CN1300375C - Method of synthesizing ferrous disulfide film by electro deposition oxidation and hot sulfurization - Google Patents
Method of synthesizing ferrous disulfide film by electro deposition oxidation and hot sulfurization Download PDFInfo
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- CN1300375C CN1300375C CNB2004100734054A CN200410073405A CN1300375C CN 1300375 C CN1300375 C CN 1300375C CN B2004100734054 A CNB2004100734054 A CN B2004100734054A CN 200410073405 A CN200410073405 A CN 200410073405A CN 1300375 C CN1300375 C CN 1300375C
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- ferrous disulfide
- fes
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- hot sulfurization
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- 238000005987 sulfurization reaction Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 12
- 229940095991 ferrous disulfide Drugs 0.000 title claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 238000004070 electrodeposition Methods 0.000 title claims description 11
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 239000011521 glass Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005538 encapsulation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002659 electrodeposit Substances 0.000 claims description 2
- 230000007704 transition Effects 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000010408 film Substances 0.000 abstract 6
- 239000010409 thin film Substances 0.000 abstract 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 abstract 2
- 230000008520 organization Effects 0.000 abstract 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 abstract 1
- 235000019345 sodium thiosulphate Nutrition 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 238000005516 engineering process Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940087654 iron carbonyl Drugs 0.000 description 1
- -1 iron halide Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006101 laboratory sample Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 230000036642 wellbeing Effects 0.000 description 1
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Abstract
The present invention discloses a method for synthesizing a ferrous disulfide thin film by electrodepositing oxidation and thermal sulfuration. The method comprises the following steps: adopting a conductive glass substrate; electrodepositing a Fe-S compound film in the water solution of FeSO4 and Na2S2O3 with the pH value of 3.0 to 5.0; obtaining an FeSO4 prefabricated film via oxidation treatment at the temperature of 180 to 220 DEG C; treating the prefabricated film under the nominal sulfuration pressure of 20 to 40 kPa at the sulfuration temperature of 350 to 450 DEG C for 5 to 20 hours by keeping the same temperature; converting the prefabricated film to the ferrous disulfide thin film in a cube crystal system. The present invention prevents a transition phase organization from existing in the ferrous disulfide thin film; the made thin film has a transparent substrate, and the diffusion of metal or submetallic simple substance atoms to a film body does not exist; the combination of a film layer and the substrate is reliable; the present invention has the advantages of simple process and equipment and high efficiency.
Description
Technical field
The present invention relates to a kind of technology of preparing of function film.
Background technology
Along with the development of progress of science and technology and human civilization, the disposable energy such as coal, petroleum and natural gas more and more can not be satisfied the demand, and its reserves are also in rapid minimizing.And, in the use of these disposable energy, can discharge in a large number the deleterious gas of the mankind, destroy human environment of depending on for existence.Therefore, to the utilization of renewable resources, become the primary content of current scientific research.In various renewable resourcess, inexhaustible, nexhaustible sun power has become the emphasis of utilization of new energy resources exploitation, and wherein one of mainly exploitation form is to try hard to that solar energy is converted into electric energy effectively promote the well-being of mankind.
Solar cell is the device that luminous energy is converted into electric energy, and optoelectronic pole material wherein is the core of solar cell, and except that silicon materials commonly used at present, some new solar cell materials constantly are being developed exploitation.In these materials, the pyrite (FeS of isometric system
2) owing to have a suitable energy gap (about 0.95eV), and high photoelectric absorption coefficient (when λ≤700nm, d 〉=5 * 10
5Cm
-1), stable in properties under the natural condition, Environmental compatibility is good, and is nontoxic, and the component reserves enrich the great attention that reaches series of advantages such as material uses that consumption is lacked and be subjected to scientific and technological circle.
As solar cell material, FeS
2Should use with form of film, existing multiple technology of preparing can synthetic FeS
2Film.Patent US6635942 proposes a kind of FeS that contains that is used for solar cell
2The rete semiconducter device, monocrystalline wherein or polycrystalline FeS
2Can take from natural mineral, just have suitable carrier concentration but must adopt the multi-region cleaning technique to handle.In addition, above-mentioned patent has proposed to adopt vapor transportation, colloidal sol-gel reaction deposition, FeS
2Target as sputter, metal-organic chemical vapor deposition equipment, synthetic technologys such as spray pyrolysis and molecular beam epitaxial growth prepare FeS
2Similarly, patent US6630257 has proposed a kind of FeS of containing
2The technology of preparing of membrane electrode, FeS wherein
2Be considered to adopt chemical vapor transportation chemical vapour deposition, thermal spray deposition, ferriferous oxide sulfuration, reactive sputtering, prepared such as iron film electrodeposition and silk screen printing.
Patent US4649227 has announced two kinds of photosensitive FeS that multiple doped element is arranged
2Membrane prepare technology.First kind of technology is by the natural materials thermochemical treatment being obtained the FeS of required crystal type, purity and metering composition
2, and rely on chemical vapor transportation to form film.Second kind of technology is to prepare FeS by the building-up reactions between iron or iron containing compounds and sulphur or the sulfocompound
2, can adopt that reactant directly contacts, thermograde conversion and vapor transportation realize crystal growth, also can be by reaction formation FeS again after iron carbonyl or iron halide and sulphur or the hydrogen sulfide thermolysis
2Film.Patent ZL02111221.5 has announced the synthetic FeS of a kind of magnetron sputtering iron film of monocrystalline silicon piece substrate
2The preparation method, magnetron sputtering pure iron film on monocrystalline silicon piece carries out the pure iron film hot sulfurization reaction again and forms and have the FeS that standard chemical metering composition there is no transition phase
2Film has higher sticking power between film and the substrate, can be used for FeS
2The laboratory sample of film growth research.
At above-mentioned preparation FeS
2In the technology of film, comparatively speaking, galvanic deposit prefabricated membrane hot sulfurization technology again has processing parameter and controls easily, film forming is even, with low cost, be easy to advantages such as practical application, and can improve film quality and performance by control pre-deposition and hot vulcanization process parameter easily.Yamamoto etc. (SolarEnergy Materials and Solar Cells, 2003, vol.75 pp.451-456) has reported a kind of FeS close with the electrochemical deposition effect
2Film preparing technology is mainly with FeSO
4And (NH
4)
2S
xThe aqueous solution is sprayed at glass and Si sheet, and adds the thermosetting prefabricated membrane at 120 ℃, then at H
2Sulfuration annealing forms the FeS of p type conduction among the S
2Film.Prepare FeS about galvanic deposit and hot sulfurization
2Film, and Nakamura etc. (Solar EnergyMaterials and Solar Cells, 2001, vol.65 pp.79-85) has proposed to use FeSO
4And Na
2S
2O
3The method of aqueous solution revulcanization behind electrolytic deposition FeS prefabricated membrane in the Ti substrate is synthesized FeS
2Film, sulfur vapor N
2Carry.(Materials Research Bulletin, 2003, vol.38, pp.1123-1133 such as Gomes; Electrochimica Acta, 2004, vol.49, pp.2155-2165) 1: 3 (NH of employing
4)
2Fe (SO
4)
2The aqueous solution and Na
2S
2O
3Galvanic deposit Fe-S transition compound film, electroplate liquid adds H
2SO
4Be adjusted to pH=3, substrate is the Ti sheet, the S in the solution
2O
3 2+/ Fe
2+Molar ratio can not equal 1, the Fe-S film is annealed to change into the FeS of n type conduction subsequently in 250～500 ℃ sulphur atmosphere
2Film.Li Enling etc. (Xi'an University of Technology's journal, 2002, vol.18 pp.48-50) adopts FeSO
47H
2O+Na
2S
2O
35H
2The galvanic deposit in Si (111) substrate of the O aqueous solution has FeS
2, FeS and Fe
7S
8The film of mixed structure is subsequently at N
2Or under the vacuum condition through 400～500 ℃ of drying treatment, film uncured annealing.
Yet existing galvanic deposit is the FeS of hot sulfurization preparation again
2Film is because prefabricated membrane is a transition Fe-S compound phase often, and sulfidation is difficult to make transition phase all to be converted into FeS
2, or make FeS
2In have the S room inevitably and form lattice imperfection.In addition, for realizing galvanic deposit, elemental metals or single crystalline Si are adopted in substrate, uncontrollable substrate atom spreads to film body in sulfidation, causes the improper doping of film, causes the conduction type instability, these substrates simultaneously are opaque, can intercept incident light in the practical application.
If prefabricated membrane is a ferriferous oxide, then ferriferous oxide and active S atom direct reaction generate FeS in sulfidation
2Film can avoid occurring poor S transition phase.Smestad etc. (Solar Energy Materials, 1990, vol.20 pp.149-165) adopts pyrolysis FeCl
2Or FeCl
3On substrate of glass, prepared Fe
3O
4Or Fe
2O
3Prefabricated membrane places prefabricated membrane 350 ℃ of following sulfidizing to form FeS again
2Film.In addition, prefabricated membrane also can obtain with the method that the pure Fe film of evaporation reoxidizes processing.Raturi etc. (Renewable Energy, 2000, vol.20 pp.37-43) sprays FeCl on 370 ℃ of sheet glass
3Solution oxide has formed Fe
2O
3, annealing makes prefabricated membrane change FeS in vulcanized gas again
2Film.
Form FeS with the sulfuration of ferric oxide prefabricated membrane
2The technology of film can prevent effectively that poor S transition phase from occurring, adopt substrate of glass as another, avoid substrate that the obstruct of incident light and substrate atomic diffusion are entered film body and caused uncontrollable improper doping, but the prefabricated membrane preparation must be adopted evaporation or chemical vapour deposition, with respect to electro-deposition techniques, the equipment more complicated, film combines insecure with substrate, and efficient is not high yet.
Summary of the invention
The purpose of this invention is to provide the method for a kind of electro deposition oxidation and hot sulfurization synthesizing ferrous disulfide film, processing parameter is controlled easily, does not have transition phase and improper foreign atom in the film, film body adhere to reliable and substrate transparent.
For achieving the above object, the technical solution used in the present invention is:
1) the film carrier substrate is a conductive glass, successively rinses well with deionized water behind the ultrasonic cleaning 15min in acetone and ethanolic soln again;
2) electrodeposit liquid is FeSO
4And Na
2S
2O
3The aqueous solution, molar concentration rate is 1: 5, the pH value is 5.0;
3) make counter electrode with the Pt sheet, 20min obtains deposited film in 0.75mA electric current deposit;
4) electrodeposited film is carried out oxide treatment, obtain having Fe
3O
4The prefabricated membrane of structure;
5) be that 99.5% sublimed sulphur powder is packaged in the silica tube with prefabricated membrane and purity, be evacuated to before the encapsulation to be lower than 1 * 10
-2Pa, and argon filling is replaced 3～8 times repeatedly;
6) sample after will encapsulating carries out sulfidizing in constant-temperature oven, obtains FeS
2Film.
Described film carrier substrate is In for the conducting film composition
2O
3: SnO
2=9: 1 ITO conductive glass.
Described electrodeposited film oxidation processing technique is to be incubated 2h in 180～220 ℃ of dry airs.
Sulfur vapor pressure is 20～40kPa in the described sulfidizing, and curing temperature is 350～450 ℃, and curing time is 5～20h.
The useful effect that the present invention has is:
1) introduced the oxidation link after galvanic deposit, the Fe-S compound that galvanic deposit is formed is converted into Fe in advance
3O
4, avoided the FeS after the hot sulfurization
2The transition phase tissue of residual harmful in the film;
2) used the substrate of ITO conductive glass, avoided the iris action of base material, be practical application in solar cell and FeS incident light
2The test of film photoelectric performance provides the condition that makes things convenient for;
3) do not exist in the substrate metal or metalloid simple substance atom in film body diffusion and cause improper doping and influence the film electric property;
4) compare with evaporation and chemical vapour deposition, because the FeS of prepared by electrodeposition
2The associative key of rete and substrate is stronger, causes film that higher sticking power is arranged;
5) preparation technology and equipment are simple, and efficient is higher.
Description of drawings
Fig. 1 is the prefabricated membrane crystalline structure X-ray diffraction spectrum in the embodiment of the invention 1;
Fig. 2 is the FeS in the embodiment of the invention 1
2Film crystalline structure X-ray diffraction spectrum;
Fig. 3 is the prefabricated membrane crystalline structure X-ray diffraction spectrum in the embodiment of the invention 2;
Fig. 4 is the FeS in the embodiment of the invention 2
2Film crystalline structure X-ray diffraction spectrum.
Embodiment
Embodiment 1:
The ITO conductive glass that will be of a size of 20 * 15mm2 is as the film carrier substrate, and the conducting film composition is In
2O
3: SnO
2=9: 1, first ultrasonic cleaning 15min in acetone soln, ultrasonic cleaning 15min in ethanolic soln again, ultrasonic cleaning is after the ionized water cleaning down is removed residual organic solution.
The preparation molar concentration rate is 1: 5 FeSO
4And Na
2S
2O
3The aqueous solution is with the H of dilution
2SO
4The pH value to 5.0 of regulator solution.Make counter electrode with the Pt sheet, deposition Fe-S compound film in substrate, the constant current of maintenance 0.75mA, depositing time is 20min.Deposition gained sample soaks 1h after with deionized water rinsing in dehydrated alcohol, place the baking oven insulation 2h of 180 ℃ of dry airs to carry out oxide treatment again, obtains crystalline structure Fe as shown in Figure 1
3O
4Prefabricated membrane.
Calculate and to produce the required quality of 20kPa name sulphur pressure sublimed sulphur powder (purity is 99.5%) under 350 ℃ of conditions, prefabricated membrane and required quality sulphur powder are packaged in the silica tube, vacuumize also argon filling displacement 3 times repeatedly before the encapsulation, be evacuated to residual gas pressure during encapsulation and be lower than 1 * 10
-2Pa.With the sample sulfidizing 20h in 350 ℃ of constant-temperature ovens after the encapsulation.For preventing that film from cracking and peeling off, the control temperature rise rate is not higher than 4 ℃/min before the isothermal, and rate of temperature fall is not higher than 2 ℃/min behind the isothermal.The FeS that obtains after the sulfuration
2Membrane structure as shown in Figure 2.
Embodiment 2:
Method according to embodiment 1 prepares the Fe-S compound film, places the baking oven insulation 2h of 220 ℃ of dry airs to carry out oxide treatment electrodeposited film and obtains Fe
3O
4Prefabricated membrane, its crystalline structure as shown in Figure 3.
Calculate and to produce the required quality of 40kPa name sulphur pressure sublimed sulphur powder (purity is 99.5%) under 450 ℃ of conditions, according to the method among the embodiment 1 prefabricated membrane is converted into FeS at 450 ℃ of following sulfidizing 5h again
2Film (vacuumizing also argon filling displacement 8 times repeatedly before the silica tube encapsulation), crystalline structure as shown in Figure 4.
Claims (4)
1. the method for electro deposition oxidation and hot sulfurization synthesizing ferrous disulfide film is characterized in that:
1) the film carrier substrate is a conductive glass, successively rinses well with deionized water behind the ultrasonic cleaning 15min in acetone and ethanolic soln again;
2) electrodeposit liquid is FeSO
4And Na
2S
2O
3The aqueous solution, molar concentration rate is 1: 5, the pH value is 5.0;
3) make counter electrode with the Pt sheet, 20min obtains deposited film in 0.75mA electric current deposit;
4) electrodeposited film is carried out oxide treatment, obtain having Fe
3O
4The prefabricated membrane of structure;
5) be that 99.5% sublimed sulphur powder is packaged in the silica tube with prefabricated membrane and purity, be evacuated to before the encapsulation to be lower than 1 * 10
-2Pa, and argon filling is replaced 3～8 times repeatedly;
6) sample after will encapsulating carries out sulfidizing in constant-temperature oven, obtains FeS
2Film.
2. the method for electro deposition oxidation according to claim 1 and hot sulfurization synthesizing ferrous disulfide film is characterized in that: described film carrier substrate is In for the conducting film composition
2O
3: SnO
2=9: 1 ITO conductive glass.
3. the method for electro deposition oxidation according to claim 1 and hot sulfurization synthesizing ferrous disulfide film is characterized in that: described electrodeposited film oxidation processing technique is to be incubated 2h in 180～220 ℃ of dry airs.
4. the method for electro deposition oxidation according to claim 1 and hot sulfurization synthesizing ferrous disulfide film is characterized in that: sulfur vapor pressure is 20～40kPa in the described sulfidizing, and curing temperature is 350～450 ℃, and curing time is 5～20h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100734054A CN1300375C (en) | 2004-12-07 | 2004-12-07 | Method of synthesizing ferrous disulfide film by electro deposition oxidation and hot sulfurization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100734054A CN1300375C (en) | 2004-12-07 | 2004-12-07 | Method of synthesizing ferrous disulfide film by electro deposition oxidation and hot sulfurization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1624196A CN1624196A (en) | 2005-06-08 |
| CN1300375C true CN1300375C (en) | 2007-02-14 |
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|---|---|---|---|
| CNB2004100734054A Expired - Fee Related CN1300375C (en) | 2004-12-07 | 2004-12-07 | Method of synthesizing ferrous disulfide film by electro deposition oxidation and hot sulfurization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432290C (en) * | 2006-07-13 | 2008-11-12 | 陕西科技大学 | Preparation method of Sb2S3 thermal electric film |
| CN102485654B (en) * | 2009-09-23 | 2014-11-05 | 东北大学 | Method for preparing pyrite crystals under heat curing condition |
| CN112062165A (en) * | 2020-08-19 | 2020-12-11 | 浙江工业大学 | Regulation and control FeS2Method for reducing graphene oxide compact assembly structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0173642B1 (en) * | 1984-07-27 | 1991-01-23 | Hahn-Meitner-Institut Berlin Gesellschaft mit beschränkter Haftung | Photoactive pyrite film, method for its preparation and application of such a pyrite film |
| CN1387265A (en) * | 2002-03-29 | 2002-12-25 | 浙江大学 | Process for preparing FeS2 on monosilicon substrate by magnetically controlled sputter to Fe film |
| US6635942B2 (en) * | 1998-04-29 | 2003-10-21 | LA VECCHIA Nunzio | Semiconductor element, especially a solar cell, and method for the production thereof |
-
2004
- 2004-12-07 CN CNB2004100734054A patent/CN1300375C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0173642B1 (en) * | 1984-07-27 | 1991-01-23 | Hahn-Meitner-Institut Berlin Gesellschaft mit beschränkter Haftung | Photoactive pyrite film, method for its preparation and application of such a pyrite film |
| US6635942B2 (en) * | 1998-04-29 | 2003-10-21 | LA VECCHIA Nunzio | Semiconductor element, especially a solar cell, and method for the production thereof |
| CN1387265A (en) * | 2002-03-29 | 2002-12-25 | 浙江大学 | Process for preparing FeS2 on monosilicon substrate by magnetically controlled sputter to Fe film |
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|---|---|
| CN1624196A (en) | 2005-06-08 |
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