CN104495762A - Preparation method of ZnSe nanocrystal, ZnSe nanocrystal and preparation method of ZnSe buffer layer - Google Patents
Preparation method of ZnSe nanocrystal, ZnSe nanocrystal and preparation method of ZnSe buffer layer Download PDFInfo
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- CN104495762A CN104495762A CN201410766659.8A CN201410766659A CN104495762A CN 104495762 A CN104495762 A CN 104495762A CN 201410766659 A CN201410766659 A CN 201410766659A CN 104495762 A CN104495762 A CN 104495762A
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- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000002159 nanocrystal Substances 0.000 title abstract 8
- 239000002243 precursor Substances 0.000 claims abstract description 41
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 37
- 239000011669 selenium Substances 0.000 claims abstract description 37
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 230000002829 reductive effect Effects 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- -1 octadecylene Chemical group 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical group CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 7
- 229910000085 borane Inorganic materials 0.000 claims description 7
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical group [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 6
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract 3
- 235000021355 Stearic acid Nutrition 0.000 abstract 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical group [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 abstract 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 abstract 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 abstract 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000008117 stearic acid Substances 0.000 abstract 1
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 3
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a preparation method of ZnSe nanocrystal. The preparation method of the ZnSe nanocrystal comprises the following steps: S1, preparing selenium precursor solution, namely preparing a reaction solution by utilizing oleylamine, a selenium simple substance and a reducing agent, heating and reacting, and thus the selenium precursor solution is obtained, wherein concentration of the selenium precursor solution in the reaction solution is 0.25-1.5mol/L, the mole ratio of the reducing agent to the selenium simple substance is more than 1:1, and the reducing agent is dimethylamine borane or sodium borohydride; S2, preparing a zinc precursor solution, namely dispersing a zinc source in a reaction solvent to obtain the zinc precursor solution, wherein mole ratio of the zinc source to the selenium simple substance is 1:(1-1.5), and the reaction solvent is oleylamine or a mixed solvent of octadecene and stearic acid; and S3, preparing ZnSe nanocrystal, namely heating the zinc precursor solution obtained in the step S2 to 150-350 DEG C in an anhydrous oxygen-free system, then injecting the selenium precursor solution obtained in the step S1 into the zinc precursor solution, and reacting for at least 10 minutes, and thus the ZnSe nanocrystal is obtained. By adopting the preparation method of the ZnSe nanocrystal, high-quality ZnSe nanocrystal can be prepared.
Description
Technical field
The present invention relates to the preparation of the buffer layer of nano material and thin film solar cell, particularly relate to the preparation method of the nanocrystalline and ZnSe buffer layer of the nanocrystalline preparation method of a kind of ZnSe, ZnSe.
Background technology
Semiconductor nano material has broad application prospects because of the photoelectric characteristic of its uniqueness, as ZnSe, it is a kind of important metal selenide, the nanocrystalline Liquid preparation methods of current ZnSe generally all needs to use the organic phosphoric compounds such as tri-n-octyl phosphine (TOP) or trioctylphosphine oxide (TOPO) (TOPO), but that to be highly toxic substance, character unstable is oxidizable and expensive for TOP and TOPO, and by the restriction of other conditions, the nanocrystalline quality of the ZnSe that existing preparation method obtains is lower, is unfavorable for the application that ZnSe is nanocrystalline.
At thin film solar cell as in CIGS thin film solar cell, buffer layer, between absorption layer and Window layer, has very important influence to the efficiency of conversion of battery.At present, be no matter that the CIGS thin film solar cell of laboratory or suitability for industrialized production mostly uses CdS buffer layer.But well-known, cadmium is heavy metal toxic element, significantly limit the extensive development of CIGS solar cell every pollution problem.In addition, the energy gap of CdS is 2.4eV, and band gap is partially narrow, has certain influence to the absorption of shortwave and opto-electronic conversion response.Therefore, develop without the CIGS thin film solar cell of cadmium and become a study hotspot without the research and development of cadmium buffer layer.Zinc selenide is hopeful most at present one of cushioning layer material replacing Cadmium Sulfide, and its energy gap is about 2.7eV, slightly wider than Cadmium Sulfide, with CIGS absorption layer and ZnO Window layer lattice good, the more important thing is that zinc selenide does not exist environmental pollution.
Summary of the invention
In order to make up above-mentioned the deficiencies in the prior art, the present invention proposes the preparation method of the nanocrystalline and ZnSe buffer layer of the nanocrystalline preparation method of a kind of ZnSe, ZnSe.
Technical problem of the present invention is solved by following technical scheme:
The preparation method that ZnSe is nanocrystalline, comprises the steps:
S1, prepare selenium precursor solution: oleyl amine, selenium simple substance and reductive agent are made into reaction soln, and reacting by heating obtains described selenium precursor solution; In described reaction soln, the concentration of described selenium precursor solution is 0.25-1.5mol/L, the mol ratio >=1:1 of described reductive agent and described selenium simple substance, and described reductive agent is dimethyamine borane or sodium borohydride;
S2, preparation zinc precursor solution: be dispersed in reaction solvent in zinc source and join to obtain described zinc precursor solution, the mol ratio of described zinc source and described selenium simple substance is 1:1 ~ 1:1.5, described reaction solvent is oleyl amine or the mixed solvent for octadecylene and hard fatty acids;
ZnSe is nanocrystalline for S3, preparation: under anhydrous and oxygen-free system, described zinc precursor solution in step S2 is heated to 150-350 DEG C, be expelled in described zinc precursor solution by selenium precursor solution described in step S1, the reaction times is 10min at least again, obtains described ZnSe nanocrystalline.
Preferably, before described step S3, also comprise the step described selenium precursor solution in step S1 being cooled to 70-100 DEG C.
Preferably, the described zinc source in step S2 is the one in zinc acetylacetonate, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate, zinc oleate and zinc ethyl.
Preferably, in step sl, described reductive agent is dimethyamine borane, and the temperature of described reacting by heating is 130-150 DEG C.
Preferably, in described octadecylene in step s 2 and the mixed solvent of hard fatty acids, the volume of described octadecylene is 8-12mL:2-5mmol with the ratio of the amount of substance of described hard fatty acids.
Preferably, after described step S3, also comprise S4: wash described ZnSe is nanocrystalline with organic solvent, described organic solvent is selected from least one in toluene, chloroform, normal hexane, methyl alcohol, ethanol and Virahol.
Preferably, described organic solvent is the mixed solvent of toluene and ethanol, and the volume ratio of toluene and ethanol is 1:2.
A kind of ZnSe obtained by above-mentioned preparation method is nanocrystalline, and described ZnSe is nanocrystalline is zincblende lattce structure, and size distribution is between 5-150nm.
A preparation method for ZnSe buffer layer, comprises the steps:
(1) described ZnSe preparation method nanocrystalline for above-mentioned ZnSe prepared is nanocrystalline is that 100-500mg/mL dispersion is mixed with the nanocrystalline ink of homogeneous, stable ZnSe in organic solvent by solid-to-liquid ratio;
(2) obtained ZnSe buffer layer on the absorption layer nanocrystalline for described ZnSe ink being coated in thin film solar cell, the thickness of described ZnSe buffer layer is 50-100nm.
Preferably, the solid-to-liquid ratio in described step (1) is 150-250mg/mL.
The beneficial effect that the present invention is compared with the prior art is: preparation method of the present invention does not adopt organic phosphine reagent, preparation technology is simple, the obtained nanocrystalline quality of ZnSe is higher, the ZnSe prepared by method of the present invention is nanocrystalline is zincblende lattce structure, size distribution is between 5-150nm, and composition meets stoichiometric ratio.The present invention is by the nanocrystalline ink cladding process of the nanocrystalline employing of ZnSe, good stability, high-quality polycrystalline semiconductor thin film (zinc selenide film) can be obtained, this zinc selenide film can substitute CdS buffer layer and use as the buffer layer of thin film solar cell, avoid cadmium pollution, high-quality ZnSe buffer layer is fine and close, nothing is empty and slight crack, can ensure the transformation efficiency of thin film solar cell (as copper-indium-galliun-selenium (CIGS) thin film solar cell).
Accompanying drawing explanation
Fig. 1 is the nanocrystalline X ray diffracting spectrum (XRD) of ZnSe obtained in the embodiment of the present invention 1.
Embodiment
Below contrast accompanying drawing and combine preferred embodiment the invention will be further described.
The invention provides the preparation method that a kind of ZnSe is nanocrystalline, in a specific embodiment, this preparation method comprises the steps:
S1, prepare selenium precursor solution: oleyl amine, selenium simple substance and reductive agent are made into reaction soln, and reacting by heating obtains selenium precursor solution; In described reaction soln, the concentration of selenium precursor solution is 0.25-1.5mol/L, the mol ratio >=1:1 of described reductive agent and described selenium simple substance, and described reductive agent is dimethyamine borane or sodium borohydride;
S2, preparation zinc precursor solution: be dispersed in reaction solvent in zinc source and join to obtain described zinc precursor solution, the mol ratio of described zinc source and described selenium simple substance is 1:1 ~ 1:1.5, described reaction solvent is oleyl amine or the mixed solvent for octadecylene and hard fatty acids;
ZnSe is nanocrystalline for S3, preparation: under anhydrous and oxygen-free system, described zinc precursor solution in step S2 is heated to 150-350 DEG C, be expelled in described zinc precursor solution by selenium precursor solution described in step S1, the reaction times is 10min at least again, obtains described ZnSe nanocrystalline.
Some preferred embodiment in, can also at least one in preferred following scheme:
Before described step S3, also comprise the step described selenium precursor solution in step S1 being cooled to 70-100 DEG C.
The mol ratio of the reductive agent in step S1 and described selenium simple substance is 1:1 ~ 1:2.
Described zinc source in step S2 is the one in zinc acetylacetonate, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate, zinc oleate and zinc ethyl; Preferred zinc acetylacetonate further.
In step sl, described reductive agent is dimethyamine borane, and the temperature of described reacting by heating is 130-150 DEG C.
In octadecylene in step s 2 and the mixed solvent of hard fatty acids, the volume of described octadecylene is 8-12mL:2-5mmol with the ratio of the amount of substance of described hard fatty acids.
Reaction times in step S3 is 10min ~ 6 hour.
After described step S3, also comprise S4: wash described ZnSe is nanocrystalline with organic solvent, described organic solvent is selected from least one in toluene, chloroform, normal hexane, methyl alcohol, ethanol and Virahol.
Described organic solvent is the mixed solvent of toluene and ethanol, and the volume ratio of toluene and ethanol is 1:2.
The present invention also provides a kind of ZnSe obtained by aforesaid method nanocrystalline, and it is zincblende lattce structure, and size distribution is between 5-150nm.
The preparation method of the present invention's also a kind of ZnSe buffer layer, in a kind of embodiment, comprises the steps:
(1) ZnSe preparation method nanocrystalline for above-mentioned ZnSe prepared is nanocrystalline is that 100-500mg/mL dispersion is mixed with the nanocrystalline ink of homogeneous, stable ZnSe in organic solvent by solid-to-liquid ratio;
(2) obtained ZnSe buffer layer on the absorption layer nanocrystalline for described ZnSe ink being coated in thin film solar cell, the thickness of described ZnSe buffer layer is 50-100nm.
In some preferred implementations, can preferably by the following technical solutions at least one:
Solid-to-liquid ratio in described step (1) is 150-250mg/mL.
Wherein, before step (1), the absorption layer of deposited on substrates thin film solar cell is also included in; The optional molybdenum glass of material of substrate, molybdenum sheet, also can select the flexible substrate material such as stainless steel, plastics, preferably with molybdenum glass or molybdenum sheet for substrate.
Organic solvent in step (1) is selected from least one in toluene, chloroform, normal hexane, methyl alcohol, ethanol, Virahol and hexylmercaptan.
The method of the coating in step (2) can for dripping painting, blade coating, spin coating, spraying or be stained with the one in painting, preferred blade coating.
Below by way of preferred embodiment, the present invention is further elaborated.
Embodiment 1
The preparation method that ZnSe is nanocrystalline, comprises the steps:
S1, prepare selenium precursor solution: by the oleyl amine of 1.5mL, the selenium powder of 1.5mmol and the dimethyamine borane of 0.75mmol are added in the flask of 25mL, be heated to 130 DEG C stir simultaneously, after 5 minutes, selenium powder dissolves, the color of solution becomes chocolate from colourless, and then becomes water white selenium precursor solution.This selenium precursor solution is cooled to 70 DEG C for subsequent use.
S2, preparation zinc precursor solution: the octadecylene of 1.5mmol zinc acetylacetonate, 10mL and the hard fatty acids of 3mmol are joined in the there-necked flask of 50mL.
ZnSe is nanocrystalline for S3, preparation: under the there-necked flask in this step S2 being positioned over the anhydrous and oxygen-free system (Schlenk system) of standard, carry out the deoxygenation 1h that dewaters.Then be warming up to 230 DEG C, at such a temperature, use syringe, be expelled to rapidly by the selenium precursor solution of step S1 gained in the zinc precursor solution stirred rapidly, 10min is to guarantee the growth of nano particle in reaction.After reaction terminates, by reaction soln naturally cooling, synthesize ZnSe nanocrystalline.
S4: use toluene and alcohol mixing solutions that volume ratio is 1:2, reaction product is washed, cleans 2-5 time, after centrifugation, supernatant liquor is outwelled, obtain ZnSe nanocrystalline, gained ZnSe is nanocrystalline is zincblende lattce structure, and particle diameter is at about 10nm, and composition meets stoichiometric ratio.
The nanocrystalline XRD detected result of the ZnSe that the present embodiment obtains as shown in Figure 1.As seen from Figure 1: completely the same with the ZnSe diffraction peak in the 80-0021 on JCPDS card, illustrate that product ZnSe is nanocrystalline for Emission in Cubic zincblende lattce structure.
Embodiment 2
A preparation method for ZnSe buffer layer, comprises the steps:
(1) by nanocrystalline for ZnSe that embodiment 1 is obtained be that 200mg/mL is dispersed in toluene and is mixed with the nanocrystalline ink of homogeneous, stable ZnSe by solid-to-liquid ratio.
(2) adopt the method for galvanic deposit on molybdenum glass, deposit the absorption layer of CIGS thin film solar cell, this absorption layer drips the nanocrystalline ink of ZnSe in step (1), with scraper by nanocrystalline for ZnSe ink blade coating film forming.Then 100 DEG C of heat preservation and drynesses in vacuum drying oven, form zinc selenide film that is fine and close, consistency of thickness, the thickness of film is 50nm, and the sample of the zinc selenide buffer layer prepared is preserved under normal temperature, dry environment, for follow-up technique uses.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For those skilled in the art, without departing from the inventive concept of the premise, some equivalent to substitute or obvious modification can also be made, and performance or purposes identical, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. the preparation method that ZnSe is nanocrystalline, is characterized in that, comprises the steps:
S1, prepare selenium precursor solution: oleyl amine, selenium simple substance and reductive agent are made into reaction soln, and reacting by heating obtains described selenium precursor solution; In described reaction soln, the concentration of described selenium precursor solution is 0.25-1.5mol/L, the mol ratio >=1:1 of described reductive agent and described selenium simple substance, and described reductive agent is dimethyamine borane or sodium borohydride;
S2, preparation zinc precursor solution: be dispersed in reaction solvent in zinc source and join to obtain described zinc precursor solution, the mol ratio of described zinc source and described selenium simple substance is 1:1 ~ 1:1.5, described reaction solvent is oleyl amine or the mixed solvent for octadecylene and hard fatty acids;
ZnSe is nanocrystalline for S3, preparation: under anhydrous and oxygen-free system, described zinc precursor solution in step S2 is heated to 150-350 DEG C, be expelled in described zinc precursor solution by selenium precursor solution described in step S1, the reaction times is 10min at least again, obtains described ZnSe nanocrystalline.
2. the preparation method that ZnSe as claimed in claim 1 is nanocrystalline, is characterized in that: before described step S3, also comprises the step described selenium precursor solution in step S1 being cooled to 70-100 DEG C.
3. the preparation method that ZnSe as claimed in claim 1 is nanocrystalline, is characterized in that: the described zinc source in step S2 is the one in zinc acetylacetonate, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate, zinc oleate and zinc ethyl.
4. the preparation method that ZnSe as claimed in claim 1 is nanocrystalline, it is characterized in that: in step sl, described reductive agent is dimethyamine borane, and the temperature of described reacting by heating is 130-150 DEG C.
5. the preparation method that ZnSe as claimed in claim 1 is nanocrystalline, is characterized in that: in described octadecylene in step s 2 and the mixed solvent of hard fatty acids, the volume of described octadecylene is 8-12mL:2-5mmol with the ratio of the amount of substance of described hard fatty acids.
6. the preparation method that ZnSe as claimed in claim 1 is nanocrystalline, it is characterized in that: after described step S3, also comprise S4: wash described ZnSe is nanocrystalline with organic solvent, described organic solvent is selected from least one in toluene, chloroform, normal hexane, methyl alcohol, ethanol and Virahol.
7. the preparation method that ZnSe as claimed in claim 6 is nanocrystalline, it is characterized in that: described organic solvent is the mixed solvent of toluene and ethanol, the volume ratio of toluene and ethanol is 1:2.
8. the ZnSe obtained by the preparation method described in claim 1-7 any one is nanocrystalline, it is characterized in that: described ZnSe is nanocrystalline is zincblende lattce structure, and size distribution is between 5-150nm.
9. a preparation method for ZnSe buffer layer, is characterized in that, comprises the steps:
(1) described ZnSe preparation method nanocrystalline for the ZnSe described in claim 1-7 any one prepared is nanocrystalline is that 100-500mg/mL dispersion is mixed with the nanocrystalline ink of homogeneous, stable ZnSe in organic solvent by solid-to-liquid ratio;
(2) obtained ZnSe buffer layer on the absorption layer nanocrystalline for described ZnSe ink being coated in thin film solar cell, the thickness of described ZnSe buffer layer is 50-100nm.
10. the preparation method of ZnSe buffer layer as claimed in claim 9, is characterized in that: the solid-to-liquid ratio in described step (1) is 150-250mg/mL.
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| CN114506824A (en) * | 2021-12-02 | 2022-05-17 | 佛山市铁人环保科技有限公司 | Zinc selenide sol and preparation method and application thereof |
| CN115818582A (en) * | 2021-09-16 | 2023-03-21 | 浙江大学 | Precursor composition and preparation method thereof, and preparation method of inorganic nanocrystal |
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| CN115818582A (en) * | 2021-09-16 | 2023-03-21 | 浙江大学 | Precursor composition and preparation method thereof, and preparation method of inorganic nanocrystal |
| CN114506824A (en) * | 2021-12-02 | 2022-05-17 | 佛山市铁人环保科技有限公司 | Zinc selenide sol and preparation method and application thereof |
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