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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
reaction
ultrasonic
microwave
semiconductor material
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201210503986.5A
Other languages
Chinese (zh)
Other versions
CN103011261A (en
Inventor
龙飞
池上森
莫淑一
郑国源
邹正光
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guilin University of Technology
Original Assignee
Guilin University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guilin University of Technology filed Critical Guilin University of Technology
Priority to CN201210503986.5A priority Critical patent/CN103011261B/en
Publication of CN103011261A publication Critical patent/CN103011261A/en
Application granted granted Critical
Publication of CN103011261B publication Critical patent/CN103011261B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a solvothermal synthesis method of a wurtzite structure Cu2ZnSnS4 or Cu2ZnSnSe4 semiconductor material under a synergistic effect of ultrasonic waves/microwaves. The solvothermal synthesis method comprises the following steps of: dissolving a reaction raw material in an organic solvent and then placing in an ultrasonic wave and microwave combined reaction system, completing the solvothermal reaction synthesis in an ultrasonic filed through microwave heating, and controlling the reaction temperature, reaction time, ultrasonic power and ultrasonic time of the reaction system in a reaction process to achieve the purpose of synthesizing a target product, namely a wurtzite structure Cu2ZnSnS4 and Cu2ZnSnSe4 semiconductor material. The chemical element composition of the product can be accurately controlled through a mol ratio of the reaction raw material, and the morphology and crystallization form of the product can be regulated and controlled through all parameters of the reaction process. The solvothermal synthesis method is reduced in requirements for synthesis conditions, is capable of more flexibly controlling the whole synthesis process so as to form a specific structure, and has the characteristics of simple reaction device, high reaction speed, strong controllability and intervention in the reaction process, and the like.

Description

The method of solvent thermal compounding wurtzite structure C ZTS (Se) semiconductor material under the effect of ultrasonic wave microwave cooperating
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)

1. Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under ultrasonic wave/microwave cooperating effect 2znSnS 4or Cu 2znSnSe 4the method of semiconductor material, is characterized in that 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, 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.
2. synthetic method according to claim 1, it is characterized in that: by controlling the structure and composition of the synergy realization response thing of ultrasonic in solvent thermal building-up process and microwave, control, the uniform heat-field that utilizes microwave heating to obtain provides reaction required basal heat mechanical condition, and 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.
3. synthetic method according to claim 1 and 2, is characterized in that: by what control temperature of reaction, reaction times, microwave power, ultrasonic power, ultrasonic time of origin and control reaction ultrasonic off time, carry out speed and degree.
CN201210503986.5A 2012-12-02 2012-12-02 Solvothermal synthesis method of wurtzite structure CZTS(Se) (Copper Zinc Tin Sulfide) semiconductor material under synergistic effect of ultrasonic waves and microwaves Expired - Fee Related CN103011261B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210503986.5A CN103011261B (en) 2012-12-02 2012-12-02 Solvothermal synthesis method of wurtzite structure CZTS(Se) (Copper Zinc Tin Sulfide) semiconductor material under synergistic effect of ultrasonic waves and microwaves

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210503986.5A CN103011261B (en) 2012-12-02 2012-12-02 Solvothermal synthesis method of wurtzite structure CZTS(Se) (Copper Zinc Tin Sulfide) semiconductor material under synergistic effect of ultrasonic waves and microwaves

Publications (2)

Publication Number Publication Date
CN103011261A CN103011261A (en) 2013-04-03
CN103011261B true CN103011261B (en) 2014-08-20

Family

ID=47960444

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210503986.5A Expired - Fee Related CN103011261B (en) 2012-12-02 2012-12-02 Solvothermal synthesis method of wurtzite structure CZTS(Se) (Copper Zinc Tin Sulfide) semiconductor material under synergistic effect of ultrasonic waves and microwaves

Country Status (1)

Country Link
CN (1) CN103011261B (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103420411A (en) * 2013-07-11 2013-12-04 南京航空航天大学 Ultrasonic-assisted microwave controllable preparation method of Cu2ZnSnS4 nano-particles
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
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
CN103613119B (en) * 2013-11-21 2015-07-29 电子科技大学 The preparation method of copper-zinc-tin-sulfur and purposes
CN104037267B (en) * 2014-06-30 2016-07-06 电子科技大学 A kind of method that copper-zinc-tin-selefilm film solar battery obsorbing layer is modified
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
CN108265189B (en) * 2018-01-24 2019-09-13 福州大学 A kind of Bi doping cubic phase germanium calcium thermoelectric material and its Microwave Solid preparation method
CN108165790B (en) * 2018-01-24 2019-06-04 福州大学 A kind of cubic phase Ca2Ge alloy material and its Microwave Solid preparation method
CN114914710B (en) * 2022-05-18 2023-06-27 山东大学 Electromagnetic wave absorbing material and preparation method and application thereof
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101844797B (en) * 2010-05-14 2011-12-14 东华大学 Method for preparing solar energy absorbing layer material Cu2ZnSnS4 by hydrothermal synthesis
CN102557117A (en) * 2012-03-08 2012-07-11 桂林理工大学 Method for thermally synthesizing Cu2ZnSnS4 semiconductor material by solvent through microwaves
CN102583510A (en) * 2012-03-05 2012-07-18 南京航空航天大学 Microwave-synthesis method for preparation of copper-zinc-tin-sulphur (CZTS) nanoparticles
CN102627315A (en) * 2012-04-25 2012-08-08 桂林理工大学 Preparation method of wurtzite structure CZTS (Se) system powder
CN102107905B (en) * 2011-01-12 2012-08-29 东华大学 Method for preparing Cu2ZnSnS4 solar battery material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8414862B2 (en) * 2009-11-25 2013-04-09 E I Du Pont De Nemours And Company Preparation of CZTS and its analogs in ionic liquids

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101844797B (en) * 2010-05-14 2011-12-14 东华大学 Method for preparing solar energy absorbing layer material Cu2ZnSnS4 by hydrothermal synthesis
CN102107905B (en) * 2011-01-12 2012-08-29 东华大学 Method for preparing Cu2ZnSnS4 solar battery material
CN102583510A (en) * 2012-03-05 2012-07-18 南京航空航天大学 Microwave-synthesis method for preparation of copper-zinc-tin-sulphur (CZTS) nanoparticles
CN102557117A (en) * 2012-03-08 2012-07-11 桂林理工大学 Method for thermally synthesizing Cu2ZnSnS4 semiconductor material by solvent through microwaves
CN102627315A (en) * 2012-04-25 2012-08-08 桂林理工大学 Preparation method of wurtzite structure CZTS (Se) system powder

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
溶剂热法制备球状Cu2ZnSnS4纳米晶及其表征;蔡倩等;《物理化学学报(Wuli Huaxue Xuebao)》;20111231;第27卷(第12期);第2920-2926页 *
蔡倩等.溶剂热法制备球状Cu2ZnSnS4纳米晶及其表征.《物理化学学报(Wuli Huaxue Xuebao)》.2011,第27卷(第12期),第2920-2926页.

Also Published As

Publication number Publication date
CN103011261A (en) 2013-04-03

Similar Documents

Publication Publication Date Title
CN103011261B (en) Solvothermal synthesis method of wurtzite structure CZTS(Se) (Copper Zinc Tin Sulfide) semiconductor material under synergistic effect of ultrasonic waves and microwaves
CN102923760B (en) Ultrasonic/microwave synergistic constant-pressure solvothermal synthesis method of cubic-structure and hexagonal-structure nano ZnS semiconductor material
CN103594561B (en) Method for manufacturing Cu2ZnSn(S, Se)4 solar battery absorbing layer through oxide thin film in vulcanizing and selenizing mode
Wang et al. Preparation and properties of Cu2FeSnS4 nanocrystals by ultrasound-assisted microwave irradiation
CN102616829B (en) Production method for aluminum-doped zinc oxide nanometer material
CN102557117A (en) Method for thermally synthesizing Cu2ZnSnS4 semiconductor material by solvent through microwaves
CN102060273A (en) Method for preparing I-III-VI group semiconductor material through solvothermal synthesis in constant pressure open system
CN102079541B (en) Method for preparing doping type hexagonal system nano ZnS at low temperature
Wang et al. Effects of sulfur sources on properties of Cu 2 ZnSnS 4 nanoparticles
CN103043628B (en) Method for thermally synthesizing sphalerite structure CZTSSe semiconductor material through solvent under synergistic action of ultrasonic microwave
CN106379931A (en) Method for rapidly preparing copper-zinc-tin-sulfur nanoparticles
CN101857428A (en) Preparation method of conductive zinc oxide powder
CN104060241B (en) Liquid-phase preparation method of high-oriented vanadium dioxide film
CN111285394A (en) Preparation method of polycrystalline nano cuprous oxide particles
CN102390856B (en) Method for preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature
CN102249199A (en) Microwave-assisted solvothermal synthesis method of I-III-VI semiconductor material nano-powder
CN105314672B (en) A kind of sol-gel process for preparing of Co-doped ZnO nanometer rods
KR101509332B1 (en) Preparation of copper selenide compound controlling particle size and composition
Li et al. Simultaneous phase and morphology controllable synthesis of copper selenide films by microwave-assisted nonaqueous approach
Shan et al. Effect of sulphur pressure on properties of ZnS thin film prepared by chemical bath deposition technique
Guan et al. Flower-like Cu2FeSnS4 particles synthesized by microwave irradiation method
CN107955600B (en) Red CuInS2Preparation method of-ZnS core-shell structure quantum dot
CN108217732B (en) Preparation method of wurtzite CMTS (CMTS) nanocrystal
CN102585588B (en) Preparation method of copper-zinc-tin-sulfur ink
CN109264769A (en) A kind of preparation method of IGZO superlattice nano line array

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20140820

Termination date: 20211202