CN103011261A - 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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- CN103011261A CN103011261A CN2012105039865A CN201210503986A CN103011261A CN 103011261 A CN103011261 A CN 103011261A CN 2012105039865 A CN2012105039865 A CN 2012105039865A CN 201210503986 A CN201210503986 A CN 201210503986A CN 103011261 A CN103011261 A CN 103011261A
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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
Technical field
The present invention relates to Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under a kind of ultrasonic wave/microwave cooperating effect
2ZnSnS
4(Wurtzite CZTS) or Cu
2ZnSnSe
4The method of (Wurtzite CZTSe) semiconductor material, the semiconductor material that is synthesized are 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) have 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 the reaction pilot process; The present invention utilizes characteristics 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 purpose of synthesizing fast target product under normal pressure.
Summary of the invention
The objective of the invention is in water, ethanol, ethylene glycol, glycerol, diethanolamine, acetic acid, propionic acid, oxalic acid and the oleic acid one or more as solvent, take mantoquita, zinc salt, pink salt and sulphur source (selenium source) as raw material, under normal pressure, utilize ultrasonic wave and microwave cooperating effect by the quick compounding wurtzite structure C of solvent thermal process u
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 by weighing mantoquita, zinc salt and pink salt and are dissolved in solvent and make solution A in molar ratio, taking by weighing sulphur source or selenium source is dissolved in or is dispersed in solvent and make solution B, above-mentioned A, B two solution mix in the rear adding there-necked flask, described there-necked flask places 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 described in the step (1)/microwave composite reaction system parameters is as follows: the 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 of unlatching step (2) setting begins reaction, insulation reaction is 0.5 ~ 3 hour after temperature rises to set temperature, finish to treat system's naturally cooling after the reaction, the gained reaction solution is distinguished centrifuge washing 3 ~ 4 times through deionized water and dehydrated alcohol, and products therefrom is put into 70 ~ 90 ℃ of lower vacuum-dryings of vacuum drying oven and namely made wurtzite structure Cu in 7 ~ 9 hours
2ZnSnS
4Or Cu
2ZnSnSe
4Semiconductor material.
Described mantoquita is a kind of in venus crystals, copper chloride dihydrate, copper sulfate and other mantoquita, described zinc salt is a kind of in zinc acetate, zinc chloride, zinc sulfate and other zinc salt, and described pink salt is a kind of in two hydrated stannous chlorides, crystallization tin tetrachloride and other pink salt.
Described sulphur source is a kind of in thiocarbamide, sulphur powder and the thioacetamide.
Described selenium source is a kind of in diphenyl disenenide, selenous acid and the selenium powder.
Described solvent is one or more in water, ethanol, ethylene glycol, glycerol, diethanolamine, acetic acid, propionic acid, oxalic acid and the oleic acid, when being multiple, the solvent that uses can be with arbitrary volume than mixing.
The present invention is by the structure and composition control of the synergy realization response thing of ultrasonic in the control 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 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 is utilized focusing effect quick, even, controlled grow up of ultrasonic wave on nucleus and reaction soln two-phase interface.
The present invention is by the control temperature of reaction, the reaction times, microwave power, ultrasonic power, the control reaction of ultrasonic time of origin and ultrasonic off time carry out speed and degree.
Compare with common solvent thermal synthesis technique, ultrasonic wave/microwave-assisted Solvent at Atmospheric Pressure thermal synthesis prepares wurtzite structure Cu
2ZnSnS
4Or Cu
2ZnSnSe
4Semiconductor material greatly reduces the requirement to synthesis condition, thereby and can the whole reaction building-up process of more flexible control form specific structure, ultrasonic wave microwave cooperating of the present invention effect has significant reaction activity power, can make building-up reactions rapidly reaction under the condition that conventional solvent thermal is difficult to occur; It is simple to have simultaneously reaction unit, and speed of response is fast, but reaction process controllability and the characteristics such as intervention is strong.
Description of drawings:
Fig. 1 is preparation technology's schema of the present invention.
Fig. 2 be the embodiment of the invention 1 take ethylene glycol as solvent supersonic Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under ripple/microwave cooperating effect
2ZnSnS
4The XRD diffractogram of semiconductor material.
Fig. 3 be the embodiment of the invention 1 take ethylene glycol as solvent supersonic Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under ripple/microwave cooperating effect
2ZnSnS
4The SEM shape appearance figure of semiconductor material.
Fig. 4 be the embodiment of the invention 2 take glycerol as solvent supersonic Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under ripple/microwave cooperating effect
2ZnSnSe
4The XRD diffractogram of semiconductor material.
Fig. 5 be the embodiment of the invention 2 take glycerol as solvent supersonic Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under ripple/microwave cooperating effect
2ZnSnSe
4The SEM shape appearance figure of semiconductor material.
Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under Fig. 6 is the embodiment of the invention 3 take glycerol and oleic acid as double solvents ultrasonic wave/microwave cooperating effect
2ZnSnS
4The XRD diffractogram of semiconductor material.
Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under Fig. 7 is the embodiment of the invention 3 take glycerol and oleic acid as double solvents ultrasonic wave/microwave cooperating effect
2ZnSnS
4The SEM shape appearance figure of semiconductor material.
Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under Fig. 8 is the embodiment of the invention 4 take glycerol and diethanolamine as double solvents ultrasonic wave/microwave cooperating effect
2ZnSnS
4The XRD diffractogram of semiconductor material.
Solvent at Atmospheric Pressure thermal synthesis wurtzite structure Cu under Fig. 9 is the embodiment of the invention 4 take glycerol and diethanolamine as double solvents ultrasonic wave/microwave cooperating effect
2ZnSnS
4The SEM shape appearance figure of semiconductor material.
Embodiment:
(1) with 0.2991 gram venus crystals (Cu (CH
3COO)
2H
2O), 0.2744 gram zinc acetate (Zn (CH
3COO)
22H
2O) and 0.2821 the gram two hydrated stannous chloride (SnCl
22H
2O) be dissolved in 40ml ethylene glycol, with 0.4282 gram thiocarbamide (CS (NH
2)
2) being dissolved in 20ml ethylene glycol, obtained solution mixes in the rear adding there-necked flask, and described there-necked flask places 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 described in the step (1)/microwave composite reaction system parameters is as follows: 150 ℃ of the 1st stages, 10 minutes, 500 watts of maximum microwave powers; 150 ℃ of the 2nd 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 that arranges according to step (2), system's naturally cooling after finishing reaction, the gained reaction solution is distinguished centrifuge washing 4 times through deionized water and dehydrated alcohol, and products therefrom is put into 80 ℃ of lower vacuum-dryings of vacuum drying oven and namely made Cu in 8 hours
2ZnSnS
4Semiconductor material.
Gained Cu
2ZnSnS
4Through XRD analysis as shown in Figure 2, be wurtzite structure Cu
2ZnSnS
4Scanning electron microscope analysis as shown in Figure 3, powder is mainly by the irregular roundness granulometric composition, the diameter of particle is approximately 1 ~ 3 μ m.
Embodiment 2
(1) with 0.2991 gram venus crystals (Cu (CH
3COO)
2H
2O), 0.2744 gram zinc acetate (Zn (CH
3COO)
22H
2O) and 0.2821 the gram two hydrated stannous chloride (SnCl
22H
2O) be dissolved in the 40ml glycerol, with 1.6855 gram diphenyl disenenide (C
12H
10Se
2) being dissolved in the 20ml glycerol, obtained solution mixes in the rear adding there-necked flask, and described there-necked flask places 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 described in the step (1)/microwave composite reaction system parameters is as follows: 210 ℃ of the 1st stages, 10 minutes, 500 watts of maximum microwave powers; 210 ℃ of the 2nd 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 that arranges according to step (2), system's naturally cooling after finishing reaction, the gained reaction solution is distinguished centrifuge washing 4 times through deionized water and dehydrated alcohol, and products therefrom is put into 80 ℃ of lower vacuum-dryings of vacuum drying oven and namely made Cu in 8 hours
2ZnSnSe
4Semiconductor material.
Gained Cu
2ZnSnSe
4Semiconductor material is wurtzite Cu through XRD analysis as shown in Figure 4
2ZnSnSe
4Scanning electron microscope analysis as shown in Figure 5, mainly by the granulometric composition of irregular bar-shaped, bullet shaped, the diameter of particle is 50 ~ 150nm to powder, length is 50 ~ 100nm.
Embodiment 3
(1) with 0.2991 gram venus crystals (Cu (CH
3COO)
2H
2O), 0.2744 gram zinc acetate (Zn (CH
3COO)
22H
2O) and 0.2821 the gram two hydrated stannous chloride (SnCl
22H
2O) be dissolved in 22ml glycerol and 18ml oleic acid mixed solvent, with 0.4282 gram thiocarbamide (CS (NH
2)
2) being dissolved in the 20ml glycerol, obtained solution mixes in the rear adding there-necked flask, and described there-necked flask places 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 described in the step (1)/microwave composite reaction system parameters is as follows: 200 ℃ of the 1st stages, 10 minutes, 500 watts of maximum microwave powers; 200 ℃ of the 2nd 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 that arranges according to step (2), system's naturally cooling after finishing reaction, the gained reaction solution is distinguished centrifuge washing 4 times through deionized water and dehydrated alcohol, and products therefrom is put into 80 ℃ of lower vacuum-dryings of vacuum drying oven and namely made Cu in 8 hours
2ZnSnS
4Semiconductor material.
Gained Cu
2ZnSnS
4Semiconductor material is wurtzite Cu through XRD analysis as shown in Figure 6
2ZnSnS
4With cubic zinc blende structure C u
2ZnSnS
4Scanning electron microscope analysis as shown in Figure 7, powder mainly is comprised of irregular ball particle, the diameter of particle is approximately about 500nm.
Embodiment 4
(1) with 0.2991 gram venus crystals (Cu (CH
3COO)
2H
2O), 0.2744 gram zinc acetate (Zn (CH
3COO)
22H
2O) and 0.2821 the gram two hydrated stannous chloride (SnCl
22H
2O) be dissolved in 34ml glycerol and 6ml diethanolamine mixed solvent, with 0.4282 gram thiocarbamide (CS (NH
2)
2) being dissolved in the 20ml glycerol, obtained solution mixes in the rear adding there-necked flask, and described there-necked flask places 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 described in the step (1)/microwave composite reaction system parameters is as follows: 200 ℃ of the 1st stages, 10 minutes, 500 watts of maximum microwave powers; 200 ℃ of the 2nd 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 that arranges according to step (2), system's naturally cooling after finishing reaction, the gained reaction solution is distinguished centrifuge washing 4 times through deionized water and dehydrated alcohol, and products therefrom is put into 80 ℃ of lower vacuum-dryings of vacuum drying oven and namely made Cu in 8 hours
2ZnSnS
4Semiconductor material.
Gained Cu
2ZnSnS
4Semiconductor material is wurtzite Cu through XRD analysis as shown in Figure 8
2ZnSnS
4With cubic zinc blende structure C u
2ZnSnS
4Scanning electron microscope analysis as shown in Figure 9, powder mainly is comprised of irregular ball particle, the diameter of particle is approximately about 100nm.
Embodiment 5
(1) with 0.2046 gram copper chloride dihydrate (CuCl
22H
2O), 0.1636 gram zinc chloride (ZnCl
2) and 0.4207 gram crystallization tin tetrachloride (SnCl
45H
2O) be dissolved in 22ml glycerol and 18ml oleic acid mixed solvent, 0.4226 gram thioacetamide is dissolved in the 20ml glycerol, obtained solution mixes in the rear adding there-necked flask, described there-necked flask places 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 described in the step (1)/microwave composite reaction system parameters is as follows: 200 ℃ of the 1st stages, 10 minutes, 500 watts of maximum microwave powers; 200 ℃ of the 2nd 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 that arranges according to step (2), system's naturally cooling after finishing reaction, the gained reaction solution is distinguished centrifuge washing 4 times through deionized water and dehydrated alcohol, and products therefrom is put into 80 ℃ of lower vacuum-dryings of vacuum drying oven and namely made Cu in 8 hours
2ZnSnS
4Semiconductor material.
Embodiment 6
(1) with 0.1915 gram copper sulfate (CuSO
4), 0.1939 gram zinc sulfate (ZnSO
4) and 0.4207 gram crystallization tin tetrachloride (SnCl
45H
2O) or other pink salt be dissolved in 22ml glycerol and 18ml oxalic acid mixed solvent, with 0.4282 gram thiocarbamide (CS (NH
2)
2) being dissolved in the 20ml glycerol, obtained solution mixes in the rear adding there-necked flask, and described there-necked flask places 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 described in the step (1)/microwave composite reaction system parameters is as follows: 200 ℃ of the 1st stages, 10 minutes, 500 watts of maximum microwave powers; 200 ℃ of the 2nd 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 that arranges according to step (2), system's naturally cooling after finishing reaction, the gained reaction solution is distinguished centrifuge washing 4 times through deionized water and dehydrated alcohol, and products therefrom is put into 80 ℃ of lower vacuum-dryings of vacuum drying oven and namely made Cu in 8 hours
2ZnSnS
4Semiconductor material.
Embodiment 7
(1) with 0.2046 gram copper chloride dihydrate (CuCl
22H
2O), 0.1636 gram zinc chloride (ZnCl
2) and 0.4207 gram crystallization tin tetrachloride (SnCl
45H
2O) be dissolved in 34ml glycerol and 6ml diethanolamine mixed solvent, 0.1803 gram sulphur powder is dissolved in the 20ml glycerol, obtained solution mixes in the rear adding there-necked flask, described there-necked flask places 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 described in the step (1)/microwave composite reaction system parameters is as follows: 200 ℃ of the 1st stages, 10 minutes, 500 watts of maximum microwave powers; 200 ℃ of the 2nd 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 that arranges according to step (2), system's naturally cooling after finishing reaction, the gained reaction solution is distinguished centrifuge washing 4 times through deionized water and dehydrated alcohol, and products therefrom is put into 80 ℃ of lower vacuum-dryings of vacuum drying oven and namely made Cu in 8 hours
2ZnSnS
4Semiconductor material.
Embodiment 8
(1) with 0.1915 gram copper sulfate (CuSO
4), 0.1939 gram zinc sulfate (ZnSO
4) and 0.2821 gram, two hydrated stannous chloride (SnCl
22H
2O) be dissolved in 34ml glycerol and 6ml diethanolamine mixed solvent, with 0.4282 gram thiocarbamide (CS (NH
2)
2) being dissolved in the 20ml glycerol, obtained solution mixes in the rear adding there-necked flask, and described there-necked flask places 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 described in the step (1)/microwave composite reaction system parameters is as follows: 200 ℃ of the 1st stages, 10 minutes, 500 watts of maximum microwave powers; 200 ℃ of the 2nd 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 that arranges according to step (2), system's naturally cooling after finishing reaction, the gained reaction solution is distinguished centrifuge washing 4 times through deionized water and dehydrated alcohol, and products therefrom is put into 80 ℃ of lower vacuum-dryings of vacuum drying oven and namely made Cu in 8 hours
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 by weighing mantoquita, zinc salt, pink salt and are dissolved in solvent and make solution A in molar ratio, taking by weighing sulphur source or selenium source is dissolved in or is dispersed in solvent and make solution B, above-mentioned A, B two solution mix in the rear adding there-necked flask, described there-necked flask places 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 described in the step (1)/microwave composite reaction system parameters is as follows: the 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 of unlatching step (2) setting begins reaction, insulation reaction is 0.5 ~ 3 hour after temperature rises to set temperature, finish to treat system's naturally cooling after the reaction, the gained reaction solution is distinguished centrifuge washing 3 ~ 4 times through deionized water and dehydrated alcohol, and products therefrom is put into 70 ~ 90 ℃ of lower vacuum-dryings of vacuum drying oven and namely made wurtzite structure Cu in 7 ~ 9 hours
2ZnSnS
4Or Cu
2ZnSnSe
4Semiconductor material;
Described mantoquita is a kind of in venus crystals, copper chloride dihydrate, copper sulfate and other mantoquita, described zinc salt is a kind of in zinc acetate, zinc chloride, zinc sulfate and other zinc salt, and described pink salt is a kind of in two hydrated stannous chlorides, crystallization tin tetrachloride and other pink salt;
Described sulphur source is a kind of in thiocarbamide, sulphur powder and the thioacetamide;
Described selenium source is a kind of in diphenyl disenenide, selenous acid and the selenium powder;
Described solvent is one or more in water, ethanol, ethylene glycol, glycerol, diethanolamine, acetic acid, propionic acid, oxalic acid and the 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: the structure and composition control of the synergy realization response thing by ultrasonic in the control solvent thermal building-up process and microwave, 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 is utilized 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 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.
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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)》 * |
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