrate 100 is immersed in the second cationic solution, keep 20 seconds ~ 30 seconds, then slowly lift taking-up, wherein, pull rate is 100 mm/min ~ 300 mm/min.Described the second cationic solution is made up of deionized water and zinc salt.The purity of described zinc salt is more than or equal to 99.99%.Described zinc salt is ZnSO
4or ZnCl
2.The pH of described the second cationic solution is 5.0.In described the second cationic solution, Zn
2+ion concentration be 0.1 mol/L ~ 0.8 mol/L.
Described zinc ion layer 132 comprises that multiple continuously arranged zinc-tin ions 130 form the stratiform cationic layer of a densification.The surface that is appreciated that described zinc ion layer 132 also can hang some discontinuous zinc ions 130, is below called unnecessary zinc ion 130.
In step S15, the method for this zinc ion layer 132 of described cleaning specifically comprises: substrate 100 is immersed in high purity deionized water, keeps 10 seconds ~ 30 seconds, then take out.In this cleaning step, the described zinc ion layer 132 unnecessary zinc ion 130 in surface are removed.
In step S16, described by the substrate 100 that is formed with zinc ion layer 132 in the second anion solutions, flood after take out method specifically comprise: substrate 100 is immersed in the second anion solutions, keep 10 seconds ~ 30 seconds, then slowly lift taking-up, wherein, pull rate is 100 mm/min ~ 300 mm/min.Described the second anion solutions is N
2s salt or H
3cCSNH
2deionized water solution, and S
2-ion concentration be 0.01 mol/L ~ 0.08 mol/L.
Be appreciated that in this step S16, the zinc ion 130 on the sulphion in described the second anion solutions and substrate 100 surfaces reacts and forms a zinc sulphide compound film 142.The surface that is appreciated that described zinc sulphide compound film 142 also can hang some discontinuous second sulphions 140, is below called the second unnecessary sulphion 140.
In step S17, the method for this zinc sulphide compound film 142 of described cleaning specifically comprises: substrate 100 is immersed in high purity deionized water, keeps 10 seconds ~ 30 seconds, then take out.In this cleaning step, described zinc sulphide compound film 142 the second unnecessary sulphions 140 of surface are removed.Described copper-zinc-tin-sulfur film presoma 150 comprises copper sulfide and artificial gold mixing cpd film 122 and the zinc sulphide compound film 142 of stacked setting.
Further, all right repeating step S14 to S17 of the present invention, obtains certain thickness zinc sulphide compound film 142.Preferably, number of repetition can be 100 times ~ 200 times, to obtain the zinc sulphide compound film 142 of thickness as 100 nanometer ~ 200 nanometers.
In described step S18, the described method that has the substrate 100 of copper-zinc-tin-sulfur film presoma 150 to carry out vulcanizing treatment to this absorption specifically comprises the following steps: first, the above-mentioned substrate 100 that deposits copper-zinc-tin-sulfur film presoma 150 is placed in to two temperature-area tubular furnaces high-temperature region, wherein, solid-state sulphur source is placed in the low-temperature space of two temperature-area tubular furnaces, and sulphur purity is more than or equal to 99.999%; Secondly, vacuumize the oxygen of removing tube furnace the inside, and be filled with argon gas in tube furnace, wherein, argon pressure 4 × 10
-4bar ~ 5 × 10
-4bar; Then, be rapidly heated to 460 DEG C ~ 580 DEG C, be incubated 0.5 hour ~ 3 hours, wherein, heating rate is 10 degrees celsius/minute ~ 20 degrees celsius/minute.After described vulcanizing treatment, cooling naturally, obtains copper-zinc-tin-sulfur film 152.
Embodiment 1
(1), clean substrate.By 70 millimeters of length, the soda-lime glass that width is 30 millimeters adopts alkaline cleaning fluid, acetone, isopropyl alcohol and high purity deionized water ultrasonic cleaning 20 minutes successively, and nitrogen dries up.Then, use UV cleaning machine to soda-lime glass surface ozone clean 10 minutes, then put it into vacuum drying chamber for subsequent use.
(2), solution preparation.The slaine of employing 99.99% and high purity deionized water obtain solution A, B, C.A solution is CuSO
4, SnSO
4, trisodium citrate and deionized water composition mixed solution, wherein, Cu
2+ion concentration is 0.01 mol/L, Sn
2+ion concentration is 0.02 mol/L, and pH value of solution is 5.5.B solution is ZnSO
4deionized water solution, wherein, Zn
2+ion concentration is 0.5 mol/L, and B pH value of solution is 5.0.C solution is N
2the deionized water solution of S salt, wherein, S
2-ion concentration is 0.05 mol/L.
(3), prepare copper sulfide and artificial gold compound film.First, soda-lime glass is immersed in A solution to 20 seconds, now soda-lime glass surface will Adsorption of Cu
2+ion and Sn
2+ion, slowly lifts taking-up, pull rate 200 mm/min.Then, adopt high purity deionized water to clean ito glass surface, remove the unnecessary ion in surface.Then, soda-lime glass is immersed in C solution to 30 seconds, the S in C solution
2-ion will with the Cu on soda-lime glass surface
2+ion and Sn
2+ion reacts and forms copper sulfide and artificial gold, slowly lifts taking-up, pull rate 200 mm/min.Then, again adopt high purity deionized water to clean soda-lime glass surface, remove the unnecessary ion of adsorption.Lift continuously repetition 80 times, can obtain copper sulfide and artificial gold mixing cpd film that thickness is about 340 nanometers.
(4), zinc sulphide compound film preparation.First, the soda-lime glass that is prepared with copper sulfide and artificial gold film is immersed in B solution to 20 seconds, now Zn will be adsorbed in soda-lime glass surface
2+ion, slowly lifts taking-up, pull rate 200 mm/min.Then, adopt high purity deionized water to clean soda-lime glass surface, remove the unnecessary ion in surface.Then, soda-lime glass is immersed in C solution to 100 seconds, the S in C solution
2-ion will with the Zn on soda-lime glass surface
2+the ion formation zinc sulphide that reacts, slowly lifts taking-up, pull rate 200 mm/min.Then, again adopt high purity deionized water to clean soda-lime glass surface, remove the unnecessary ion in surface.Lift continuously repetition 150 times, can obtain the zinc sulphide compound film that thickness is about 160 nanometers.
(5), vulcanizing treatment.The above-mentioned heavy soda-lime glass that has copper sulfide and artificial gold mixing cpd film and zinc sulphide compound film is placed in to two temperature-area tubular furnaces high-temperature region inert atmosphere vulcanizing treatment, solid-state sulphur source is placed in low-temperature space, sulphur purity 99.999%, before sulfuration, vacuumize the oxygen of removing tube furnace the inside for 3 times, then be filled with argon gas, argon pressure is 5 × 10
-4bar, then, is rapidly heated to 500 DEG C of vulcanizing treatment, and heating rate 10 degrees celsius/minute, are incubated 1 hour, and natural cooling can obtain the copper-zinc-tin-sulfur film of 550 nanometer left and right thicknesses.
Referring to Fig. 2-5, the test result of the copper-zinc-tin-sulfur film of preparing for the embodiment of the present invention 1.From the SEM photo of Fig. 2, copper-zinc-tin-sulfur film prepared by the embodiment of the present invention 1 is made up of uniform nano particle, there is no hole and crackle.From the EDS power spectrum of Fig. 3, the element set of copper-zinc-tin-sulfur film prepared by the embodiment of the present invention 1 is proportional is Cu:Zn:Sn:S=21.49:15.48:12.11:50.92, wherein, and Cu/ (Zn+Sn)=0.78, Zn/Sn=1.28, copper-zinc-tin-sulfur film composition is the rich copper of poor zinc.Therefore, copper-zinc-tin-sulfur film composition can be controlled.Characterize from the XRD of Fig. 4, the XRD diffraction maximum of copper-zinc-tin-sulfur film prepared by the embodiment of the present invention 1 is mainly positioned at (101), (112), (200), (202), (220) are located, occur without other diffraction maximums, meet very much with the standard card (JCPDS#26-0575) of the XRD of copper-zinc-tin-sulfur.Characterize from the Raman of Fig. 5, the Raman peak value of copper-zinc-tin-sulfur film prepared by the embodiment of the present invention 1 is mainly positioned at 331cm
-1, also without ZnS phase (348cm
-1, 356cm
-1), Cu
2s phase (474cm
-1) and Cu
2snS
3phase (351cm
-1) etc. impurity phase, this copper-zinc-tin-sulfur film of preparing of explanation embodiment of the present invention 1 is single-phase copper zinc-tin-sulfur film.
The preparation method of copper-zinc-tin-sulfur film provided by the invention has following beneficial effect.The first, first deposit Cu
2+and Sn
2+filming compound, then deposit Zn
2+filming compound, can solve Cu
2+, Sn
2+and Zn
2+in the common adsorption process of ion, because ion competition causes the inhomogeneous of thin film composition, effectively control the ratio of each composition in copper-zinc-tin-sulfur film, preparation single-phase copper zinc-tin-sulfur film.The second, first deposit Cu
2+and Sn
2+filming compound, then deposit Zn
2+filming compound, can effectively control CZTS film deposition rate, make the copper-zinc-tin-sulfur film pattern that formed by nano particle more even, there is no hole crackle.
In addition, those skilled in the art can also do other and change in spirit of the present invention, and the variation that these do according to spirit of the present invention, all should be included in the present invention's scope required for protection.
Claims (10)
1. a preparation method for copper-zinc-tin-sulfur film, the method comprises the following steps:
S10, takes out after a substrate is flooded in one first cationic solution, makes adsorption one copper ion of this substrate and the hybrid ionic layer of tin ion;
S11, cleans the hybrid ionic layer of this copper ion and tin ion;
S12, the substrate of the hybrid ionic layer that is formed with copper ion and tin ion is flooded to rear taking-up in one first anion solutions, make multiple first sulphions of adsorption of the hybrid ionic layer of this copper ion and tin ion, and the hybrid ionic layer of the plurality of the first sulphion and this copper ion and tin ion reacts and forms a copper sulfide and artificial gold mixing cpd film;
S13, cleans this copper sulfide and artificial gold mixing cpd film;
S14, takes out after the substrate that is formed with copper sulfide and artificial gold mixing cpd film is flooded in one second cationic solution, makes the adsorption one zinc ion layer of this copper sulfide and artificial gold mixing cpd film;
S15, cleans this zinc ion layer;
S16, after being flooded in one second anion solutions, the substrate that is formed with zinc ion layer takes out, make multiple second sulphions of adsorption of this second cationic layer, and the plurality of the second sulphion and this zinc ion layer react and form a zinc sulphide compound film;
S17, obtains an absorption and has the substrate of copper-zinc-tin-sulfur film presoma thereby clean this zinc sulphide compound film; And
S18, has the substrate of copper-zinc-tin-sulfur film presoma to carry out vulcanizing treatment to this absorption.
2. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 1, is characterized in that, described substrate is soda-lime glass, indium tin oxide-coated glass, fluorine doped tin oxide electro-conductive glass, sheet metal or metal coating glass.
3. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 1, is characterized in that, described the first cationic solution is made up of deionized water, mantoquita, pink salt and complexing additive; In described the first cationic solution, Cu
2+ion concentration be 0.005 mol/L ~ 0.02 mol/L, Sn
2+ion concentration be 0.01 mol/L ~ 0.05 mol/L; The pH of described the first cationic solution is 4.5 ~ 6.0.
4. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 3, is characterized in that, described mantoquita is CuSO
4or CuCl
2, described pink salt is SnSO
4or SnCl
2, described complexing additive is trisodium citrate or ammonium fluoride or triethanolamine.
5. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 1, is characterized in that, the deionized water solution that described the second cationic solution is zinc salt; In described the second cationic solution, Zn
2+ion concentration be 0.1 mol/L ~ 0.8 mol/L.
6. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 5, is characterized in that, described zinc salt is ZnSO
4or ZnCl
2, the pH of described the second cationic solution is 5.0.
7. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 1, is characterized in that, described the first anion solutions and the second anion solutions are N
2s salt or H
3cCSNH
2deionized water solution, and S
2-ion concentration be 0.01 mol/L ~ 0.08 mol/L.
8. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 1, is characterized in that, further, repeating step S10 to S13, obtains copper sulfide and artificial gold mixing cpd film that thickness is 300 nanometer ~ 400 nanometers; And repeating step S14 to S17, obtaining thickness is the zinc sulphide compound film of 100 nanometer ~ 200 nanometers.
9. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 1, is characterized in that, described step S11, and S13, the cleaning method of S15 and S17, for this substrate is immersed in deionized water, keeps 10 seconds ~ 30 seconds, then takes out.
10. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 1, is characterized in that, the temperature of described vulcanizing treatment is 460 DEG C ~ 580 DEG C, and temperature retention time is 0.5 hour ~ 3 hours, and atmosphere is argon gas, and argon pressure is 4 × 10
-4bar ~ 5 × 10
-4bar.
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| CN104862753A (en) * | 2015-04-18 | 2015-08-26 | 云南师范大学 | Electrochemical preparation method of copper-zinc-tin-sulfur film absorbing layer |
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