CN105776888B - A method of preparing pyrite phase ferrous disulfide film - Google Patents
A method of preparing pyrite phase ferrous disulfide film Download PDFInfo
- Publication number
- CN105776888B CN105776888B CN201610077574.8A CN201610077574A CN105776888B CN 105776888 B CN105776888 B CN 105776888B CN 201610077574 A CN201610077574 A CN 201610077574A CN 105776888 B CN105776888 B CN 105776888B
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- Prior art keywords
- ferrous disulfide
- powder
- pyrite phase
- pyrite
- phase ferrous
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- 229940095991 ferrous disulfide Drugs 0.000 title claims abstract description 76
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 61
- 239000011028 pyrite Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 53
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000005864 Sulphur Substances 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011521 glass Substances 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 238000002347 injection Methods 0.000 claims abstract description 14
- 239000007924 injection Substances 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 9
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 9
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 9
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229960004756 ethanol Drugs 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 238000007650 screen-printing Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000012300 argon atmosphere Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 6
- 229910052786 argon Inorganic materials 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 description 10
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 7
- 229910000339 iron disulfide Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000027648 face development Effects 0.000 description 1
- 239000006101 laboratory sample Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3464—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide
- C03C17/347—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide comprising a sulfide or oxysulfide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/119—Deposition methods from solutions or suspensions by printing
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of methods for preparing pyrite phase ferrous disulfide film, obtain pyrite phase ferrous disulfide powder including the use of hydro-thermal method or hot injection method；Ferrous disulfide powder and ethyl cellulose, terpinol are tuned into slurry；By silk screen print method by ferrous disulfide slurry brush on glass or FTO Conducting Glass；It is heat-treated under sulphur and nitrogen/argon gas atmosphere, obtains pyrite phase ferrous disulfide film.The pyrite phase ferrous disulfide film that the present invention obtains can effectively overcome the problems, such as sulphur omission, can be used as the light absorbing layer of solar cell or use electrode.
Description
Technical field
The present invention relates to photoelectric material, new energy materials and technical field, especially a kind of pyrite phase ferrous disulfide is thin
Film and preparation method thereof.
Background technique
Pyrite phase ferrous disulfide (FeS2) there is suitable forbidden bandwidth (0.95eV) and the very big absorption coefficient of light (α
≥5×105, λ=700nm), and its component is cheap, rich reserves are nontoxic, in lithium battery and solar battery etc.
Field is a kind of is widely studied and the material of great application potential.
Currently, there are many methods for preparing pyrite phase ferrous disulfide film both at home and abroad, such as iron sulfide embrane method, colloidal sol
Gel method, electrodeposition process, hydro-thermal method, spray-on process etc..Existing the shortcomings that preparing pyrite phase ferrous disulfide film, is: film
In generally existing sulphur it is vacant, be not easy to obtain pyrite phase ferrous disulfide film.
Summary of the invention
The present invention exactly in view of the above-mentioned deficiencies in the prior art, provides a kind of pyrite phase ferrous disulfide film
Preparation method obtains pyrite phase ferrous disulfide film the purpose is to overcome sulphur omission phenomenon.
The purpose of the present invention is achieved through the following technical solutions: as shown in Figure 1, a kind of pyrite phase ferrous disulfide
The preparation method of film, it is characterised in that realize that steps are as follows:
(1) pyrite phase ferrous disulfide powder, pyrite phase ferrous disulfide powder are obtained using hydro-thermal method or hot injection method
It is spare after cleaned, dry；
(2) pyrite phase ferrous disulfide powder and ethyl cellulose, terpinol are mixed, magnetic agitation is uniform, is starched
Material；
(3) FTO electro-conductive glass or glass substrate are successively cleaned by ultrasonic in acetone, dehydrated alcohol, deionized water, are blown open
It is spare；
(4) by silk screen print method by pyrite phase ferrous disulfide slurry brush on glass or FTO Conducting Glass；
(5) ferrous disulfide film of distil sulphur powder and silk-screen printing is heat-treated, obtains pyrite phase on substrate
Ferrous disulfide film.
The step (1) obtains pyrite phase ferrous disulfide powder method using hydro-thermal method are as follows: by ferrous sulfate heptahydrate and
Polyvinylpyrrolidone is added in 90-95 ° of aqueous solution, and thiocarbamide is added after dissolution, above-mentioned solution is poured into polytetrafluoroethylene (PTFE)
In lining, sulphur powder and ethanol in proper amount is added to the 80% of liner volume, it is small that autoclave is put into 190-210 DEG C of reaction 4-40 in baking oven
When after be cooled to room temperature taking-up, by black powder use ethyl alcohol, deionized water, carbon disulfide washing, dried for standby.
The step (1) obtains pyrite phase ferrous disulfide powder method using hot injection method are as follows: the three of nitrogen protection
Be added oleyl amine and four water frerrous chlorides in neck bottle, 110-120 DEG C reaction 1-1.5 hours, acquisition solution A；In another nitrogen protection
Container in sulphur powder is dissolved in diphenyl ether, 1-1.5 hours acquisition solution Bs of 70-80 DEG C of reaction；B solution is injected into A by needle tubing
In solution, 210-220 DEG C is cooled to room temperature after reaction 5-24 hours.Black powder is used into dehydrated alcohol, chloroform, it is dry
For use.
The ferrous sulfate heptahydrate, polyvinylpyrrolidone, thiocarbamide and sulphur powder molar ratio be 1:1.5-2:2-2.5:4-
6。
The four water frerrous chloride, sulphur powder molar ratio be 1:5-7, every mM of four water frerrous chloride use 10 milliliters of oil
Amine dissolution, every mM of sulphur powder are dissolved with 1 milliliter of diphenyl ether.
When hydro-thermal method or hot injection method obtain different-shape pyrite phase ferrous disulfide powder in the step (1), pass through
Adjusting reaction time obtains the pyrite phase ferrous disulfide powder of variable grain size.
The pyrite phase ferrous disulfide powder of the step (2), ethyl cellulose, terpinol weight ratio be 1:1:4.
Step (5) the heat treatment sublimed sulfur powder purity is greater than 99%, and heat treatment temperature is 400-550 DEG C, in sulphur
It is heat-treated 1-3 hours under nitrogen/argon gas atmosphere.It is heat-treated under sulphur and nitrogen/argon gas atmosphere, ferrous disulfide film can be overcome
Generally existing sulphur omission problem in preparation process, the pyrite phase ferrous disulfide film of acquisition.
The pyrite phase ferrous disulfide film with a thickness of 1-10 microns.The thickness of pyrite phase ferrous disulfide film can
It is adjusted by the number of silk-screen printing.
Compared with the prior art, the present invention has the following advantages:
(1) present invention obtains pyrite phase ferrous disulfide powder using hydro-thermal method or hot injection method；By ferrous disulfide powder
Slurry is tuned into ethyl cellulose, terpinol；By silk screen print method by ferrous disulfide slurry brush in glass or FTO electro-conductive glass
On substrate；It is heat-treated under sulphur and nitrogen/argon gas atmosphere, obtains pyrite phase ferrous disulfide film.The yellow iron that the present invention obtains
Mine phase ferrous disulfide film can effectively overcome the problems, such as sulphur omission, can be used as the light absorbing layer of solar cell or use electrode.
(2) present invention obtains different-shape pyrite phase ferrous disulfide powder using hydro-thermal method or hot injection method；Pass through tune
Save reaction time, the pyrite phase ferrous disulfide powder of available variable grain size.
(3) present invention adjusts the thickness of pyrite phase ferrous disulfide film using the number of silk-screen printing.
(4) present invention prepares pyrite phase ferrous disulfide powder using hydro-thermal method or hot injection method, in sulphur and nitrogen/argon gas
It is heat-treated film under atmosphere, solves the problems, such as sulphur omission, obtains pyrite phase.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is that the scanning electron microscope for the pyrite phase iron disulfide particles that the present invention reacts preparation in 24 hours using hydro-thermal method is shone
Piece；
Fig. 3 is the scanning electron microscope for the pyrite phase iron disulfide particles that the present invention reacts preparation in 24 hours using hot injection method
Photo；
Fig. 4 is that the scanning electron microscope for the pyrite phase iron disulfide particles that the present invention reacts preparation in 39 hours using hydro-thermal method is shone
Piece；
Fig. 5 is the X-ray diffraction result of pyrite phase iron disulfide particles；
Fig. 6 is the Raman test result of pyrite phase ferrous disulfide film.
Specific embodiment
With reference to the accompanying drawing and the present invention is discussed in detail in specific embodiment.But embodiment below is only limitted to explain this hair
Bright, protection scope of the present invention should include the full content of claim, be not limited only to the present embodiment.
Embodiment 1
(1) 1.39g ferrous sulfate heptahydrate and 0.83g polyvinylpyrrolidone are added in 20ml deionized water, are stirred
0.76g thiocarbamide is added after half an hour；Above-mentioned solution is transferred in autoclave liner, 0.64g sulphur powder is added, ethanol in proper amount is added
Liquid volume is set to reach 80% or so of autoclave liner volume.Autoclave is put into batch-type furnace and is heated 24 hours for 200 DEG C.To
After temperature is cooled to room temperature, liquid in autoclave liner is poured out, successively uses ethyl alcohol, deionized water, carbon disulfide washs, most
Powder is placed in dried for standby in baking oven afterwards.Fig. 2 is the stereoscan photograph of the embodiment product；Fig. 5 is the embodiment product
X-ray diffraction result；Fig. 6 is the Raman results of the embodiment product.
(2) 0.1g ferrous disulfide powder is added in 5ml ethyl alcohol, 0.1g terpinol and 0.4g ethyl cellulose is added,
Magnetic agitation one day.
(3) FTO electro-conductive glass, glass substrate are successively cleaned by ultrasonic in acetone, dehydrated alcohol, deionized water, are blown open
It is spare；
(4) by silk screen print method by ferrous disulfide slurry brush in glass, FTO Conducting Glass；
(5) ferrous disulfide film of distil sulphur powder and silk-screen printing is put into quartz boat, in the tube furnace of nitrogen protection
In 450 DEG C be heat-treated 1 hour, obtain ferrous disulfide film, 1.2 microns of thickness.
Embodiment 2
(1) 10ml oleyl amine is added in the three-necked bottle of nitrogen protection, tetra- water frerrous chloride of 0.20g is added, keeps temperature
120 DEG C are reacted 1 hour, and solution A is obtained；0.19g sulphur powder is dissolved in 5ml diphenyl ether in the container of another nitrogen protection, 70
DEG C reaction 1 hour acquisition solution B；By needle tubing by B solution inject solution A in, 220 DEG C reaction 24 hours after be cooled to room temperature.
It is repeatedly rinsed using dehydrated alcohol, chloroform, powder is finally placed in dried for standby in baking oven.Fig. 3 is sweeping for the embodiment product
Retouch electromicroscopic photograph；Fig. 5 is the X-ray diffraction result of the embodiment product；Fig. 6 is the Raman results of the embodiment product.
(2) 0.1g ferrous disulfide powder is added in 5ml ethyl alcohol, 0.1g terpinol and 0.4g ethyl cellulose is added,
Magnetic agitation one day.
(3) FTO electro-conductive glass, glass substrate are successively cleaned by ultrasonic in acetone, dehydrated alcohol, deionized water, are blown open
It is spare；
(4) by silk screen print method by ferrous disulfide slurry brush in glass, FTO Conducting Glass；
(5) ferrous disulfide film of distil sulphur powder and silk-screen printing is put into quartz boat, in the tube furnace of nitrogen protection
In 450 DEG C be heat-treated 1 hour, obtain ferrous disulfide film, 1 microns of thickness.
Embodiment 3
(1) 1.39g ferrous sulfate heptahydrate and 0.83g polyvinylpyrrolidone are added in 20ml deionized water, are stirred
0.76g thiocarbamide is added after half an hour；Above-mentioned solution is transferred in autoclave liner, 0.64g sulphur powder is added, ethanol in proper amount is added
Liquid volume is set to reach 80% or so of autoclave liner volume.Autoclave is put into batch-type furnace and is heated 39 hours for 200 DEG C.To
After temperature is cooled to room temperature, liquid in autoclave liner is poured out, successively uses ethyl alcohol, deionized water, carbon disulfide washs, most
Powder is placed in dried for standby in baking oven afterwards.Fig. 4 is the stereoscan photograph of the embodiment product；Fig. 5 is the embodiment product
X-ray diffraction result；Fig. 6 is the Raman results of the embodiment product.
(2) 0.1g ferrous disulfide powder is added in 5ml ethyl alcohol, 0.1g terpinol and 0.4g ethyl cellulose is added,
Magnetic agitation one day.
(3) FTO electro-conductive glass, glass substrate are successively cleaned by ultrasonic in acetone, dehydrated alcohol, deionized water, are blown open
It is spare；
(4) by silk screen print method by ferrous disulfide slurry brush in glass, FTO Conducting Glass；
(5) ferrous disulfide film of distil sulphur powder and silk-screen printing is put into quartz boat, in the tube furnace of nitrogen protection
In 450 DEG C be heat-treated 1 hour, obtain ferrous disulfide film, 1.2 microns of thickness.
Figure it is seen that hydro-thermal method is used to react the iron disulfide particles of preparation in 24 hours for nearly octahedron.
From figure 3, it can be seen that hot injection method is used to react the iron disulfide particles of preparation in 24 hours to be spherical.
From fig. 4, it can be seen that hydro-thermal method is used to react the iron disulfide particles of preparation in 39 hours for sheet.
Fig. 5 is that the ferrous disulfide prepared using the method for the present invention hydro-thermal method and hot injection method uses X ' Pert Pro polycrystalline X
X ray diffractometer x carries out the XRD diffracting spectrum that object is mutually tested, it can be seen from the figure that each characteristic peak of laboratory sample is stronger, half
High width is relatively narrow, and crystal face development is preferably, completely the same with the XRD standard diagram (JCPDF 42-1340) of pyrite, without marcasite
Etc. diffraction maximums occur.
Fig. 6 is that ferrous disulfide is prepared using the method for the present invention hydro-thermal method and hot injection method using Kr+-Ar+Mixed gas laser
The Raman that (λ=514.5nm) is carried out tests map, it can be seen from the figure that sample includes 340,377 and 425cm–1Pyrite
Phase ferrous disulfide Characteristic Raman peak, it is consistent with result reported in the literature, it was demonstrated that the product for using the method for the present invention to prepare for
Single-phase pyrite phase ferrous disulfide.
It should be noted that those skilled in the art are that this hair may be implemented completely according to the various embodiments described above of the present invention
Bright independent claims and the full scope of appurtenance, realize process and the same the various embodiments described above of method；And the present invention is not
It elaborates and partly belongs to techniques well known.
The above, part specific embodiment only of the present invention, but scope of protection of the present invention is not limited thereto, appoints
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, should all cover by what those skilled in the art
Within protection scope of the present invention.
Claims (7)
1. a kind of method for preparing pyrite phase ferrous disulfide film, it is characterised in that realize that steps are as follows:
(1) pyrite phase ferrous disulfide powder is obtained using hydro-thermal method or hot injection method, pyrite phase ferrous disulfide powder is through clear
It is spare after washing, drying；
(2) pyrite phase ferrous disulfide powder and ethyl cellulose, terpinol are mixed, magnetic agitation is uniform, obtains slurry；
(3) FTO Conducting Glass is successively cleaned by ultrasonic in acetone, dehydrated alcohol, deionized water, is dried up spare；
(4) by silk screen print method by pyrite phase ferrous disulfide slurry brush in FTO Conducting Glass；
(5) ferrous disulfide film of distil sulphur powder and silk-screen printing is heat-treated, obtains two sulphur of pyrite phase on substrate
Change iron thin film；
The step (1) obtains pyrite phase ferrous disulfide powder method using hydro-thermal method are as follows: by ferrous sulfate heptahydrate and poly- second
Alkene pyrrolidone is added in 90-95 ° of temperature of aqueous solution, and thiocarbamide is added after dissolution, above-mentioned solution is poured into polytetrafluoroethylene (PTFE)
In lining, sulphur powder and ethanol in proper amount is added to the 80% of liner volume, it is small that autoclave is put into 190-210 DEG C of reaction 4-40 in baking oven
When after be cooled to room temperature taking-up, by black powder use ethyl alcohol, deionized water, carbon disulfide washing, dried for standby；
The step (1) obtains pyrite phase ferrous disulfide powder method using hot injection method are as follows: in the three-necked bottle of nitrogen protection
Middle addition oleyl amine and four water frerrous chlorides, 110-120 DEG C reaction 1-1.5 hours, obtain solution A；In the appearance of another nitrogen protection
Sulphur powder is dissolved in diphenyl ether in device, 1-1.5 hours acquisition solution Bs of 70-80 DEG C of reaction；B solution is injected into solution A by needle tubing
In, 210-220 DEG C is cooled to room temperature after reaction 5-24 hours；Black powder is used into dehydrated alcohol, chloroform, it is dry to
With；
Step (5) heat treatment temperature is 400-550 DEG C, is heat-treated 1-3 hours under sulphur and nitrogen or argon atmosphere.
2. the method according to claim 1 for preparing pyrite phase ferrous disulfide film, it is characterised in that: the seven water sulphur
Sour ferrous iron, polyvinylpyrrolidone, thiocarbamide and sulphur powder molar ratio be 1:1.5-2:2-2.5:4-6.
3. preparing the method for pyrite phase ferrous disulfide film according to claim 1, it is characterised in that: the four water chlorination
Ferrous, sulphur powder molar ratio is 1:5-7, and every mM of four water frerrous chlorides are dissolved using 10 milliliters of oleyl amines, every mM of sulphur powder
It is dissolved with 1 milliliter of diphenyl ether.
4. the method according to claim 1 for preparing pyrite phase ferrous disulfide film, it is characterised in that: the step
(1) it when hydro-thermal method or hot injection method obtain different-shape pyrite phase ferrous disulfide powder in, by adjusting reaction time, obtains
The pyrite phase ferrous disulfide powder of variable grain size.
5. the method according to claim 1 for preparing pyrite phase ferrous disulfide film, it is characterised in that: the step
(2) pyrite phase ferrous disulfide powder, ethyl cellulose, terpinol weight ratio be 1:1:4.
6. the method according to claim 1 for preparing pyrite phase ferrous disulfide film, it is characterised in that: the step
(5) heat treatment sublimed sulfur powder purity is greater than 99%.
7. the method according to claim 1 for preparing pyrite phase ferrous disulfide film, it is characterised in that: the pyrite
Phase ferrous disulfide film with a thickness of 1-10 microns；The thickness of pyrite phase ferrous disulfide film passes through the number tune of silk-screen printing
Section.
Priority Applications (1)
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| CN102424429A (en) * | 2011-08-25 | 2012-04-25 | 重庆大学 | Method for preparing iron sulfide thin film from natural pyrite |
| CN102642874A (en) * | 2012-04-27 | 2012-08-22 | 中南大学 | Ferrous disulfide semiconductor film preparation method |
| CN103950989A (en) * | 2014-05-07 | 2014-07-30 | 安徽师范大学 | FeS nano-material and preparation method thereof |
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| CN102424429A (en) * | 2011-08-25 | 2012-04-25 | 重庆大学 | Method for preparing iron sulfide thin film from natural pyrite |
| CN102642874A (en) * | 2012-04-27 | 2012-08-22 | 中南大学 | Ferrous disulfide semiconductor film preparation method |
| CN103950989A (en) * | 2014-05-07 | 2014-07-30 | 安徽师范大学 | FeS nano-material and preparation method thereof |
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