CN105957920B - A kind of Cu3BiS3The preparation method of film - Google Patents
A kind of Cu3BiS3The preparation method of film Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 78
- 239000002243 precursor Substances 0.000 claims abstract description 77
- 239000010408 film Substances 0.000 claims abstract description 63
- 239000007864 aqueous solution Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000000137 annealing Methods 0.000 claims abstract description 33
- 239000010409 thin film Substances 0.000 claims abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000000873 masking effect Effects 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000005864 Sulphur Substances 0.000 claims abstract description 13
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical group CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229960002447 thiram Drugs 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 238000004528 spin coating Methods 0.000 claims description 32
- 239000012298 atmosphere Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 9
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- 239000012071 phase Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 9
- WKLWZEWIYUTZNJ-UHFFFAOYSA-K diacetyloxybismuthanyl acetate Chemical class [Bi+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WKLWZEWIYUTZNJ-UHFFFAOYSA-K 0.000 description 7
- 229910052738 indium Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910004613 CdTe Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a kind of Cu3BiS3The preparation method of film, comprises the following steps：First, sulphur source, copper source and bismuth source are dissolved in solvent, precursor aqueous solution is obtained after being well mixed, wherein sulphur source is thiuram；2nd, precursor aqueous solution is obtained into precursor thin film by liquid phase method masking after drying；3rd, anneal, obtain Cu3BiS3Film.Preparation process is simple of the present invention, precursor aqueous solution composition is simple, and equipment requirement is low, and the film for preparing is Cu3BiS3Pure phase, the selection window of its parameter and annealing is big.
Description
Technical field
The invention belongs to thin-film material technical field, and in particular to a kind of Cu3BiS3The preparation method of film.
Background technology
To solve the serious energy crisis that today's society is present, the mankind are gradually increased the profit to clean energy resourcies such as solar energy
With.Solar cell is the mode effectively using solar energy.In second generation thin-film solar cells, only GIGS batteries and
CdTe battery has obtained practical application.But both hull cells there are problems that respective.For CIGS solar cells, material
Metal In reserves in material are less, expensive, and raw material supply problem is there may be in large-scale application；For the CdTe sun
Energy battery, the reserves of Te elements are also less, while the toxicity of Cd will produce potential problem of environmental pollution.
Therefore, inexpensively, environmental protection, the absorbing layer of thin film solar cell material of rich reserves turns into the target that everybody finds.
The material paid close attention to by everybody has CZTS and Cu3BiS3Material.Wherein Cu3BiS3All elements are in nature in material
In reserves it is very abundant, and environmental sound.Additionally, Cu3BiS3Material have suitable energy gap (1.4-1.5eV) and
The absorption coefficient of light high (>105cm-1), it is highly suitable as solar battery obsorbing layer material.
Existing Cu3BiS3Method for manufacturing thin film includes sputtering method, thermal evaporation, alloy after cure method etc., these physics classes
Method has the problems such as equipment cost is high, and area battery prepares difficult, and these preparation methods are also not apparent from advancing Cu3BiS3
The rapid progress of battery.It is by Cu3BiS3Material obtains practical application in solar cells, the Cu for also needing exploitation new3BiS3It is thin
The preparation method of film.
The content of the invention
The technical problems to be solved by the invention are for above-mentioned the deficiencies in the prior art, there is provided a kind of Cu3BiS3Film
Preparation method., from thiuram as the sulphur source in precursor aqueous solution, precursor aqueous solution composition is simple, and equipment requirement is low for the method,
The film for preparing is Cu3BiS3Pure phase, the selection window of its parameter and annealing is big.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of Cu3BiS3The preparation method of film, its
It is characterised by, the method is comprised the following steps：
Step one, precursor aqueous solution processed：Copper source, bismuth source and sulphur source are dissolved in solvent, precursor aqueous solution is obtained after being well mixed；
Copper source is copper nitrate, copper chloride or copper acetate, and the bismuth source is bismuth nitrate, bismuth chloride or bismuth acetate, and the sulphur source is the autumn
Lan Mu, the solvent is DMF or dimethyl sulfoxide (DMSO)；Copper source, bismuth source and sulphur source rubs in the precursor aqueous solution
You are than being (2.8~3.5): (0.9~1.1): (0.9~1.1)；
Step 2, masking：By precursor aqueous solution described in step one by liquid phase method masking, precursor thin film is obtained after drying；
Step 3, annealing：Precursor thin film described in step 2 is made annealing treatment under atmosphere protection, Cu is obtained3BiS3
Film.
A kind of above-mentioned Cu3BiS3The preparation method of film, it is characterised in that precursor aqueous solution mid-autumn described in step one is blue
The concentration of nurse is 0.05mol/L~0.5mol/L.
A kind of above-mentioned Cu3BiS3The preparation method of film, it is characterised in that liquid phase method described in step 2 is spin-coating method.
A kind of above-mentioned Cu3BiS3The preparation method of film, it is characterised in that the temperature dried described in step 2 is 100
DEG C~300 DEG C.
A kind of above-mentioned Cu3BiS3The preparation method of film, it is characterised in that atmosphere described in step 3 be S atmosphere or
H2S atmosphere.
A kind of above-mentioned Cu3BiS3The preparation method of film, it is characterised in that the temperature made annealing treatment described in step 3
It it is 300 DEG C~500 DEG C, the time of the annealing is 0.5h~10h.
A kind of above-mentioned Cu3BiS3The preparation method of film, it is characterised in that the solvent also includes water, the body of the water
Product is the 0.1%~1.5% of precursor aqueous solution cumulative volume.
The present invention has advantages below compared with prior art：
1st, from thiuram as the sulphur source in precursor aqueous solution, the chemical name of thiuram is tetramethyl autumn orchid to the present invention
Nurse disulphide, chemical formula is C6H12N2S4, because having 4 sulphur atoms in a thiuram molecule, make it have and preferably match somebody with somebody
Capability, the precursor aqueous solution stabilization of preparation, while thiuram can also provide the sulphur source of abundance in precursor aqueous solution, particularly with
Cu3BiS3Material, the stoichiometric proportion of element sulphur itself is higher, due to having 4 sulphur atoms in a thiuram molecule, only needs
Meet Cu by adding less amount of thiuram3BiS3Stoichiometry compares the requirement of S so that existing part sulphur in precursor thin film
Element is present, and advantageously reduces the annealing temperature and annealing time in subsequent annealing process.
2nd, the present invention has suitable viscosity and surface tension in itself added with the precursor aqueous solution of thiuram, can be easier
Obtain suitable film thickness, it may not be necessary to add other additives such as viscosity-controlling agent etc., make precursor aqueous solution composition more
Simply.The advantages of liquid phase method masking has inexpensive, easy large area is produced, can solve to be asked present in conventional physical method
Topic.
3rd, can also be to adding water as modifying agent in precursor aqueous solution in the present invention, the addition of appropriate water can be adjusted
Cu3BiS3The compactness extent of film, is conducive to obtaining more fine and close film.
The present invention is described in further detail with reference to the accompanying drawings and examples.
Brief description of the drawings
Fig. 1 is Cu prepared by the embodiment of the present invention 13BiS3The XRD spectrum of film.
Fig. 2 is Cu prepared by the embodiment of the present invention 13BiS3The SEM photograph of film.
Fig. 3 is Cu prepared by the embodiment of the present invention 23BiS3The XRD spectrum of film.
Fig. 4 is Cu prepared by the embodiment of the present invention 63BiS3The SEM photograph of film.
Specific embodiment
Embodiment 1
The present embodiment Cu3BiS3The preparation method of film is comprised the following steps：
Step one, precursor aqueous solution processed：By 3.2mmol copper acetates, 1mmol bismuth acetates and 1mmol thiurams add 2mL N,
In dinethylformamide, ultrasonic dissolution is well mixed, and prepares precursor aqueous solution；
Step 2, masking：Precursor aqueous solution is spun on FTO glass by spin-coating method, spin coating parameters are 1500rpm spin coatings
20s, then 300 DEG C of drying 2min, repeat spin coating and drying course several times, obtain precursor thin film；
Step 3, annealing：By precursor thin film under S element atmosphere in 300 DEG C anneal 30min, obtain Cu3BiS3Film.
The Cu that Fig. 1 is prepared for the present embodiment3BiS3The XRD spectrum of film, from figure 1 it appears that except FTO glass
Outside the diffraction maximum of glass, remaining diffraction maximum both corresponds to Cu3BiS3The diffraction maximum of phase, that illustrate acquisition is Cu3BiS3Pure phase.Fig. 2 is
The Cu that the present embodiment is prepared3BiS3The SEM photograph of film.The particle size in film is sub-micron as seen from Figure 2
Level.
Embodiment 2
The present embodiment Cu3BiS3The preparation method of film is comprised the following steps：
Step one, precursor aqueous solution processed：By 0.7mmol copper nitrates, 0.2mmol bismuth nitrates and 0.2mmol thiurams add 2mL
In DMF, ultrasonic dissolution is well mixed, and prepares precursor aqueous solution.
Step 2, masking：Precursor aqueous solution is spun on FTO glass by spin-coating method, spin coating parameters are 2000rpm spin coatings
20s, then 300 DEG C of drying 2min, repeat the process several times, obtain precursor thin film；
Step 3, annealing：By precursor thin film under S element atmosphere 400 DEG C annealing 10h, obtain Cu3BiS3Film.
The Cu that Fig. 3 is prepared for the present embodiment3BiS3The XRD spectrum of film, from figure 3, it can be seen that the present embodiment system
The standby film for obtaining is Cu3BiS3Pure phase.
Embodiment 3
The present embodiment Cu3BiS3The preparation method of film is comprised the following steps：
Step one, precursor aqueous solution processed：By 1.4mmol copper chlorides, 0.5mmol bismuth chlorides and 0.5mmol thiurams add 2mL
Dimethyl sulfoxide (DMSO), ultrasonic dissolution is well mixed, and prepares precursor aqueous solution；
Step 2, masking：Precursor aqueous solution is spun on the molybdenum film of glass substrate surface by spin-coating method, spin coating parameters are
1500rpm spin coating 20s, then 200 DEG C of drying 5min, repeat the process several times, obtain precursor thin film；
Step 3, annealing：By precursor thin film under hydrogen sulfide atmosphere 300 DEG C annealing 3h, obtain Cu3BiS3Film.
Embodiment 4
The present embodiment Cu3BiS3The preparation method of film is comprised the following steps：
Step one, precursor aqueous solution processed：By 3mmol copper acetates, 0.9mmol bismuth acetates and 0.9mmol thiurams add 2mL
In DMF, ultrasonic dissolution is well mixed, and prepares precursor aqueous solution；
Step 2, masking：Precursor aqueous solution is spun on slide by spin-coating method, spin coating parameters are 1500rpm spin coatings
20s, then 200 DEG C of drying 5min, repeat the process several times, obtain precursor thin film；
Step 3, annealing：By precursor thin film under S element atmosphere 300 DEG C annealing 0.5h, obtain Cu3BiS3Film.
Embodiment 5
The present embodiment Cu3BiS3The preparation method of film is comprised the following steps：
Step one, precursor aqueous solution processed：By 2.9mmol copper acetates, 1.1mmol bismuth acetates and 1.1mmol thiurams add 2mL
In DMF, ultrasonic dissolution is well mixed, and prepares precursor aqueous solution；
Step 2, masking：Precursor aqueous solution is spun on FTO glass by spin-coating method, spin coating parameters are 1500rpm spin coatings
20s, then 300 DEG C of drying 2min, repeat spin coating and drying course several times, obtain precursor thin film；
Step 3, annealing：By precursor thin film under S element atmosphere in 300 DEG C anneal 30min, obtain Cu3BiS3Film.
The Cu that the present embodiment is prepared3BiS3The non-constant width of annealing process window of film, annealing temperature is 300~400
DEG C, annealing time can form Cu in the scope of 0.5h~8h3BiS3Phase, annealing process window so wide will be highly beneficial
In further optimization annealing parameter, high-quality Cu is obtained3BiS3Film is realizing carrying for thin-film solar cells transformation efficiency
It is high.
Additionally, the ratio of Cu/Bi is also one of key parameter in precursor aqueous solution, when the ratio of Cu/Bi in precursor aqueous solution is small
When 3.3, the ratio of Cu/Bi is then less than 3.0 in the film obtained after annealing, is easier to obtain Cu in this case3BiS3It is pure
Phase, and the ratio of Cu/Bi higher in film can then cause the excess of Cu and generate copper sulfide dephasign, to Electrical performance shadow
Sound is larger, and the generation of copper sulfide dephasign is very unfavorable.Therefore, the ratio of Cu/Bi should be less than 3.3, the ratio of preferred Cu/Bi
Example is less than 3.2.
Embodiment 6
The present embodiment Cu3BiS3The preparation method of film is comprised the following steps：
Step one, precursor aqueous solution processed：By 3.2mmol copper acetates, 1mmol bismuth acetates and 1mmol thiurams add 2mL N,
In dinethylformamide, the deionized water of 20 μ L is added, ultrasonic dissolution is well mixed, and prepares precursor aqueous solution；
Step 2, masking：Precursor aqueous solution is spun on FTO glass by spin-coating method, spin coating parameters are 1500rpm spin coatings
20s, then 300 DEG C of drying 2min, repeat the process several times, obtain precursor thin film；
Step 3, annealing：By precursor thin film under S atmosphere 300 DEG C annealing 30min, obtain Cu3BiS3Film.
The Cu that Fig. 4 is prepared for the present embodiment3BiS3The SEM photograph of film.Particle chi in film as seen from Figure 4
Very little is still submicron order.Fig. 4 is compared with Fig. 2, finds to add the Cu obtained after a small amount of water3BiS3Film is more fine and close, says
The addition of bright a small amount of water is conducive to the densification of film.
Embodiment 7
The present embodiment Cu3BiS3The preparation method of film is comprised the following steps：
Step one, precursor aqueous solution processed：By 3.2mmol copper acetates, 1mmol bismuth acetates and 1mmol thiurams add 2mL N,
In dinethylformamide, the deionized water of 10 μ L is added, ultrasonic dissolution is well mixed, and prepares precursor aqueous solution；
Step 2, masking：Precursor aqueous solution is spun on FTO glass by spin-coating method, spin coating parameters are 1500rpm spin coatings
20s, then 300 DEG C of drying 2min, repeat the process several times, obtain precursor thin film；
Step 3, annealing：By precursor thin film under S element atmosphere 300 DEG C annealing 30min, obtain Cu3BiS3Film.
Embodiment 8
The present embodiment Cu3BiS3The preparation method of film is comprised the following steps：
Step one, precursor aqueous solution processed：By 3.2mmol copper acetates, 1mmol bismuth acetates and 1mmol thiurams add 2mL N,
In dinethylformamide, the deionized water of 30 μ L is added, ultrasonic dissolution is well mixed, and prepares precursor aqueous solution；
Step 2, masking：Precursor aqueous solution is spun on FTO glass by spin-coating method, spin coating parameters are 1500rpm spin coatings
20s, then 300 DEG C of drying 2min, repeat the process several times, obtain precursor thin film；
Step 3, annealing：By precursor thin film under S element atmosphere 300 DEG C annealing 30min, obtain Cu3BiS3Film.
Embodiment 9
The present embodiment Cu3BiS3The preparation method of film is comprised the following steps：
Step one, precursor aqueous solution processed：By 3.2mmol copper acetates, 1mmol bismuth acetates and 1mmol thiurams add 2mL N,
In dinethylformamide, the deionized water of 2 μ L is added, ultrasonic dissolution is well mixed, and prepares precursor aqueous solution；
Step 2, masking：Precursor aqueous solution is spun on FTO glass by spin-coating method, spin coating parameters are 1500rpm spin coatings
20s, then 300 DEG C of drying 2min, repeat the process several times, obtain precursor thin film；
Step 3, annealing：By precursor thin film under S element atmosphere 300 DEG C annealing 30min, obtain Cu3BiS3Film.
By embodiment 6 to 9, the influence of the addition of water to technique is larger, (is more than when the addition of water is too high
Precursor aqueous solution volume fraction 3%), the film planarization that spin coating is obtained is substantially reduced, and uneven situation occurs, and too low
Water addition then influences smaller to compactness extent, and the addition of water is 0.1%~1.5% more suitable for precursor aqueous solution volume,
Preferably 0.1%~1%.
The above, is only presently preferred embodiments of the present invention, and not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art is substantially made to above example, still fall within technical solution of the present invention
Protection domain in.
Claims (6)
1. a kind of Cu3BiS3The preparation method of film, it is characterised in that the method is comprised the following steps：
Step one, precursor aqueous solution processed：Copper source, bismuth source and sulphur source are dissolved in solvent, precursor aqueous solution is obtained after being well mixed；It is described
Copper source is copper nitrate, copper chloride or copper acetate, and the bismuth source is bismuth nitrate, bismuth chloride or bismuth acetate, and the sulphur source is thiuram,
The solvent is N,N-dimethylformamide or dimethyl sulfoxide (DMSO)；The mol ratio in copper source, bismuth source and sulphur source in the precursor aqueous solution
It is (2.8~3.5): (0.9~1.1): (0.9~1.1)；The solvent also includes water, and the volume of the water is that precursor aqueous solution is total
The 0.1%~1.5% of volume；
Step 2, masking：By precursor aqueous solution described in step one by liquid phase method masking, precursor thin film is obtained after drying；Step
3rd, anneal：Precursor thin film described in step 2 is made annealing treatment under atmosphere protection, Cu is obtained3BiS3Film.
2. a kind of Cu according to claim 13BiS3The preparation method of film, it is characterised in that forerunner described in step one
The concentration of thiuram is 0.05mol/L~0.5mol/L in solution.
3. a kind of Cu according to claim 13BiS3The preparation method of film, it is characterised in that liquid phase described in step 2
Method is spin-coating method.
4. a kind of Cu according to claim 13BiS3The preparation method of film, it is characterised in that dried described in step 2
Temperature be 100 DEG C~300 DEG C.
5. a kind of Cu according to claim 13BiS3The preparation method of film, it is characterised in that atmosphere described in step 3
It is S atmosphere or H2S atmosphere.
6. a kind of Cu according to claim 13BiS3The preparation method of film, it is characterised in that annealed described in step 3
The temperature for the treatment of is 300 DEG C~500 DEG C, and the time of the annealing is 0.5h~10h.
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| CN201610452771.3A CN105957920B (en) | 2016-06-21 | 2016-06-21 | A kind of Cu3BiS3The preparation method of film |
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| CN201610452771.3A CN105957920B (en) | 2016-06-21 | 2016-06-21 | A kind of Cu3BiS3The preparation method of film |
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