CN107452834B - The adjustable CdTe of forbidden bandwidthxSe1-xSemiconductive thin film and its preparation method and application - Google Patents
The adjustable CdTe of forbidden bandwidthxSe1-xSemiconductive thin film and its preparation method and application Download PDFInfo
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- CN107452834B CN107452834B CN201710568781.8A CN201710568781A CN107452834B CN 107452834 B CN107452834 B CN 107452834B CN 201710568781 A CN201710568781 A CN 201710568781A CN 107452834 B CN107452834 B CN 107452834B
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- 229910004613 CdTe Inorganic materials 0.000 title claims abstract description 81
- 239000010409 thin film Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000011669 selenium Substances 0.000 claims abstract description 128
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 239000010408 film Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 22
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 21
- RPPBZEBXAAZZJH-UHFFFAOYSA-N cadmium telluride Chemical compound [Te]=[Cd] RPPBZEBXAAZZJH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000004528 spin coating Methods 0.000 claims description 13
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 2
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 238000001548 drop coating Methods 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000031700 light absorption Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- 229910002058 ternary alloy Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
- H01L31/1832—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising ternary compounds, e.g. Hg Cd Te
-
- 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
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
- H01L31/02963—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe characterised by the doping material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—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
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
- H01L31/02966—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe including ternary compounds, e.g. HgCdTe
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
- H01L31/1836—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising a growth substrate not being an AIIBVI compound
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The invention discloses a kind of adjustable CdTe of forbidden bandwidthxSe1‑xSemiconductive thin film and its preparation method and application.The preparation method of the film includes the following steps: that the source Cd, the source Te and the source Se are dissolved into solvent by (1), obtains cadmium tellurium selenium precursor liquid, wherein solvent is the mixed solution of ethylenediamine and mercaptan；(2) cadmium tellurium selenium precursor liquid obtained in step (1) is coated on substrate, obtains CdTexSe1‑xPrecursor thin-film；(3) by CdTe obtained in step (2)xSe1‑xPrecursor thin-film is heat-treated, cooling, obtains the adjustable CdTe of forbidden bandwidthxSe1‑xSemiconductive thin film；(4) to this termination；Or step (2)~(3) reciprocation cycle.The semiconductive thin film with gradient band gap can be prepared using method of the invention, be applied to CdTe thin film solar cell, the light absorption of battery long-wave band can be improved, improve the photoelectric conversion efficiency of battery.
Description
Technical field
The invention belongs to Photovoltaic new energy material and devices field, in particular to a kind of forbidden bandwidth is adjustable
CdTexSe1-xSemiconductive thin film and its preparation method and application.
Background technique
CdTe is a kind of ideal photovoltaic material, is the direct band-gap semicondictor that forbidden bandwidth is 1.45eV, to visible light
Absorption coefficient be higher than 100 times (> 10 of silicon materials5cm-1), it is only necessary to about 2 microns of thickness is just able to satisfy light absorption and photoelectricity turns
The needs changed, material consumption are few；CdTe belongs to II-VI race's binary compound, and component is simple, wide to thin-film material deposition condition
Capacitive height is easy to industrialization；The temperature power coefficient of CdTe is low, and dim light effect is good, and comprehensive photoelectric conversion efficiency is high.CdTe thin film
Solar cell has both high conversion efficiency and low cost as most competitive one of solar cell, quick by nearly 20 years
Development, it has also become the photovoltaic products second largest product system other than crystal silicon solar battery in the market at present, great researching value and
Market potential.It since 2011, has been broken for the world record of CdTe solar cell transfer efficiency continuous nine times, CdTe is too at present
The laboratory highest transfer efficiency in positive electricity pond has reached 22.1%, and Developments are known as CdTe thin film solar cell system
" the 4th leap " of standby technology, the extensive concern by scientific research and industrial circle.
It is limited by CdTe material doping characteristic, CdTe absorbed layer has a determining band gap, and battery is theoretic most
High conversion efficiency is 29%.The progress of nearest CdTe absorbed layer p-type doping technology, so that this theory limitation is changing
Become.The short-circuit current density J of First Solar company small area CdTe solar cellscFor 30.94mA/cm2, surmounted and be based on
Band gap is the CdTe battery J of 1.45eVscTheoretical maximum 30.5mA/cm2.The promotion of short circuit current mainly has benefited from having ladder
Spend the CdTe absorbed layer of bandgap structure.The regulation of CdTe band gap width is realized by displacement to Te doping, but specific
Technical matters is undisclosed.
Studies have shown that forming CdTe by introducing Se in CdTexSe1-xTernary alloy three-partalloy can reduce CdTe absorbed layer
Forbidden bandwidth can obtain the CdTe with gradient band gap structure by controlling the relative amount of different depth SexSe1-xIt absorbs
Layer (bandgap range 1.30~1.45), so that being based on CdTexSe1-xThe long-wave response of the solar cell of absorbed layer is from 850nm
Expand to 950nm, corresponding short-circuit current gain~2 mA/cm2.Current CdTexSe1-xFilm preparation means are mainly physics
Vacuum method, and for, the simpler liquid phase preparation process of technique less expensive to cost, CdTexSe1-xThe preparation of film always ten
Divide difficulty, only technology of preparing is mostly about CdTexSe1-xThe preparation method of quantum dot.Therefore it provides a kind of at low cost, work
Skill is simple, the adjustable CdTe of forbidden bandwidthxSe1-xFilm preparing technology is of great significance.
Summary of the invention
The primary purpose of the present invention is that the shortcomings that overcoming the prior art and deficiency, it is adjustable to provide a kind of forbidden bandwidth
CdTexSe1-xThe preparation method of semiconductive thin film.
Another object of the present invention is to provide the forbidden bandwidth being prepared by the method is adjustable
CdTexSe1-xSemiconductive thin film.
Another object of the present invention is to provide the forbidden bandwidth adjustable CdTexSe1-xThe application of semiconductive thin film.
The purpose of the invention is achieved by the following technical solution: a kind of adjustable CdTe of forbidden bandwidthxSe1-xSemiconductor film
The preparation method of film, wherein 0 < x≤1 specifically comprises the following steps:
(1) it prepares cadmium tellurium selenium precursor solution: the source Cd, the source Te and the source Se is dissolved into solvent, obtain cadmium tellurium selenium forerunner
Liquid, wherein solvent is the mixed solution of ethylenediamine and mercaptan；
(2) CdTe is preparedxSe1-xPrecursor thin-film: cadmium tellurium selenium precursor liquid obtained in step (1) is coated on substrate,
Obtain CdTexSe1-xPrecursor thin-film；
(3) CdTe is preparedxSe1-xFilm: by CdTe obtained in step (2)xSe1-xPrecursor thin-film is heat-treated, cold
But, the adjustable CdTe of forbidden bandwidth is obtainedxSe1-xSemiconductive thin film；
(4) to this termination；Or step (2)~(3) reciprocation cycle, it is adjustable to obtain the different forbidden bandwidth of multilayer overall thickness
CdTexSe1-xSemiconductive thin film.
The x numberical range is preferably 0 < x < 1.
The source Cd described in step (1) is preferably one of caddy, cadmium sulfate and cadmium acetate or more.
The source Te described in step (1) is preferably Te simple substance.
The source Se described in step (1) is preferably Se simple substance.
Dissolution described in step (1) preferably uses magnetic agitation to be dissolved.
The time of the magnetic agitation is 2~6 hours, preferably 2~4 hours.
Solvent described in step (1) is preferably ethylenediamine and the mercaptan solvent that 2~10:1 is matched by volume.
Mercaptan described in step (1) is preferably one or both of propanethiol and dithioglycol.
Solute (source Cd, the source Te and the source Se) concentration in cadmium tellurium selenium precursor liquid described in step (1) is 0.05~
0.5mol/L。
The adjustable CdTe of the forbidden bandwidthxSe1-xThe preparation method of semiconductive thin film further includes that will obtain in step (1)
To cadmium tellurium selenium precursor liquid be filtered.
The filtering preferably uses aperture to be filtered for the filter of 220nm.
The method of coating described in step (2) is spin-coating method, drop-coating, dip-coating method, spray coating method or inkjet printing
Method.
The spin coating revolving speed of the spin-coating method is preferably 1500~2000 revs/min, and rotational time is preferably 20~30
Second.
The spray coating method is preferably spray pyrolysis method.
Substrate temperature is preferably 300 DEG C when the spray pyrolysis method sprays.
Substrate described in step (2) is glass substrate；Preferably clean glass/FTO/CdS substrate.
The temperature of heat treatment described in step (3) is 300~500 DEG C；Preferably 300~450 DEG C.
The time of heat treatment described in step (3) is 1~20 minute；Preferably 5~10 minutes.
Cooling described in step (3) is preferably that Temperature fall is cooled down；It is more preferably placed on heat insulated supporter certainly
So cooling is cooled down.
The number of circulation described in step (4) can film thickness according to actual needs determine.
The adjustable CdTe of the forbidden bandwidthxSe1-xThe preparation method of semiconductive thin film, preparation process are in drying
Inert gas atmosphere under carry out.
The inert gas is preferably N2。
The CdTexSe1-xThe thickness of semiconductive thin film can pass through preparation parameter (the cadmium tellurium selenium of change single film
Concentration of precursor solution, spin coating revolving speed etc.) it is controlled, it can also be controlled by the way that step (2)~(3) are repeated several times；Described
CdTexSe1-xThe thickness of film is preferably 500nm~2 μm.
A kind of adjustable CdTe of forbidden bandwidthxSe1-xSemiconductive thin film is prepared by method described in any of the above embodiments
It arrives.
The adjustable CdTe of the forbidden bandwidthxSe1-xSemiconductive thin film answering in preparation CdTe thin film solar cell
With.
A kind of CdTe with gradient band gapxSe1-xFilm, by any of the above-described institute for depositing multilayer difference Se content
The adjustable CdTe of the forbidden bandwidth that the method stated is preparedxSe1-xSemiconductive thin film obtains (note: single stoichiometric ratio
CdTexSe1-xFilm has single band gap, and gradient band gap is that have different stoichiometric ratios by deposition multilayer
CdTexSe1-xFilm makes film through-thickness that there is different Se contents to obtain), wherein 0 < x≤1, and multilayer
CdTexSe1-xSe content is not zero (i.e. x is not simultaneously 1) simultaneously in semiconductive thin film.
The present invention has the following advantages and effects with respect to the prior art:
1, CdTe is a kind of solar cell material haveing excellent performance, forbidden bandwidth 1.45eV, by drawing in CdTe
CdTe can be formed to the Se of Te atom displacement by enteringxSe1-xTernary alloy three-partalloy can be controllable reduction CdTe forbidden bandwidth.Liquid phase system
Preparation Method has many advantages, such as that preparation process is simple, at low cost, component is easy to control.It is limited by itself physical property, is lacked always
Effective solvent makes II-VI compounds of group (the CdTe, CdSe etc.) dissolution of Cd form uniform solution presoma, Jin Erjin
The preparation of row liquid phase.The object of the present invention is to provide a kind of CdTe that new stoichiometric ratio is controllablexSe1-xIt is prepared by the liquid phase of film
Method regulates and controls CdTe by controlling x valuexSe1-xThe forbidden bandwidth of material prepares the semiconductive thin film with gradient band gap, and
It is applied in CdTe thin film solar cell as light absorbing layer, improves the light absorption of battery long-wave band, improve the light of battery
Photoelectric transformation efficiency.
2, the CdTe being prepared in the present invention based on the liquid phase methodxSe1-xFilm, even compact, adhesion is good, with object
The film quality that reason vacuum method obtains is suitable, by controlling the adjustable CdTe of the available band gap of its stoichiometric ratioxSe1-xIt is thin
Film, and the film with gradient band gap can be prepared.CdTexSe1-xIt is a kind of compound semiconductor material with excellent photoelectric properties
Material, the total moles and the source Cd molal quantity of (Te+Se) are almost the same, and wherein the relative scale of Te and Se can be according to ingredient need
Any change is wanted, by Se/ (Te+Se) atomic ratio in change material, it can be achieved that CdTexSe1-xMaterial forbidden bandwidth it is effective
Regulation.
3, the controllable CdTe of stoichiometric ratio in the present inventionxSe1-xThe preparation method of film has simple process, cost
Cheap feature.By controlling CdTexSe1-xThe chemical component of film can prepare the controllable semiconductive thin film of band gap, and will
It is applied in CdTe thin film solar cell as light absorbing layer, improves the light absorption of battery long-wave band, promotes photo-generated carrier
Separated transmission, improve the photoelectric conversion efficiency of battery.CdTe thin film solar cell is that crystal silicon is too in the market for current photovoltaic products
The second largest product system other than positive electricity pond has both high conversion efficiency and low cost, great researching value and market potential.
Detailed description of the invention
The CdTe with gradient band gap that Fig. 1 embodiment 3 obtainsxSe1-xScanning electron microscopy (SEM) cross-section diagram of film
With X-ray diffraction (XRD) figure；Wherein, figure (a) is SEM figure, and figure (b) is XRD diagram.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
Following experimental implementations are the N in glove box2It is carried out under atmosphere:
(1) prepare ethylenediamine: the volume ratio of propanethiol is the mixed solution 5mL of 5:2.
(2) 0.183g CdCl is sequentially added in Xiang Shangshu solution2, 0.064g Te and 0.0395g Se, magneton under room temperature
It stirs 4 hours, via hole diameter is that cadmium tellurium selenium precursor liquid is obtained by filtration in the filter of 220nm.
(3) cadmium tellurium selenium precursor liquid is covered on clean Glass/FTO/CdS substrate surface using pipettor, utilizes spin coating
Method obtains CdTexSe1-xPrecursor thin-film, the revolving speed of spin coating are 2000 revs/min, and rotational time is 20 seconds.
(4) by CdTexSe1-xPrecursor thin-film is heat-treated 5 minutes on the hot plate that temperature is 400 DEG C, is then placed into absolutely
Temperature fall on hot bracket, obtains CdTexSe1-xFilm.
(5) step (3) are repeated (4) five times, prepares the CdTe of thickness about 500nmxSe1-xFilm, wherein x 0.5.
Embodiment 2
Following experimental implementations are the N in glove box2It is carried out under atmosphere:
(1) prepare ethylenediamine: the volume ratio of dithioglycol is the mixed solution 5mL of 10:1.
(2) 0.367g CdCl is sequentially added in Xiang Shangshu solution2, 0.064g Te and 0.119g Se, magneton stirs under room temperature
It mixes 2 hours, via hole diameter is that cadmium tellurium selenium precursor liquid is obtained by filtration in the filter of 220nm.
(3) cadmium tellurium selenium precursor liquid is covered on clean Glass/FTO/CdS substrate surface using pipettor, utilizes spraying
Pyrolysismethod obtains CdTexSe1-xPrecursor thin-film, underlayer temperature is 300 DEG C when spraying.
(4) by CdTe after sprayingxSe1-xPrecursor thin-film is heat-treated 5 minutes under the conditions of 350 DEG C, is then placed into
Temperature fall on heat insulated supporter, obtains CdTexSe1-xFilm；Wherein, 0.25, CdTe xxSe1-xThe thickness of film about 600nm.
Embodiment 3
Following experimental implementations are the N in glove box2It is carried out under atmosphere:
(1) prepare ethylenediamine respectively in three reagent bottles (being named as reagent bottle a, b, c): the volume ratio of propanethiol is 2:
1 mixed solution 5mL.
(2) 0.183g CdCl is separately added into above three reagent bottle a, b, c2, 0.064g Te, 0.0395g Se,
0.183g CdCl2, 0.096g Te, 0.020g Se, 0.183g CdCl2, 0.128g Te, magneton stirs 3 hours under room temperature,
Via hole diameter is that three kinds of cadmium tellurium selenium precursor liquids are obtained by filtration in the filter of 220nm.
(3) the cadmium tellurium selenium precursor liquid in mentioned reagent bottle a is covered on clean Glass/FTO/CdS using pipettor
Substrate surface obtains CdTe using spin-coating methodxSe1-xThe revolving speed of precursor thin-film, spin coating is 1500 revs/min, and rotational time is
30 seconds.
(4) by CdTexSe1-xPrecursor thin-film is heat-treated 2 minutes on the hot plate that temperature is 450 DEG C, is then placed within absolutely
Temperature fall on hot bracket, obtains CdTexSe1-xFilm.
(5) step (3) (4) is repeated 3 times.
(6) the cadmium tellurium selenium precursor liquid in mentioned reagent bottle b is covered on the substrate table that step (5) obtains using pipettor
Face obtains CdTe using spin-coating methodxSe1-xPrecursor thin-film, the revolving speed of spin coating are 1500 revs/min, and rotational time is 30 seconds.
(7) by CdTexSe1-xPrecursor thin-film is heat-treated 2 minutes on the hot plate that temperature is 450 DEG C, is then placed within absolutely
Temperature fall on hot bracket, obtains CdTexSe1-xFilm.
(8) step (6) (7) is repeated 3 times.
(9) the cadmium tellurium selenium precursor liquid in mentioned reagent bottle c is covered on the substrate table that step (8) obtains using pipettor
Face obtains CdTe precursor thin-film using spin-coating method, and the revolving speed of spin coating is 1500 revs/min, and rotational time is 30 seconds.
(10) CdTe precursor thin-film is heat-treated 2 minutes on the hot plate that temperature is 450 DEG C, is then placed within insulation branch
Temperature fall on frame, obtains CdTe thin film.
(11) step (9) (10) is repeated 3 times.
(12) film for obtaining process (11) is heat-treated 10 minutes, is then placed Temperature fall on heat insulated supporter, is obtained
CdTe with gradient band gapxSe1-xFilm, CdTexSe1-xThe thickness of film is about 2um.
In the present embodiment, the corresponding x value of cadmium tellurium selenium precursor liquid a, b, c is 0.5,0.75 and 1 respectively；The present embodiment is intended to lead to
The counterdiffusion crossed between different layer films prepares different-thickness with different Se contents and then has the absorbed layer of gradient band gap, so
As the film of multilayer difference stoichiometric ratio deposits, the value of x is change of gradient.
By the CdTe obtained above with gradient band gapxSe1-xFilm is observed by scanning electron microscope, knot
Shown in fruit such as Fig. 1 (a)；X-ray diffraction is carried out again, shown in result such as 1 (b).The characterization result of XRD and SEM is shown based on this
The CdTe that invention solwution method is preparedxSe1-xThin film composition and good crystallinity, crystallite dimension is at 1~2 micron, the structure
The separated transmission of light absorption and photo-generated carrier is realized advantageous as the core function layer of photoelectric device with pattern.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of adjustable CdTe of forbidden bandwidthxSe1-xThe preparation method of semiconductive thin film, wherein 0 < x≤1, which is characterized in that
Specifically comprise the following steps:
(1) it prepares cadmium tellurium selenium precursor solution: the source Cd, the source Te and the source Se is dissolved into solvent, obtain cadmium tellurium selenium precursor liquid,
In, solvent is the mixed solution of ethylenediamine and mercaptan；
(2) CdTe is preparedxSe1-xPrecursor thin-film: cadmium tellurium selenium precursor liquid obtained in step (1) is coated on substrate, is obtained
CdTexSe1-xPrecursor thin-film；
(3) CdTe is preparedxSe1-xFilm: by CdTe obtained in step (2)xSe1-xPrecursor thin-film is heat-treated, cooling,
Obtain CdTexSe1-xFilm；
(4) to this termination, the as adjustable CdTe of forbidden bandwidthxSe1-xSemiconductive thin film；Or step (2)~(3) are past
Multiple circulation, obtains CdTexSe1-xSemiconductive thin film, the as adjustable CdTe of forbidden bandwidthxSe1-xSemiconductive thin film.
2. the adjustable CdTe of forbidden bandwidth according to claim 1xSe1-xThe preparation method of semiconductive thin film, feature exist
In:
The source Cd described in step (1) is one of caddy, cadmium sulfate and cadmium acetate or more；
The source Te described in step (1) is Te simple substance；
The source Se described in step (1) is Se simple substance；
Mercaptan described in step (1) is one or both of propanethiol and dithioglycol.
3. the adjustable CdTe of forbidden bandwidth according to claim 1xSe1-xThe preparation method of semiconductive thin film, feature exist
In: solvent described in step (1) is ethylenediamine and the mercaptan solvent that 2~10:1 is matched by volume.
4. the adjustable CdTe of forbidden bandwidth according to claim 1xSe1-xThe preparation method of semiconductive thin film, feature exist
In:
The temperature of heat treatment described in step (3) is 300~500 DEG C；
The time of heat treatment described in step (3) is 1~20 minute.
5. the adjustable CdTe of forbidden bandwidth according to claim 1xSe1-xThe preparation method of semiconductive thin film, feature exist
In: it further include being filtered cadmium tellurium selenium precursor liquid obtained in step (1)；Described being filtered into uses aperture for 220nm's
Filter is filtered.
6. the adjustable CdTe of forbidden bandwidth according to claim 1xSe1-xThe preparation method of semiconductive thin film, feature exist
In:
It is dissolved as being dissolved using magnetic agitation described in step (1)；
Substrate described in step (2) is glass/FTO/CdS substrate；
The method of coating described in step (2) is spin-coating method, drop-coating, dip-coating method, spray coating method or ink-jet printing；
It is cooled to be placed on Temperature fall on heat insulated supporter described in step (3) to be cooled down.
7. a kind of adjustable CdTe of forbidden bandwidthxSe1-xSemiconductive thin film, it is characterised in that: pass through any one of claim 1~6
The method is prepared.
8. the adjustable CdTe of forbidden bandwidth according to claim 7xSe1-xSemiconductive thin film, it is characterised in that: the taboo
The adjustable CdTe of bandwidthxSe1-xSemiconductive thin film with a thickness of 500nm~2 μm.
9. the adjustable CdTe of forbidden bandwidth described in claim 7 or 8xSe1-xSemiconductive thin film is in preparation CdTe thin film sun electricity
Application in pond.
10. a kind of CdTe with gradient band gapxSe1-xFilm, it is characterised in that: by described in Multiple depositions claim 7 or 8
The adjustable CdTe of forbidden bandwidthxSe1-xSemiconductive thin film obtains；Wherein, the adjustable CdTe of the forbidden bandwidthxSe1-xPartly lead
The CdTe deposited every time in body thin filmxSe1-xThe content of the Se of film is not identical.
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| CN101554999A (en) * | 2009-04-30 | 2009-10-14 | 河南大学 | Method for synthesizing tellurium-contained semiconductor nanocrystal |
| CN105390393A (en) * | 2014-08-25 | 2016-03-09 | 新能光电科技股份有限公司 | Heat treatment process and products made thereby |
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