CN105957920A - Preparation method for Cu<3>BiS<3> thin film - Google Patents
Preparation method for Cu<3>BiS<3> thin film Download PDFInfo
- Publication number
- CN105957920A CN105957920A CN201610452771.3A CN201610452771A CN105957920A CN 105957920 A CN105957920 A CN 105957920A CN 201610452771 A CN201610452771 A CN 201610452771A CN 105957920 A CN105957920 A CN 105957920A
- Authority
- CN
- China
- Prior art keywords
- thin film
- bis
- preparation
- aqueous solution
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000010949 copper Substances 0.000 claims abstract description 78
- 239000002243 precursor Substances 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000000137 annealing Methods 0.000 claims abstract description 34
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229960002447 thiram Drugs 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 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
- 239000002904 solvent Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 45
- 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
- 230000000873 masking effect Effects 0.000 claims description 14
- 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 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 12
- 239000012071 phase Substances 0.000 abstract description 9
- 239000010408 film Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000004090 dissolution Methods 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
- 230000008859 change Effects 0.000 description 3
- 229910004613 CdTe Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 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
- 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
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 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
- 238000000053 physical method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 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
-
- 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
Landscapes
- 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 preparation method for a Cu<3>BiS<3> thin film. The preparation method comprises the following steps of step 1, dissolving a sulfur source, a copper source and a bismuth source into a solvent to be mixed uniformly to obtain a precursor solution, wherein thiuram is taken as the sulfur source; step 2, preparing a film from the precursor solution through a liquid phase method, and drying the film to obtain a precursor thin film; and step 3, performing annealing on the thin film to obtain the Cu<3>BiS<3> thin film. According to the preparation method, the preparation process is simple; the precursor solution has simple compositions; the requirement on the equipment is low; the prepared thin film is Cu<3>BiS<3> pure phase; and the selection window of the annealing process parameters is large.
Description
Technical field
The invention belongs to thin-film material technical field, be specifically related to a kind of Cu3BiS3The preparation side of thin film
Method.
Background technology
For solving the serious energy crisis that society exists, the mankind are gradually increased and clean solar energy etc.
The utilization of the energy.Solaode is the mode effectively utilizing solar energy.At second filial generation thin film solar
In battery, only GIGS battery and CdTe battery have obtained actual application.But both thin film
There is respective problem in battery.For CIGS solaode, the metal In reserves in material are less,
Expensive, raw material supply problem is there may be when large-scale application；For CdTe solar-electricity
Pond, the reserves of Te element are the most less, and the toxicity of Cd will produce potential problem of environmental pollution simultaneously.
Therefore, inexpensively, environmental protection, the absorbing layer of thin film solar cell material of rich reserves becomes everybody
The target found.The material paid close attention to by everybody has CZTS and Cu3BiS3Material.Wherein
Cu3BiS3In material, all elements reserves in nature are the abundantest, and environmental sound.This
Outward, Cu3BiS3Material has suitable energy gap (1.4-1.5eV) and the high absorption coefficient of light (>
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
Deng, the problems such as it is high that these physics class methods also exist equipment cost, area battery preparation difficulty, this
A little preparation methoies are also not apparent from advancing Cu3BiS3The rapid progress of battery.For by Cu3BiS3Material exists
Solaode obtains actual application, also needs to develop new Cu3BiS3The preparation method of thin film.
Summary of the invention
The technical problem to be solved is for above-mentioned the deficiencies in the prior art, it is provided that a kind of
Cu3BiS3The preparation method of thin film.The method selection thiuram is as the sulfur source in precursor aqueous solution, front
Driving solution composition simple, equipment requirements is low, and the thin film prepared is Cu3BiS3Pure phase, its annealing
The selection window of technological parameter is big.
For solving above-mentioned technical problem, the technical solution used in the present invention is: a kind of Cu3BiS3Thin film
Preparation method, it is characterised in that the method comprises the following steps:
Step one, precursor aqueous solution processed: Jiang Tongyuan, bismuth source and sulfur source are dissolved in solvent, after mix homogeneously
Obtain precursor aqueous solution；Copper source is copper nitrate, copper chloride or Schweinfurt green, described bismuth source be bismuth nitrate,
Bismuth chloride or bismuth acetate, described sulfur source is thiuram, and described solvent is DMF or two
Methyl sulfoxide；In described precursor aqueous solution, the mol ratio in copper source, bismuth source and sulfur source is
(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, after drying
To precursor thin film；
Step 3, annealing: precursor thin film described in step 2 is made annealing treatment under atmosphere protection,
Obtain Cu3BiS3Thin film.
Above-mentioned a kind of Cu3BiS3The preparation method of thin film, it is characterised in that before described in step one
Driving the concentration of thiuram in solution is 0.05mol/L～0.5mol/L.
Above-mentioned a kind of Cu3BiS3The preparation method of thin film, it is characterised in that liquid described in step 2
Phase method is spin-coating method.
Above-mentioned a kind of Cu3BiS3The preparation method of thin film, it is characterised in that dry described in step 2
Dry temperature is 100 DEG C～300 DEG C.
Above-mentioned a kind of Cu3BiS3The preparation method of thin film, it is characterised in that gas described in step 3
Atmosphere is S atmosphere or H2S atmosphere.
Above-mentioned a kind of Cu3BiS3The preparation method of thin film, it is characterised in that move back described in step 3
The temperature that fire processes is 300 DEG C～500 DEG C, and the time of described annealing is 0.5h～10h.
Above-mentioned a kind of Cu3BiS3The preparation method of thin film, it is characterised in that described solvent also includes
Water, the volume of described water is the 0.1%～1.5% of precursor aqueous solution cumulative volume.
The present invention compared with prior art has the advantage that
1, the present invention selects the thiuram as the sulfur source in precursor aqueous solution, the chemical name of thiuram to be
Tetramethyl thiuram disulfide, chemical formula is C6H12N2S4, because a thiuram molecule has
Having 4 sulphur atoms so that it is have preferable coordination ability, the precursor aqueous solution of preparation is stable, the autumn simultaneously
Blue nurse can also provide sufficient sulfur source in precursor aqueous solution, particularly with Cu3BiS3Material, itself
The stoichiometric proportion of element sulphur is higher, owing to there being 4 sulphur atoms in a thiuram molecule, only needs
Add less amount of thiuram and can meet Cu3BiS3The requirement of stoichiometry comparison S so that forerunner
In thin film, existing part element sulphur exists, and advantageously reduces the annealing temperature in subsequent annealing process and moves back
The fire time.
2, the present invention i.e. has suitable viscosity and surface tension added with the precursor aqueous solution of thiuram itself,
Can easier obtain suitable film thickness, it may not be necessary to add the regulation of other additives such as viscosity
Agent etc., make precursor aqueous solution composition simpler.Liquid phase method masking has low cost, and easy large area produces
Etc. advantage, problem present in conventional physical method can be solved.
3, the present invention can also add in precursor aqueous solution water as modifying agent, adding of appropriate water
Enter and can regulate Cu3BiS3The compactness extent of thin film, is conducive to obtaining the finest and close thin film.
With embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings.
Accompanying drawing explanation
Fig. 1 is the Cu of the embodiment of the present invention 1 preparation3BiS3The XRD figure spectrum of thin film.
Fig. 2 is the Cu of the embodiment of the present invention 1 preparation3BiS3The SEM photograph of thin film.
Fig. 3 is the Cu of the embodiment of the present invention 2 preparation3BiS3The XRD figure spectrum of thin film.
Fig. 4 is the Cu of the embodiment of the present invention 6 preparation3BiS3The SEM photograph of thin film.
Detailed description of the invention
Embodiment 1
The present embodiment Cu3BiS3The preparation method of thin film comprises the following steps:
Step one, precursor aqueous solution processed: by 3.2mmol Schweinfurt green, 1mmol bismuth acetate and 1mmol
Thiuram adds in 2mL DMF, and ultrasonic dissolution mix homogeneously, before preparing
Drive solution；
Step 2, masking: be spun on FTO glass by precursor aqueous solution by spin-coating method, spin coating is joined
Number is 1500rpm spin coating 20s, then dries 2min for 300 DEG C, repeats spin coating and drying course is some
Secondary, obtain precursor thin film；
Step 3, annealing: by precursor thin film under S element atmosphere in 300 DEG C anneal 30min,
To Cu3BiS3Thin film.
Fig. 1 is the Cu that the present embodiment prepares3BiS3The XRD figure spectrum of thin film, can from Fig. 1
To find out, in addition to the diffraction maximum of FTO glass, remaining diffraction maximum both corresponds to Cu3BiS3Spreading out of phase
Penetrate peak, illustrate to obtain for Cu3BiS3Pure phase.Fig. 2 is the Cu that the present embodiment prepares3BiS3
The SEM photograph of thin film.Particle size in thin film is submicron order as seen from Figure 2.
Embodiment 2
The present embodiment Cu3BiS3The preparation method of thin film comprises the following steps:
Step one, precursor aqueous solution processed: by 0.7mmol copper nitrate, 0.2mmol bismuth nitrate and 0.2mmol
Thiuram adds in 2mL DMF, and ultrasonic dissolution mix homogeneously, before preparing
Drive solution.
Step 2, masking: be spun on FTO glass by precursor aqueous solution by spin-coating method, spin coating is joined
Number is 2000rpm spin coating 20s, then dries 2min for 300 DEG C, repeats this process several times, obtain
Precursor thin film；
Step 3, annealing: by precursor thin film 400 DEG C of annealing 10h under S element atmosphere, obtain
Cu3BiS3Thin film.
Fig. 3 is the Cu that the present embodiment prepares3BiS3The XRD figure spectrum of thin film, can from Fig. 3
To find out, the thin film that the present embodiment prepares is Cu3BiS3Pure phase.
Embodiment 3
The present embodiment Cu3BiS3The preparation method of thin film comprises the following steps:
Step one, precursor aqueous solution processed: by 1.4mmol copper chloride, 0.5mmol bismuth chloride and 0.5mmol
Thiuram adds 2mL dimethyl sulfoxide, ultrasonic dissolution mix homogeneously, 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 is 1500rpm spin coating 20s, then dries 5min for 200 DEG C, repeats this process several times,
Obtain precursor thin film；
Step 3, annealing: by precursor thin film 300 DEG C of annealing 3h under hydrogen sulfide atmosphere, obtain Cu3BiS3
Thin film.
Embodiment 4
The present embodiment Cu3BiS3The preparation method of thin film comprises the following steps:
Step one, precursor aqueous solution processed: by 3mmol Schweinfurt green, 0.9mmol bismuth acetate and 0.9mmol
Thiuram adds in 2mL DMF, and ultrasonic dissolution mix homogeneously, before preparing
Drive solution；
Step 2, masking: be spun on microscope slide by precursor aqueous solution by spin-coating method, spin coating parameters is
1500rpm spin coating 20s, then dries 5min for 200 DEG C, repeats this process several times, obtain forerunner
Thin film；
Step 3, annealing: by precursor thin film 300 DEG C of annealing 0.5h under S element atmosphere, obtain
Cu3BiS3Thin film.
Embodiment 5
The present embodiment Cu3BiS3The preparation method of thin film comprises the following steps:
Step one, precursor aqueous solution processed: by 2.9mmol Schweinfurt green, 1.1mmol bismuth acetate and 1.1mmol
Thiuram adds in 2mL DMF, and ultrasonic dissolution mix homogeneously, before preparing
Drive solution；
Step 2, masking: be spun on FTO glass by precursor aqueous solution by spin-coating method, spin coating is joined
Number is 1500rpm spin coating 20s, then dries 2min for 300 DEG C, repeats spin coating and drying course is some
Secondary, obtain precursor thin film；
Step 3, annealing: by precursor thin film under S element atmosphere in 300 DEG C anneal 30min,
To Cu3BiS3Thin film.
The Cu that the present embodiment prepares3BiS3The non-constant width of annealing process window of thin film, annealing temperature
At 300～400 DEG C, annealing time all can form Cu in the scope of 0.5h～8h3BiS3Phase, the widest
Annealing process window will be very beneficial for optimizing annealing parameter further, it is thus achieved that high-quality
Cu3BiS3Thin film is to realize the raising of thin-film solar cells transformation efficiency.
Additionally, in precursor aqueous solution, the ratio of Cu/Bi is also one of key parameter, when in precursor aqueous solution
When the ratio of Cu/Bi is less than 3.3, in the thin film obtained after annealing, the ratio of Cu/Bi is then less than 3.0,
It is easier in this case obtain Cu3BiS3Pure phase, the ratio of Cu/Bi higher in thin film then can
The excess of Cu is caused to generate copper sulfide dephasign, relatively big to Electrical performance impact, vulcanize cupra
The generation of phase is the most disadvantageous.Therefore, the ratio of Cu/Bi should be less than 3.3, preferred Cu/Bi's
Ratio is less than 3.2.
Embodiment 6
The present embodiment Cu3BiS3The preparation method of thin film comprises the following steps:
Step one, precursor aqueous solution processed: by 3.2mmol Schweinfurt green, 1mmol bismuth acetate and 1mmol
Thiuram adds in 2mL DMF, adds the deionized water of 20 μ L, ultrasonic molten
Solve mix homogeneously, prepare precursor aqueous solution；
Step 2, masking: be spun on FTO glass by precursor aqueous solution by spin-coating method, spin coating is joined
Number is 1500rpm spin coating 20s, then dries 2min for 300 DEG C, repeats this process several times, obtain
Precursor thin film；
Step 3, annealing: by precursor thin film 300 DEG C of annealing 30min under S atmosphere, obtain Cu3BiS3
Thin film.
Fig. 4 is the Cu that the present embodiment prepares3BiS3The SEM photograph of thin film.Can be seen by Fig. 4
Going out particle size in thin film is still submicron order.Compared with Fig. 4 with Fig. 2, find to add on a small quantity
The Cu obtained after water3BiS3Thin film is the finest and close, and the densification that there was added beneficially thin film of a small amount of water is described
Change.
Embodiment 7
The present embodiment Cu3BiS3The preparation method of thin film comprises the following steps:
Step one, precursor aqueous solution processed: by 3.2mmol Schweinfurt green, 1mmol bismuth acetate and 1mmol
Thiuram adds in 2mL DMF, adds the deionized water of 10 μ L, ultrasonic molten
Solve mix homogeneously, prepare precursor aqueous solution；
Step 2, masking: be spun on FTO glass by precursor aqueous solution by spin-coating method, spin coating is joined
Number is 1500rpm spin coating 20s, then dries 2min for 300 DEG C, repeats this process several times, obtain
Precursor thin film；
Step 3, annealing: by precursor thin film 300 DEG C of annealing 30min under S element atmosphere, obtain
Cu3BiS3Thin film.
Embodiment 8
The present embodiment Cu3BiS3The preparation method of thin film comprises the following steps:
Step one, precursor aqueous solution processed: by 3.2mmol Schweinfurt green, 1mmol bismuth acetate and 1mmol
Thiuram adds in 2mL DMF, adds the deionized water of 30 μ L, ultrasonic molten
Solve mix homogeneously, prepare precursor aqueous solution；
Step 2, masking: be spun on FTO glass by precursor aqueous solution by spin-coating method, spin coating is joined
Number is 1500rpm spin coating 20s, then dries 2min for 300 DEG C, repeats this process several times, obtain
Precursor thin film；
Step 3, annealing: by precursor thin film 300 DEG C of annealing 30min under S element atmosphere, obtain
Cu3BiS3Thin film.
Embodiment 9
The present embodiment Cu3BiS3The preparation method of thin film comprises the following steps:
Step one, precursor aqueous solution processed: by 3.2mmol Schweinfurt green, 1mmol bismuth acetate and 1mmol
Thiuram adds in 2mL DMF, adds the deionized water of 2 μ L, ultrasonic molten
Solve mix homogeneously, prepare precursor aqueous solution；
Step 2, masking: be spun on FTO glass by precursor aqueous solution by spin-coating method, spin coating is joined
Number is 1500rpm spin coating 20s, then dries 2min for 300 DEG C, repeats this process several times, obtain
Precursor thin film；
Step 3, annealing: by precursor thin film 300 DEG C of annealing 30min under S element atmosphere, obtain
Cu3BiS3Thin film.
By embodiment 6 to 9, the addition of water is relatively big, when the addition of water on the impact of technique
(more than the 3% of precursor aqueous solution volume fraction) when measuring too high, the thin film planarization that spin coating obtains is significantly
Reducing, uneven situation occur, the lowest water addition is then less on compactness extent impact, water
Addition is precursor aqueous solution volume 0.1%～1.5% more suitable, preferably 0.1%～1%.
The above, be only presently preferred embodiments of the present invention, not impose any restrictions the present invention.All
It is that any simple modification, change and the equivalence made above example according to inventive technique essence becomes
Change, all still fall within the protection domain of technical solution of the present invention.
Claims (7)
1. a Cu3BiS3The preparation method of thin film, it is characterised in that the method comprises the following steps:
Step one, precursor aqueous solution processed: Jiang Tongyuan, bismuth source and sulfur source are dissolved in solvent, after mix homogeneously
Obtain precursor aqueous solution；Copper source is copper nitrate, copper chloride or Schweinfurt green, described bismuth source be bismuth nitrate,
Bismuth chloride or bismuth acetate, described sulfur source is thiuram, and described solvent is DMF or two
Methyl sulfoxide；In described precursor aqueous solution, the mol ratio in copper source, bismuth source and sulfur source is
(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, after drying
To precursor thin film；
Step 3, annealing: precursor thin film described in step 2 is made annealing treatment under atmosphere protection,
Obtain Cu3BiS3Thin film.
A kind of Cu the most according to claim 13BiS3The preparation method of thin film, it is characterised in that
Described in step one, in precursor aqueous solution, the concentration of thiuram is 0.05mol/L～0.5mol/L.
A kind of Cu the most according to claim 13BiS3The preparation method of thin film, it is characterised in that
Liquid phase method described in step 2 is spin-coating method.
A kind of Cu the most according to claim 13BiS3The preparation method of thin film, it is characterised in that
The temperature dried described in step 2 is 100 DEG C～300 DEG C.
A kind of Cu the most according to claim 13BiS3The preparation method of thin film, it is characterised in that
Atmosphere described in step 3 is S atmosphere or H2S atmosphere.
A kind of Cu the most according to claim 13BiS3The preparation method of thin film, it is characterised in that
Described in step 3, the temperature of annealing is 300 DEG C～500 DEG C, and the time of described annealing is
0.5h～10h.
A kind of Cu the most according to claim 13BiS3The preparation method of thin film, it is characterised in that
Solvent described in step one also includes that water, the volume of described water are precursor aqueous solution cumulative volume
0.1%～1.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610452771.3A CN105957920B (en) | 2016-06-21 | 2016-06-21 | A kind of Cu3BiS3The preparation method of film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610452771.3A CN105957920B (en) | 2016-06-21 | 2016-06-21 | A kind of Cu3BiS3The preparation method of film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105957920A true CN105957920A (en) | 2016-09-21 |
| CN105957920B CN105957920B (en) | 2017-06-06 |
Family
ID=56907016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610452771.3A Active CN105957920B (en) | 2016-06-21 | 2016-06-21 | A kind of Cu3BiS3The preparation method of film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105957920B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107256825A (en) * | 2017-07-04 | 2017-10-17 | 河北工业大学 | A kind of method that copper-zinc-tin-selefilm film is prepared based on the nanocrystalline ink of polyalcohol |
| CN113463109A (en) * | 2021-06-16 | 2021-10-01 | 华南师范大学 | Ternary copper-based compound semiconductor photoelectrode, unbiased sunlight water decomposition hydrogen production and oxygen production device and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002149A (en) * | 2010-11-10 | 2011-04-06 | 上海交通大学 | Method for preparing polylactic acid-zinc sulfide nano composite material |
| JP2014022569A (en) * | 2012-07-18 | 2014-02-03 | Kobe Steel Ltd | Photoelectric conversion element and manufacturing method therefor |
| CN103553130A (en) * | 2013-10-30 | 2014-02-05 | 上海师范大学 | Cu3BiS3 ternary sulfur nano material and preparation method thereof |
| CN104659123A (en) * | 2013-11-25 | 2015-05-27 | 华中科技大学 | Compound film solar battery and manufacturing method thereof |
| CN104709941A (en) * | 2015-03-16 | 2015-06-17 | 浙江大学宁波理工学院 | Preparation method for Cu3BiS3 micro/nanosheet |
-
2016
- 2016-06-21 CN CN201610452771.3A patent/CN105957920B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002149A (en) * | 2010-11-10 | 2011-04-06 | 上海交通大学 | Method for preparing polylactic acid-zinc sulfide nano composite material |
| JP2014022569A (en) * | 2012-07-18 | 2014-02-03 | Kobe Steel Ltd | Photoelectric conversion element and manufacturing method therefor |
| CN103553130A (en) * | 2013-10-30 | 2014-02-05 | 上海师范大学 | Cu3BiS3 ternary sulfur nano material and preparation method thereof |
| CN104659123A (en) * | 2013-11-25 | 2015-05-27 | 华中科技大学 | Compound film solar battery and manufacturing method thereof |
| CN104709941A (en) * | 2015-03-16 | 2015-06-17 | 浙江大学宁波理工学院 | Preparation method for Cu3BiS3 micro/nanosheet |
| CN104709941B (en) * | 2015-03-16 | 2016-04-27 | 浙江大学宁波理工学院 | A kind of Cu 3biS 3micro-/to receive the preparation method of sheet |
Non-Patent Citations (1)
| Title |
|---|
| SHENG LIU等: "Spray pyrolysis deposition of Cu3BiS3 thin films", 《THIN SOLID FILMS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107256825A (en) * | 2017-07-04 | 2017-10-17 | 河北工业大学 | A kind of method that copper-zinc-tin-selefilm film is prepared based on the nanocrystalline ink of polyalcohol |
| CN113463109A (en) * | 2021-06-16 | 2021-10-01 | 华南师范大学 | Ternary copper-based compound semiconductor photoelectrode, unbiased sunlight water decomposition hydrogen production and oxygen production device and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105957920B (en) | 2017-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Grain engineering for perovskite/silicon monolithic tandem solar cells with efficiency of 25.4% | |
| Liu et al. | Controlling CH3NH3PbI3–x Cl x film morphology with two-step annealing method for efficient hybrid perovskite solar cells | |
| Wan et al. | An alloy small molecule acceptor for green printing organic solar cells overcoming the scaling lag of efficiency | |
| CN110483745B (en) | Amphiphilic conjugated polymer and application thereof in preparation of reverse perovskite solar cell | |
| CN107275490B (en) | It is a kind of using penta pair of thiophene derivant of ring as the organic photovoltaic cell of electron acceptor | |
| CN107195697B (en) | A kind of preparation method of copper barium (strontium/calcium) tin sulphur (selenium) film | |
| CN105932114A (en) | Method for preparing solar cell absorbing layer film based on water bath and post-selenization | |
| CN109950404A (en) | A method of improving perovskite solar battery efficiency and hydrothermal stability | |
| CN107093650A (en) | A kind of method for preparing copper antimony sulphur solar battery obsorbing layer | |
| CN110518128A (en) | A kind of ACI type two dimension perovskite solar cell and preparation method thereof | |
| CN108389969A (en) | A kind of green solvent system and mixed solution being used to prepare perovskite solar cell calcium titanium ore bed | |
| CN104900810A (en) | Preparation method for uniform organic-inorganic perovskite film solar cell | |
| Ou et al. | Boosting the stability and efficiency of Cs2AgBiBr6 perovskite solar cells via Zn doping | |
| CN102503161A (en) | SnS nanocrystalline thin film preparation method | |
| CN108649124B (en) | High-efficiency inorganic perovskite solar cell and preparation method thereof | |
| CN105810831A (en) | Lead-tin hybrid perovskite thin film, and preparation method and application therefor | |
| Chen et al. | Self-sacrifice alkali acetate seed layer for efficient four-terminal perovskite/silicon tandem solar cells | |
| CN103318851B (en) | Copper-indium-gallium-sulfur-selenium solar cell, film absorbing layer and preparation method thereof | |
| Xu et al. | Low temperature-processed stable and high-efficiency carbon-based CsPbI2Br perovskite solar cells by additive strategy | |
| Chang et al. | Large-grain and smooth cesium doped CH3NH3PbI3 perovskite films by cesium iodide post-treatment for improved solar cells | |
| CN105957920A (en) | Preparation method for Cu<3>BiS<3> thin film | |
| Feng et al. | Enhanced performance in perovskite solar cells via bromide ion substitution and ethanol treatment | |
| Hu et al. | Highly efficient inverted planar solar cell using formamidinium-based quasi-two dimensional perovskites | |
| CN107768460B (en) | Bi2FeMo1-xNixO6Double-perovskite ferroelectric thin film and preparation method thereof | |
| Yuan et al. | CsPbI3 all-inorganic perovskite solar cells: Development Status and Theoretical Prediction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Ke Sanmin Inventor after: Hou Zhaoyang Inventor before: Hou Zhaoyang Inventor before: Ke Sanmin |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |