CN103011261B - Solvothermal synthesis method of wurtzite structure CZTS(Se) (Copper Zinc Tin Sulfide) semiconductor material under synergistic effect of ultrasonic waves and microwaves - Google Patents
Solvothermal synthesis method of wurtzite structure CZTS(Se) (Copper Zinc Tin Sulfide) semiconductor material under synergistic effect of ultrasonic waves and microwaves Download PDFInfo
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- CN103011261B CN103011261B CN201210503986.5A CN201210503986A CN103011261B CN 103011261 B CN103011261 B CN 103011261B CN 201210503986 A CN201210503986 A CN 201210503986A CN 103011261 B CN103011261 B CN 103011261B
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- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000004065 semiconductor Substances 0.000 title claims abstract description 31
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000004729 solvothermal method Methods 0.000 title claims abstract 5
- 230000002195 synergetic effect Effects 0.000 title claims 2
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 69
- 239000010949 copper Substances 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 19
- 230000000694 effects Effects 0.000 claims description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 238000002604 ultrasonography Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000523 sample Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 235000021313 oleic acid Nutrition 0.000 claims description 7
- 239000011669 selenium Substances 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 230000012010 growth Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 claims 3
- 238000010899 nucleation Methods 0.000 claims 3
- 150000001879 copper Chemical class 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 claims 2
- 239000011593 sulfur Substances 0.000 claims 2
- 238000010189 synthetic method Methods 0.000 claims 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims 1
- 150000004683 dihydrates Chemical group 0.000 claims 1
- YWWZCHLUQSHMCL-UHFFFAOYSA-N diphenyl diselenide Chemical compound C=1C=CC=CC=1[Se][Se]C1=CC=CC=C1 YWWZCHLUQSHMCL-UHFFFAOYSA-N 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 17
- 238000003786 synthesis reaction Methods 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 229910052729 chemical element Inorganic materials 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000003541 multi-stage reaction Methods 0.000 description 18
- 238000002156 mixing Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 229960000935 dehydrated alcohol Drugs 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 235000011150 stannous chloride Nutrition 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 5
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 241000545067 Venus Species 0.000 description 5
- 239000001119 stannous chloride Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical group [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 2
- 238000002525 ultrasonication Methods 0.000 description 2
- 230000010748 Photoabsorption Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- KYRUBSWVBPYWEF-UHFFFAOYSA-N copper;iron;sulfane;tin Chemical compound S.S.S.S.[Fe].[Cu].[Cu].[Sn] KYRUBSWVBPYWEF-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 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
- 230000005855 radiation Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Abstract
本发明公开了一种超声波/微波协同作用下常压溶剂热合成纤锌矿结构Cu2ZnSnS4或Cu2ZnSnSe4半导体材料的方法。将反应原料溶于有机溶剂后置于超声波微波组合反应***内，在超声场中通过微波加热完成溶剂热反应合成，反应过程中控制反应体系的反应温度，反应时间，超声功率以及超声时间进而达到合成目标产物—纤锌矿结构Cu2ZnSnS4和Cu2ZnSnSe4半导体材料之目的。产物的化学元素组成可以通过反应原料的摩尔配比进行精确控制，产物的形貌和结晶形态可通过反应过程各参数进行调控。本发明降低了对合成条件的要求，并且可以更灵活控制整个合成过程从而形成特定的结构，且本发明还具有反应装置简单、反应速度快速、反应过程可控性和可干预性强等特点。
The invention discloses a method for synthesizing Cu 2 ZnSnS 4 or Cu 2 ZnSnSe 4 semiconductor materials with a wurtzite structure under normal pressure solvothermal synthesis under ultrasonic/microwave synergy. The reaction raw materials are dissolved in an organic solvent and placed in an ultrasonic and microwave combined reaction system. Solvothermal reaction synthesis is completed by microwave heating in an ultrasonic field. During the reaction, the reaction temperature, reaction time, ultrasonic power and ultrasonic time of the reaction system are controlled to achieve The purpose of synthesizing target products—wurtzite structure Cu 2 ZnSnS 4 and Cu 2 ZnSnSe 4 semiconductor materials. The chemical element composition of the product can be precisely controlled by the molar ratio of the reaction raw materials, and the morphology and crystal form of the product can be regulated by the parameters of the reaction process. The present invention reduces the requirements on synthesis conditions, and can more flexibly control the entire synthesis process to form a specific structure, and the present invention also has the characteristics of simple reaction device, fast reaction speed, controllable reaction process and strong intervening ability.
Description
Technical field
The present invention relates to Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under the effect of a kind of ultrasonic wave/microwave cooperating
2znSnS
4(Wurtzite CZTS) or Cu
2znSnSe
4the method of (Wurtzite CZTSe) semiconductor material, the semiconductor material of synthesized is applied to the exploitation of thin film solar cell precursor, the technical fields such as photo-sensor.
Background technology
Novel wurtzite structure Cu
2znSnS
4and Cu
2znSnSe
4semiconductor material has very high photoabsorption coefficient (10
4cm
-1), than cube custerite structure (kesterite) and two kinds of structures of tin pyrite (stannite) there is better sintering activity, application prospect is considerable; Generally, solvent thermal compounding wurtzite structure C u
2znSnS
4and Cu
2znSnSe
4need in the hot environment of inert atmosphere, long-time insulation reaction just can carry out, this synthesis mode very flexible, the time of reaction is longer, and can not intervene reaction pilot process; The present invention utilizes feature and the ultrasonic activation effect of ultrasonic wave in liquid of carry out microwave radiation heating uniformity, reduces synthesis temperature, and fast reaction speed reaches the object of synthesizing fast target product under normal pressure.
Summary of the invention
The object of the invention is take one or more in water, ethanol, ethylene glycol, glycerol, diethanolamine, acetic acid, propionic acid, oxalic acid and oleic acid is solvent, take mantoquita, zinc salt, pink salt and sulphur source (selenium source) is raw material, utilizes ultrasonic wave and microwave cooperating effect by the quick compounding wurtzite structure C of solvent thermal process u under normal pressure
2znSnS
4or Cu
2znSnSe
4semiconductor material.
Concrete steps are:
(1) Cu:Zn:Sn:S=2:1:1:4～5 or Cu:Zn:Sn:Se=2:1:1:4～5 take mantoquita, zinc salt and pink salt and are dissolved in solvent and make solution A in molar ratio, taking sulphur source or selenium source is dissolved in or is dispersed in solvent and make solution B, above-mentioned A, B two solution add in there-necked flask after mixing, described there-necked flask is placed in ultrasonic wave/microwave composite reaction system, and prolong is inserted respectively on the both sides of there-necked flask and ultrasound probe is inserted in thermometer, centre.
(2) ultrasonic wave/microwave composite reaction system parameters described in step (1) is as follows: microwave heating power setting is 50～1000 watts, ultrasonic power is set to 10～80%, temperature of reaction is set to 100～250 ℃, ultrasonic time is set to 1～10 second, and be set to 1～10 second ultrasonic off time.
(3) reactive system that unlatching step (2) arranges starts reaction, after temperature rises to set temperature, insulation reaction is 0.5～3 hour, finish to treat system naturally cooling after reaction, gained reaction solution is through deionized water and dehydrated alcohol centrifuge washing 3～4 times respectively, and products therefrom is put into vacuum-drying at 70～90 ℃ of vacuum drying ovens and within 7～9 hours, made wurtzite structure Cu
2znSnS
4or Cu
2znSnSe
4semiconductor material.
Described mantoquita is a kind of in venus crystals, copper chloride dihydrate, copper sulfate, and described zinc salt is a kind of in zinc acetate, zinc chloride, zinc sulfate, and described pink salt is a kind of in two hydrated stannous chlorides, crystallization tin tetrachloride.
Described sulphur source is a kind of in thiocarbamide, sulphur powder and thioacetamide.
Described selenium source is a kind of in diphenyl disenenide, selenous acid and selenium powder.
Described solvent is one or more in water, ethanol, ethylene glycol, glycerol, diethanolamine, acetic acid, propionic acid, oxalic acid and oleic acid, when being multiple, the solvent that uses can be with arbitrary volume than mixing.
The present invention controls by controlling the structure and composition of the synergy realization response thing of ultrasonic in solvent thermal building-up process and microwave, and the uniform heat-field that utilizes microwave heating to obtain provides reaction required basal heat mechanical condition; Utilize ultrasonication to control forming core and growth, in the forming core stage, utilize quick, a large amount of forming core of the cavatition of ultrasonication in uniform liquid; Crystal growth phase, utilizes focusing effect quick, even, controlled grow up of ultrasonic wave on nucleus and reaction soln two-phase interface.
The present invention is by controlling temperature of reaction, the reaction times, and microwave power, ultrasonic power, that control ultrasonic time of origin and ultrasonic off time reaction carries out speed and degree.
Compare with common solvent thermal synthesis technique, wurtzite structure Cu is prepared in the thermal synthesis of ultrasonic wave/microwave-assisted Solvent at Atmospheric Pressure
2znSnS
4or Cu
2znSnSe
4semiconductor material greatly reduces the requirement to synthesis condition, thereby and can control more flexibly whole reaction building-up process and form specific structure, ultrasonic wave microwave cooperating of the present invention effect has significant reaction activity power, under the condition that can make building-up reactions be difficult to occur in conventional solvent thermal, reacts rapidly; Have reaction unit simple, speed of response is fast simultaneously, reaction process controllability and the feature such as can intervention strong.
Accompanying drawing explanation:
Fig. 1 is preparation technology's schema of the present invention.
Fig. 2 is that the embodiment of the present invention 1 be take ethylene glycol Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under the effect of solvent supersonic ripple/microwave cooperating
2znSnS
4the XRD diffractogram of semiconductor material.
Fig. 3 is that the embodiment of the present invention 1 be take ethylene glycol Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under the effect of solvent supersonic ripple/microwave cooperating
2znSnS
4the SEM shape appearance figure of semiconductor material.
Fig. 4 is that the embodiment of the present invention 2 be take glycerol Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under the effect of solvent supersonic ripple/microwave cooperating
2znSnSe
4the XRD diffractogram of semiconductor material.
Fig. 5 is that the embodiment of the present invention 2 be take glycerol Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under the effect of solvent supersonic ripple/microwave cooperating
2znSnSe
4the SEM shape appearance figure of semiconductor material.
Fig. 6 is that the embodiment of the present invention 3 be take glycerol and oleic acid Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under the effect of double solvents ultrasonic wave/microwave cooperating
2znSnS
4the XRD diffractogram of semiconductor material.
Fig. 7 is that the embodiment of the present invention 3 be take glycerol and oleic acid Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under the effect of double solvents ultrasonic wave/microwave cooperating
2znSnS
4the SEM shape appearance figure of semiconductor material.
Fig. 8 is that the embodiment of the present invention 4 be take glycerol and diethanolamine Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under the effect of double solvents ultrasonic wave/microwave cooperating
2znSnS
4the XRD diffractogram of semiconductor material.
Fig. 9 is that the embodiment of the present invention 4 be take glycerol and diethanolamine Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under the effect of double solvents ultrasonic wave/microwave cooperating
2znSnS
4the SEM shape appearance figure of semiconductor material.
Embodiment:
Embodiment 1
(1) by 0.2991 gram of venus crystals (Cu (CH
3cOO)
2h
2o), 0.2744 gram of zinc acetate (Zn (CH
3cOO)
22H
2o) and 0.2821 gram of two hydrated stannous chloride (SnCl
22H
2o) be dissolved in 40ml ethylene glycol, by 0.4282 gram of thiocarbamide (CS (NH
2)
2) be dissolved in 20ml ethylene glycol, after mixing, obtained solution adds in there-necked flask, and described there-necked flask is placed in ultrasonic wave/microwave composite reaction system, and prolong is inserted respectively on the both sides of there-necked flask and ultrasound probe is inserted in thermometer, centre.
(2) ultrasonic wave/microwave composite reaction system parameters described in step (1) is as follows: the 1st 150 ℃ of stages, 10 minutes, 500 watts of maximum microwave powers; The 2nd 150 ℃ of stages, 60 minutes, 400 watts of maximum microwave powers; Ultrasonic power 20%, ultrasonic time 2 seconds, 10 seconds off times.
(3) the reactive system reaction arranging according to step (2), system naturally cooling after finishing reaction, gained reaction solution is through deionized water and dehydrated alcohol centrifuge washing 4 times respectively, and products therefrom is put into vacuum-drying at 80 ℃ of vacuum drying ovens and within 8 hours, made Cu
2znSnS
4semiconductor material.
Gained Cu
2znSnS
4through XRD analysis as shown in Figure 2, be wurtzite structure Cu
2znSnS
4; As shown in Figure 3, powder is mainly by irregular roundness granulometric composition for scanning electron microscope analysis, and the diameter of particle is approximately 1～3 μ m.
Embodiment 2
(1) by 0.2991 gram of venus crystals (Cu (CH
3cOO)
2h
2o), 0.2744 gram of zinc acetate (Zn (CH
3cOO)
22H
2o) and 0.2821 gram of two hydrated stannous chloride (SnCl
22H
2o) be dissolved in 40ml glycerol, by 1.6855 grams of diphenyl disenenide (C
12h
10se
2) be dissolved in 20ml glycerol, after mixing, obtained solution adds in there-necked flask, and described there-necked flask is placed in ultrasonic wave/microwave composite reaction system, and prolong is inserted respectively on the both sides of there-necked flask and ultrasound probe is inserted in thermometer, centre.
(2) ultrasonic wave/microwave composite reaction system parameters described in step (1) is as follows: the 1st 210 ℃ of stages, 10 minutes, 500 watts of maximum microwave powers; The 2nd 210 ℃ of stages, 60 minutes, 400 watts of maximum microwave powers; Ultrasonic power 20%, ultrasonic time 2 seconds, 10 seconds off times.
(3) the reactive system reaction arranging according to step (2), system naturally cooling after finishing reaction, gained reaction solution is through deionized water and dehydrated alcohol centrifuge washing 4 times respectively, and products therefrom is put into vacuum-drying at 80 ℃ of vacuum drying ovens and within 8 hours, made Cu
2znSnSe
4semiconductor material.
Gained Cu
2znSnSe
4semiconductor material through XRD analysis as shown in Figure 4, is wurtzite Cu
2znSnSe
4; As shown in Figure 5, powder is mainly by the granulometric composition of irregular bar-shaped, bullet shaped for scanning electron microscope analysis, and the diameter of particle is 50～150nm, and length is 50～100nm.
Embodiment 3
(1) by 0.2991 gram of venus crystals (Cu (CH
3cOO)
2h
2o), 0.2744 gram of zinc acetate (Zn (CH
3cOO)
22H
2o) and 0.2821 gram of two hydrated stannous chloride (SnCl
22H
2o) be dissolved in 22ml glycerol and 18ml oleic acid mixed solvent, by 0.4282 gram of thiocarbamide (CS (NH
2)
2) be dissolved in 20ml glycerol, after mixing, obtained solution adds in there-necked flask, and described there-necked flask is placed in ultrasonic wave/microwave composite reaction system, and prolong is inserted respectively on the both sides of there-necked flask and ultrasound probe is inserted in thermometer, centre.
(2) ultrasonic wave/microwave composite reaction system parameters described in step (1) is as follows: the 1st 200 ℃ of stages, 10 minutes, 500 watts of maximum microwave powers; The 2nd 200 ℃ of stages, 60 minutes, 400 watts of maximum microwave powers; Ultrasonic power 20%, ultrasonic time 2 seconds, 10 seconds off times.
(3) the reactive system reaction arranging according to step (2), system naturally cooling after finishing reaction, gained reaction solution is through deionized water and dehydrated alcohol centrifuge washing 4 times respectively, and products therefrom is put into vacuum-drying at 80 ℃ of vacuum drying ovens and within 8 hours, made Cu
2znSnS
4semiconductor material.
Gained Cu
2znSnS
4semiconductor material through XRD analysis as shown in Figure 6, is wurtzite Cu
2znSnS
4with cubic zinc blende structure C u
2znSnS
4; As shown in Figure 7, powder is mainly comprised of irregular ball particle scanning electron microscope analysis, and the diameter of particle is approximately 500nm left and right.
Embodiment 4
(1) by 0.2991 gram of venus crystals (Cu (CH
3cOO)
2h
2o), 0.2744 gram of zinc acetate (Zn (CH
3cOO)
22H
2o) and 0.2821 gram of two hydrated stannous chloride (SnCl
22H
2o) be dissolved in 34ml glycerol and 6ml diethanolamine mixed solvent, by 0.4282 gram of thiocarbamide (CS (NH
2)
2) be dissolved in 20ml glycerol, after mixing, obtained solution adds in there-necked flask, and described there-necked flask is placed in ultrasonic wave/microwave composite reaction system, and prolong is inserted respectively on the both sides of there-necked flask and ultrasound probe is inserted in thermometer, centre.
(2) ultrasonic wave/microwave composite reaction system parameters described in step (1) is as follows: the 1st 200 ℃ of stages, 10 minutes, 500 watts of maximum microwave powers; The 2nd 200 ℃ of stages, 60 minutes, 400 watts of maximum microwave powers; Ultrasonic power 20%, ultrasonic time 2 seconds, 10 seconds off times.
(3) the reactive system reaction arranging according to step (2), system naturally cooling after finishing reaction, gained reaction solution is through deionized water and dehydrated alcohol centrifuge washing 4 times respectively, and products therefrom is put into vacuum-drying at 80 ℃ of vacuum drying ovens and within 8 hours, made Cu
2znSnS
4semiconductor material.
Gained Cu
2znSnS
4semiconductor material through XRD analysis as shown in Figure 8, is wurtzite Cu
2znSnS
4with cubic zinc blende structure C u
2znSnS
4; As shown in Figure 9, powder is mainly comprised of irregular ball particle scanning electron microscope analysis, and the diameter of particle is approximately 100nm left and right.
Embodiment 5
(1) by 0.2046 gram of copper chloride dihydrate (CuCl
22H
2o), 0.1636 gram of zinc chloride (ZnCl
2) and 0.4207 gram of crystallization tin tetrachloride (SnCl
45H
2o) be dissolved in 22ml glycerol and 18ml oleic acid mixed solvent, 0.4226 gram of thioacetamide is dissolved in to 20ml glycerol, after mixing, obtained solution adds in there-necked flask, described there-necked flask is placed in ultrasonic wave/microwave composite reaction system, and prolong is inserted respectively on the both sides of there-necked flask and ultrasound probe is inserted in thermometer, centre.
(2) ultrasonic wave/microwave composite reaction system parameters described in step (1) is as follows: the 1st 200 ℃ of stages, 10 minutes, 500 watts of maximum microwave powers; The 2nd 200 ℃ of stages, 60 minutes, 400 watts of maximum microwave powers; Ultrasonic power 20%, ultrasonic time 2 seconds, 10 seconds off times.
(3) the reactive system reaction arranging according to step (2), system naturally cooling after finishing reaction, gained reaction solution is through deionized water and dehydrated alcohol centrifuge washing 4 times respectively, and products therefrom is put into vacuum-drying at 80 ℃ of vacuum drying ovens and within 8 hours, made Cu
2znSnS
4semiconductor material.
Embodiment 6
(1) by 0.1915 gram of copper sulfate (CuSO
4), 0.1939 gram of zinc sulfate (ZnSO
4) and 0.4207 gram of crystallization tin tetrachloride (SnCl
45H
2o) or other pink salt be dissolved in 22ml glycerol and 18ml oxalic acid mixed solvent, by 0.4282 gram of thiocarbamide (CS (NH
2)
2) be dissolved in 20ml glycerol, after mixing, obtained solution adds in there-necked flask, and described there-necked flask is placed in ultrasonic wave/microwave composite reaction system, and prolong is inserted respectively on the both sides of there-necked flask and ultrasound probe is inserted in thermometer, centre.
(2) ultrasonic wave/microwave composite reaction system parameters described in step (1) is as follows: the 1st 200 ℃ of stages, 10 minutes, 500 watts of maximum microwave powers; The 2nd 200 ℃ of stages, 60 minutes, 400 watts of maximum microwave powers; Ultrasonic power 20%, ultrasonic time 2 seconds, 10 seconds off times.
(3) the reactive system reaction arranging according to step (2), system naturally cooling after finishing reaction, gained reaction solution is through deionized water and dehydrated alcohol centrifuge washing 4 times respectively, and products therefrom is put into vacuum-drying at 80 ℃ of vacuum drying ovens and within 8 hours, made Cu
2znSnS
4semiconductor material.
Embodiment 7
(1) by 0.2046 gram of copper chloride dihydrate (CuCl
22H
2o), 0.1636 gram of zinc chloride (ZnCl
2) and 0.4207 gram of crystallization tin tetrachloride (SnCl
45H
2o) be dissolved in 34ml glycerol and 6ml diethanolamine mixed solvent, 0.1803 gram of sulphur powder is dissolved in to 20ml glycerol, after mixing, obtained solution adds in there-necked flask, described there-necked flask is placed in ultrasonic wave/microwave composite reaction system, and prolong is inserted respectively on the both sides of there-necked flask and ultrasound probe is inserted in thermometer, centre.
(2) ultrasonic wave/microwave composite reaction system parameters described in step (1) is as follows: the 1st 200 ℃ of stages, 10 minutes, 500 watts of maximum microwave powers; The 2nd 200 ℃ of stages, 60 minutes, 400 watts of maximum microwave powers; Ultrasonic power 20%, ultrasonic time 2 seconds, 10 seconds off times.
(3) the reactive system reaction arranging according to step (2), system naturally cooling after finishing reaction, gained reaction solution is through deionized water and dehydrated alcohol centrifuge washing 4 times respectively, and products therefrom is put into vacuum-drying at 80 ℃ of vacuum drying ovens and within 8 hours, made Cu
2znSnS
4semiconductor material.
Embodiment 8
(1) by 0.1915 gram of copper sulfate (CuSO
4), 0.1939 gram of zinc sulfate (ZnSO
4) and 0.2821 gram of two hydrated stannous chloride (SnCl
22H
2o) be dissolved in 34ml glycerol and 6ml diethanolamine mixed solvent, by 0.4282 gram of thiocarbamide (CS (NH
2)
2) be dissolved in 20ml glycerol, after mixing, obtained solution adds in there-necked flask, and described there-necked flask is placed in ultrasonic wave/microwave composite reaction system, and prolong is inserted respectively on the both sides of there-necked flask and ultrasound probe is inserted in thermometer, centre.
(2) ultrasonic wave/microwave composite reaction system parameters described in step (1) is as follows: the 1st 200 ℃ of stages, 10 minutes, 500 watts of maximum microwave powers; The 2nd 200 ℃ of stages, 60 minutes, 400 watts of maximum microwave powers; Ultrasonic power 20%, ultrasonic time 2 seconds, 10 seconds off times.
(3) the reactive system reaction arranging according to step (2), system naturally cooling after finishing reaction, gained reaction solution is through deionized water and dehydrated alcohol centrifuge washing 4 times respectively, and products therefrom is put into vacuum-drying at 80 ℃ of vacuum drying ovens and within 8 hours, made Cu
2znSnS
4semiconductor material.
Claims (3)
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| CN103474512B (en) * | 2013-09-26 | 2016-01-27 | 南京师范大学 | The method of microwave method one-step synthesis sulfide copper zinc tin quantum dot |
| CN103613119B (en) * | 2013-11-21 | 2015-07-29 | 电子科技大学 | Preparation method and application of copper-zinc-tin-sulfur |
| CN103611549B (en) * | 2013-11-21 | 2016-03-30 | 电子科技大学 | The preparation method of copper zinc tin sulfide/graphene oxide composite semiconductor photocatalyst |
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| CN105470112A (en) * | 2015-11-18 | 2016-04-06 | 广东工业大学 | Method and application for preparing copper zinc tin sulfur semiconductor film on FTO substrate |
| CN106277038B (en) * | 2016-07-27 | 2017-09-22 | 昆明理工大学 | A kind of preparation method of micro-nano compound structure buergerite copper-zinc-tin-sulfur particulate |
| CN108165790B (en) * | 2018-01-24 | 2019-06-04 | 福州大学 | A cubic phase Ca2Ge alloy material and microwave solid phase preparation method thereof |
| CN108265189B (en) * | 2018-01-24 | 2019-09-13 | 福州大学 | A kind of Bi-doped cubic-phase germanium-calcium thermoelectric material and microwave solid-phase preparation method thereof |
| CN114914710B (en) * | 2022-05-18 | 2023-06-27 | 山东大学 | A kind of electromagnetic wave absorbing material and its preparation method and application |
| CN116377729A (en) * | 2023-04-17 | 2023-07-04 | 南通宗杰纺织科技有限公司 | Preparation method of self-heating antibacterial fabric coating |
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