CN102208487A - Preparation method of nanostructure heterojunction of CuInSe nanocrystal, cadmium sulfide quantum dot and zinc oxide nanowire array - Google Patents
Preparation method of nanostructure heterojunction of CuInSe nanocrystal, cadmium sulfide quantum dot and zinc oxide nanowire array Download PDFInfo
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Abstract
Provided is a preparation method of a nanowire array nanostructure heterojunction of CuInSe nanocrystals, cadmium sulfide quantum dots and a zinc oxide nanowire array. The zinc oxide nanowire array is adopted as an n type semiconductor electron transmission layer. A layer of cadmium sulfide quantum dots is deposited on the electron transmission layer as a buffer layer and a layer of p type CuInSe nanocrystals is deposited on the buffer layer. Firstly, a sol-gel technology is used to deposit a zinc oxide film on an FTO glass flake. Then a hydro-thermal self assembly growth technology is employed to grow a zinc oxide nanowire array on the zinc oxide film. A layer of cadmium sulfide quantum dots obtained through continuous adsorption and a reaction method is deposited on the zinc oxide nanowire array. Lastly, an electrophoresis method is adopted to deposit a layer of CuInSe nanocrystals obtained from a solvent heat method on the cadmium sulfide. Through the above steps, a nanostructure heterojunction which is characterized by low cost, simple technology requirement, good repeatability, large-scale manufacture feasibility and high visible light absorptivity can be obtained.
Description
Technical field
The invention belongs to the method for nanostructure preparation, be specifically related to the preparation method of a kind of copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction.
Technical background
Copper indium diselenide and associated materials thereof are because its suitable energy gap, and high absorption coefficient and stability cause people's extensive concern and research, are thought the best replacer of silicon materials and the back person of choosing of space power system of future generation by consistent.At present, the photoelectric conversion efficiency of copper, indium and selenium film solar cell has reached more than 20% in the laboratory.In order to obtain the copper, indium and selenium film solar cell of high conversion efficiency, often need to adopt multistage high-vacuum apparatus.But this technology has certain defective, for example: complicated technical process, high manufacturing cost and can not large-scale production, these problems all need solve before the copper, indium and selenium film solar cell is commercially produced.In order to reduce production costs, many antivacuum methods that prepare copper, indium and selenium film are paid close attention to widely and are studied.
In recent years, because advantage such as low-cost and stoichiometric proportion is controlled, solvent-thermal method prepares copper-indium-selenium nanocrystalline, and its research that is prepared into film is received much attention.At present, the research of copper-indium-selenium nanocrystalline also is in the starting stage, synthetic this material of existing in the world at present scientific research personnel, but not well optimization of device causes energy conversion efficiency lower (that has reported is up to 3.2%).Consider that copper-indium-selenium nanocrystalline is all stronger than the controllability and the repeatability of copper, indium and selenium film, and in theory the former energy conversion efficiency than latter height, the copper-indium-selenium nanocrystalline solar cell is more suitable for industrialization, will have vast market and application prospect more undoubtedly.
Summary of the invention
Content of the present invention is to provide the preparation method of a kind of copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction.
For achieving the above object, the preparation method that the present invention adopts is:
1) Zinc diacetate dihydrate, monoethanol ammonia and deionized water being dissolved in the concentration of making Zinc diacetate dihydrate in the EGME by 1: 1: 0.5 mol ratio is the mixed solution of 0.1-1mol/L, to put into thermostat water bath after the mixed solution sealing again, 60 ℃ of magnetic agitation of constant temperature obtain transparent and uniform colloidal sol;
2) utilize spin coating technology on the FTO sheet glass that rotating speed is cleaning up for the 2000-3000 rev/min of sol deposition that step 1) is prepared, again the substrate after the spin coating is put into 200-275 ℃ of drying box and dried, obtained the zinc oxide inculating crystal layer in 0.5-2 hour 350-500 ℃ of annealing at last;
3) with zinc nitrate hexahydrate and the NaOH growth-promoting media of making soluble in water, the concentration of zinc nitrate hexahydrate is 0.02-0.04mol/L in the growth-promoting media, concentration sodium hydroxide is 0.4-0.8mol/L, the substrate that is coated with the zinc oxide inculating crystal layer is put into growth-promoting media, handled 1-3 hour at 60-80 ℃ of constant temperature, obtain zinc oxide nano-wire array;
4) zinc oxide nano-wire array that obtains being immersed successively caddy ethanol solution and the concentration that concentration is 0.01-0.1mol/L is the vulcanized sodium methanol solution of 0.01-0.1mol/L, soak time was for 30 seconds, repeat this cycling 3-20 time, obtain the zinc oxide nano-wire array that cadmiumsulfide quantum dot coats;
5) with copper chloride or the stannous chloride of 0.5-1.5mmol, 0.5-1.5mmol inidum chloride, the selenium powder of 1-3mmol join in the oleyl amine of 8-12ml mixed solution, copper wherein: indium: the ratio of the amount of element of selenium is 1: 1: 2, then this mixed solution is heated to 60-80 ℃ of insulation 2-3 hour, feed the nitrogen vigorous stirring simultaneously, again the mixed solution that obtains is heated to 210-240 ℃, feed nitrogen simultaneously, and condensing reflux, vigorous stirring, reacted 2-4 hour, in solution, add 10-20 milliliter ethanol afterwards and, remove supernatant and obtain precipitation with the centrifugal 3-5 of the speed of 5000-8000rpm minute;
6) in precipitation, add 5-10ml chloroform and 10-20ml ethanol, and ultrasonic make precipitation all dissolving mix, with the centrifugal 3-5 of the speed of 5000-8000rpm minute, remove supernatant and obtain precipitation, in precipitation, add 5-10ml chloroform and 10-20ml ethanol again, through ultrasonic, centrifugal, go supernatant to precipitate, repeat 3 times, chloroform wherein: ethanol is 1: 2 volume ratio, at last, add the 5-10ml chloroform in precipitation, the ultrasonic precipitation that makes is all dissolved, to remove precipitation in the centrifugal 3-5 of the speed of 5000-8000rpm minute,, obtain suspension and be required copper-indium-selenium nanocrystalline, and be 10 the concentration dilution of copper-indium-selenium nanocrystalline chloroformic solution
-6-10
-7Mol/L;
7) with two anode and negative electrodes that coat the zinc oxide nano-wire array of cadmiumsulfide quantum dot as electrophoresis, two electrodes are immersed in the copper-indium-selenium nanocrystalline chloroformic solution, use the voltage of 50-200V, electrophoresis 30-120 minute, obtain copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction.
The present invention adopts sol-gel technique in conjunction with hydro-thermal, and colloid chemistry and electrophoresis growing technology have that synthetic cost is low, technological requirement is simple and good reproducibility and advantage such as can make on a large scale.What the present invention proposed is to deposit the heterojunction of one deck copper-indium-selenium nanocrystalline as photoelectric device on the zinc oxide nano-wire array that cadmiumsulfide quantum dot coats, the characteristic of one-dimension zinc oxide nano wire at advantage aspect the electron transport and low-cost preparation copper-indium-selenium nanocrystalline film organically combined, aspect solar cell, have a wide range of applications.
Description of drawings
The zinc oxide nano-wire array that Fig. 1 cadmiumsulfide quantum dot coats and the scanning electron microscope test figure of copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction;
The zinc oxide nano-wire array that Fig. 2 zinc-oxide film, zinc oxide nano-wire array, cadmiumsulfide quantum dot coat and the absorption spectrum of copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction, wherein abscissa is a lambda1-wavelength, and ordinate is an intensity.
Current density and the voltage curve figure of Fig. 3 copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction under illumination and dark attitude, wherein abscissa is a voltage, ordinate is a current density.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
Embodiment 1,
1) Zinc diacetate dihydrate, monoethanol ammonia and deionized water being dissolved in the concentration of making Zinc diacetate dihydrate in the EGME by 1: 1: 0.5 mol ratio is the mixed solution of 0.1mol/L, to put into thermostat water bath after the mixed solution sealing again, 60 ℃ of magnetic agitation of constant temperature obtain transparent and uniform colloidal sol;
2) utilizing spin coating technology is on 3000 rev/mins of FTO sheet glass that above-mentioned sol deposition is being cleaned up at rotating speed, the substrate after the spin coating is put into 200 ℃ of drying boxes again and is dried, and obtains the zinc oxide inculating crystal layer in 2 hours 500 ℃ of annealing at last;
3) with zinc nitrate hexahydrate and the NaOH growth-promoting media of making soluble in water, the concentration of zinc nitrate hexahydrate is 0.04mol/L in the growth-promoting media, concentration sodium hydroxide is 0.8mol/L, the substrate that is coated with the zinc oxide inculating crystal layer is put into growth-promoting media, handled 1 hour at 80 ℃ of constant temperature, obtain zinc oxide nano-wire array;
4) zinc oxide nano-wire array that obtains being immersed successively caddy ethanol solution and the concentration that concentration is 0.01mol/L is the vulcanized sodium methanol solution of 0.01mol/L, soak time was for 30 seconds, repeat this cycling 10 times, can obtain the zinc oxide nano-wire array that cadmiumsulfide quantum dot coats;
5) selenium powder of the inidum chloride of the copper chloride of 1mmol or stannous chloride, 1mmol, 2mmol is joined in the oleyl amine of 10ml mixed solution, copper wherein: indium: the ratio of the amount of element of selenium is 1: 1: 2, then this mixed solution is heated to 80 ℃ of insulations 2 hours, feed the nitrogen vigorous stirring simultaneously, again the mixed solution that obtains is heated to 240 ℃, feed nitrogen simultaneously, and condensing reflux, vigorous stirring, reacted 4 hours, in solution, add 10 milliliters of ethanol afterwards and centrifugal 5 minutes, remove supernatant and obtain precipitation with the speed of 8000rpm;
6) in precipitation, add 10ml chloroform and 20ml ethanol, and ultrasonic make precipitation all dissolving mix, with the speed of 8000rpm centrifugal 5 minutes, remove supernatant and obtain precipitation, in precipitation, add 10ml chloroform and the repetition of 20ml ethanol 3 times again, chloroform wherein: ethanol is 1: 2 volume ratio, at last, in precipitation, add the 10ml chloroform, ultrasonicly make all dissolvings of precipitation, centrifugal 5 minutes with the speed of 8000rpm, obtain suspension, remove precipitation, this suspension is required copper-indium-selenium nanocrystalline, and is 10 with the concentration dilution of copper-indium-selenium nanocrystalline chloroformic solution
-7Mol/L;
7) with two anode and negative electrodes that coat the zinc oxide nano-wire array of cadmiumsulfide quantum dot as electrophoresis, two electrodes are immersed in the copper-indium-selenium nanocrystalline chloroformic solution, use the voltage of 200V, electrophoresis 120 minutes can obtain copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction.
1) Zinc diacetate dihydrate, monoethanol ammonia and deionized water being dissolved in the concentration of making Zinc diacetate dihydrate in the EGME by 1: 1: 0.5 mol ratio is the mixed solution of 0.4mol/L, to put into thermostat water bath after the mixed solution sealing again, 60 ℃ of magnetic agitation of constant temperature obtain transparent and uniform colloidal sol;
2) utilizing spin coating technology is on 2500 rev/mins of FTO sheet glass that above-mentioned sol deposition is being cleaned up at rotating speed, the substrate after the spin coating is put into 250 ℃ of drying boxes again and is dried, and obtains the zinc oxide inculating crystal layer in 1 hour 450 ℃ of annealing at last;
3) with zinc nitrate hexahydrate and the NaOH growth-promoting media of making soluble in water, the concentration of zinc nitrate hexahydrate is 0.02mol/L in the growth-promoting media, concentration sodium hydroxide is 0.4mol/L, the substrate that is coated with the zinc oxide inculating crystal layer is put into growth-promoting media, handled 3 hours at 60 ℃ of constant temperature, obtain zinc oxide nano-wire array;
4) zinc oxide nano-wire array that obtains being immersed successively caddy ethanol solution and the concentration that concentration is 0.05mol/L is the vulcanized sodium methanol solution of 0.05mol/L, soak time was for 30 seconds, repeat this cycling 7 times, can obtain the zinc oxide nano-wire array that cadmiumsulfide quantum dot coats;
5) selenium powder of the inidum chloride of the copper chloride of 0.5mmol or stannous chloride, 0.5mmol, 1mmol is joined in the oleyl amine of 8ml mixed solution, copper wherein: indium: the ratio of the amount of element of selenium is 1: 1: 2, then this mixed solution is heated to 60 ℃ of insulations 2 hours, feed the nitrogen vigorous stirring simultaneously, again the mixed solution that obtains is heated to 210 ℃, feed nitrogen simultaneously, and condensing reflux, vigorous stirring, reacted 2 hours, in solution, add 10 milliliters of ethanol afterwards and centrifugal 3 minutes, remove supernatant and obtain precipitation with the speed of 5000rpm;
6) in precipitation, add 5ml chloroform and 10ml ethanol, and ultrasonic make precipitation all dissolving mix, with the speed of 5000rpm centrifugal 3 minutes, remove supernatant and obtain precipitation, in precipitation, add 5ml chloroform and the repetition of 10ml ethanol 3 times again, chloroform wherein: ethanol is 1: 2 volume ratio, at last, in precipitation, add the 5ml chloroform, ultrasonicly make all dissolvings of precipitation, centrifugal 3 minutes with the speed of 5000rpm, obtain suspension, remove precipitation, this suspension is required copper-indium-selenium nanocrystalline, and is 10 with the concentration dilution of copper-indium-selenium nanocrystalline chloroformic solution
-6Mol/L;
7) with two anode and negative electrodes that coat the zinc oxide nano-wire array of cadmiumsulfide quantum dot as electrophoresis, two electrodes are immersed in the copper-indium-selenium nanocrystalline chloroformic solution, use the voltage of 50V, electrophoresis 30 minutes can obtain copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction.
Embodiment 3,
1) Zinc diacetate dihydrate, monoethanol ammonia and deionized water being dissolved in the concentration of making Zinc diacetate dihydrate in the EGME by 1: 1: 0.5 mol ratio is the mixed solution of 1mol/L, to put into thermostat water bath after the mixed solution sealing again, 60 ℃ of magnetic agitation of constant temperature obtain transparent and uniform colloidal sol;
2) utilizing spin coating technology is on 3000 rev/mins of FTO sheet glass that above-mentioned sol deposition is being cleaned up at rotating speed, the substrate after the spin coating is put into 275 ℃ of drying boxes again and is dried, and obtains the zinc oxide inculating crystal layer in 2 hours 500 ℃ of annealing at last;
3) with zinc nitrate hexahydrate and the NaOH growth-promoting media of making soluble in water, the concentration of zinc nitrate hexahydrate is 0.04mol/L in the growth-promoting media, concentration sodium hydroxide is 0.8mol/L, the substrate that is coated with the zinc oxide inculating crystal layer is put into growth-promoting media, handled 3 hours at 80 ℃ of constant temperature, obtain zinc oxide nano-wire array;
4) zinc oxide nano-wire array that obtains being immersed successively caddy ethanol solution and the concentration that concentration is 0.1mol/L is the vulcanized sodium methanol solution of 0.1mol/L, soak time was for 30 seconds, repeat this cycling 20 times, can obtain the zinc oxide nano-wire array that cadmiumsulfide quantum dot coats;
5) selenium powder of the inidum chloride of the copper chloride of 1.5mmol or stannous chloride, 1.5mmol, 3mmol is joined in the oleyl amine of 12ml mixed solution, copper wherein: indium: the ratio of the amount of element of selenium is 1: 1: 2, then this mixed solution is heated to 80 ℃ of insulations 3 hours, feed the nitrogen vigorous stirring simultaneously, again the mixed solution that obtains is heated to 240 ℃, feed nitrogen simultaneously, and condensing reflux, vigorous stirring, reacted 4 hours, in solution, add 20 milliliters of ethanol afterwards and centrifugal 5 minutes, remove supernatant and obtain precipitation with the speed of 8000rpm;
6) in precipitation, add 10ml chloroform and 20ml ethanol, and ultrasonic make precipitation all dissolving mix, with the speed of 8000rpm centrifugal 5 minutes, remove supernatant and obtain precipitation, in precipitation, add 10ml chloroform and the repetition of 20ml ethanol 3 times again, chloroform wherein: ethanol is 1: 2 volume ratio, at last, in precipitation, add the 10ml chloroform, ultrasonicly make all dissolvings of precipitation, centrifugal 5 minutes with the speed of 8000rpm, obtain suspension, remove precipitation, this suspension is required copper-indium-selenium nanocrystalline, and is 10 with the concentration dilution of copper-indium-selenium nanocrystalline chloroformic solution
-7Mol/L;
7) with two anode and negative electrodes that coat the zinc oxide nano-wire array of cadmiumsulfide quantum dot as electrophoresis, two electrodes are immersed in the copper-indium-selenium nanocrystalline chloroformic solution, use the voltage of 200V, electrophoresis 120 minutes can obtain copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction.
Embodiment 4,
1) Zinc diacetate dihydrate, monoethanol ammonia and deionized water being dissolved in the concentration of making Zinc diacetate dihydrate in the EGME by 1: 1: 0.5 mol ratio is the mixed solution of 0.8mol/L, to put into thermostat water bath after the mixed solution sealing again, 60 ℃ of magnetic agitation of constant temperature obtain transparent and uniform colloidal sol;
2) utilizing spin coating technology is on 3000 rev/mins of FTO sheet glass that above-mentioned sol deposition is being cleaned up at rotating speed, the substrate after the spin coating is put into 250 ℃ of drying boxes again and is dried, and obtains the zinc oxide inculating crystal layer in 0.5 hour 350 ℃ of annealing at last;
3) with zinc nitrate hexahydrate and the NaOH growth-promoting media of making soluble in water, the concentration of zinc nitrate hexahydrate is 0.03mol/L in the growth-promoting media, concentration sodium hydroxide is 0.6mol/L, the substrate that is coated with the zinc oxide inculating crystal layer is put into growth-promoting media, handled 2 hours at 70 ℃ of constant temperature, obtain zinc oxide nano-wire array;
4) zinc oxide nano-wire array that obtains being immersed successively caddy ethanol solution and the concentration that concentration is 0.08mol/L is the vulcanized sodium methanol solution of 0.08mol/L, soak time was for 30 seconds, repeat this cycling 15 times, can obtain the zinc oxide nano-wire array that cadmiumsulfide quantum dot coats;
5) selenium powder of the inidum chloride of the copper chloride of 0.8mmol or stannous chloride, 0.8mmol, 1.6mmol is joined in the oleyl amine of 8ml mixed solution, copper wherein: indium: the ratio of the amount of element of selenium is 1: 1: 2, then this mixed solution is heated to 70 ℃ of insulations 2.5 hours, feed the nitrogen vigorous stirring simultaneously, again the mixed solution that obtains is heated to 220 ℃, feed nitrogen simultaneously, and condensing reflux, vigorous stirring, reacted 3 hours, in solution, add 15 milliliters of ethanol afterwards and centrifugal 4 minutes, remove supernatant and obtain precipitation with the speed of 6000rpm;
6) in precipitation, add 8ml chloroform and 16ml ethanol, and ultrasonic make precipitation all dissolving mix, with the speed of 6000rpm centrifugal 4 minutes, remove supernatant and obtain precipitation, in precipitation, add 8ml chloroform and the repetition of 16ml ethanol 3 times again, chloroform wherein: ethanol is 1: 2 volume ratio, at last, in precipitation, add the 8ml chloroform, ultrasonicly make all dissolvings of precipitation, centrifugal 4 minutes with the speed of 6000rpm, obtain suspension, remove precipitation, this suspension is required copper-indium-selenium nanocrystalline, and is 10 with the concentration dilution of copper-indium-selenium nanocrystalline chloroformic solution
-7Mol/L;
7) with two anode and negative electrodes that coat the zinc oxide nano-wire array of cadmiumsulfide quantum dot as electrophoresis, two electrodes are immersed in the copper-indium-selenium nanocrystalline chloroformic solution, use the voltage of 100V, electrophoresis 60 minutes can obtain copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction.
1) Zinc diacetate dihydrate, monoethanol ammonia and deionized water being dissolved in the concentration of making Zinc diacetate dihydrate in the EGME by 1: 1: 0.5 mol ratio is the mixed solution of 0.5mol/L, to put into thermostat water bath after the mixed solution sealing again, 60 ℃ of magnetic agitation of constant temperature obtain transparent and uniform colloidal sol;
2) utilizing spin coating technology is on 2000 rev/mins of FTO sheet glass that above-mentioned sol deposition is being cleaned up at rotating speed, the substrate after the spin coating is put into 275 ℃ of drying boxes again and is dried, and obtains the zinc oxide inculating crystal layer in 1 hour 400 ℃ of annealing at last;
3) with zinc nitrate hexahydrate and the NaOH growth-promoting media of making soluble in water, the concentration of zinc nitrate hexahydrate is 0.04mol/L in the growth-promoting media, concentration sodium hydroxide is 0.8mol/L, the substrate that is coated with the zinc oxide inculating crystal layer is put into growth-promoting media, handled 3 hours at 80 ℃ of constant temperature, obtain zinc oxide nano-wire array;
4) zinc oxide nano-wire array that obtains being immersed successively caddy ethanol solution and the concentration that concentration is 0.03mol/L is the vulcanized sodium methanol solution of 0.03mol/L, soak time was for 30 seconds, repeat this cycling 3 times, can obtain the zinc oxide nano-wire array that cadmiumsulfide quantum dot coats;
5) selenium powder of the inidum chloride of the copper chloride of 1.2mmol or stannous chloride, 1.2mmol, 2.4mmol is joined in the oleyl amine of 12ml mixed solution, copper wherein: indium: the ratio of the amount of element of selenium is 1: 1: 2, then this mixed solution is heated to 80 ℃ of insulations 3 hours, feed the nitrogen vigorous stirring simultaneously, again the mixed solution that obtains is heated to 230 ℃, feed nitrogen simultaneously, and condensing reflux, vigorous stirring, reacted 2 hours, in solution, add 12 milliliters of ethanol afterwards and centrifugal 5 minutes, remove supernatant and obtain precipitation with the speed of 7000rpm;
6) in precipitation, add 6ml chloroform and 12ml ethanol, and ultrasonic make precipitation all dissolving mix, with the speed of 6000rpm centrifugal 5 minutes, remove supernatant and obtain precipitation, in precipitation, add 6ml chloroform and the repetition of 12ml ethanol 3 times again, chloroform wherein: ethanol is 1: 2 volume ratio, at last, in precipitation, add the 6ml chloroform, ultrasonicly make all dissolvings of precipitation, centrifugal 5 minutes with the speed of 6000rpm, obtain suspension, remove precipitation, this suspension is required copper-indium-selenium nanocrystalline, and is 10 with the concentration dilution of copper-indium-selenium nanocrystalline chloroformic solution
-6Mol/L;
7) with two anode and negative electrodes that coat the zinc oxide nano-wire array of cadmiumsulfide quantum dot as electrophoresis, two electrodes are immersed in the copper-indium-selenium nanocrystalline chloroformic solution, use the voltage of 150V, electrophoresis 100 minutes can obtain copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction.
Zinc oxide nano-wire array and copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction observed pattern in scanning electron microscopy that Fig. 1 coats for the cadmiumsulfide quantum dot that obtains among the embodiment 1, Fig. 1 (a) is the scanning electron microscope diagram of the zinc oxide nano-wire array of cadmiumsulfide quantum dot coating, be not blocked in as can be seen between the zinc oxide nanowire but be coated on nanowire surface uniformly, in Fig. 1 (b), can see nearly 500 nanometer thickness of copper-indium-selenium nanocrystalline layer, and a part of copper-indium-selenium nanocrystalline has been mounted in the middle of the zinc oxide nano-wire array.Fig. 1 (c) is the scanning electron microscope diagram of copper-indium-selenium nanocrystalline layer, can observe copper-indium-selenium nanocrystalline and form fine and close and smooth film.
Fig. 2 is zinc-oxide film, zinc oxide nano-wire array, the zinc oxide nano-wire array of cadmiumsulfide quantum dot coating and the absorption spectrum of copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction that obtains among the embodiment 1, as seen from the figure, along with the growth of zinc oxide nano-wire array, the coating of cadmiumsulfide quantum dot and the deposition of copper-indium-selenium nanocrystalline, whole film is more and more higher in the absorptivity of visible region.
Copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction current density and the voltage curve figure under illumination and dark attitude of Fig. 3 for obtaining among the embodiment 1, as seen from the figure, the open circuit voltage of device and short circuit current are respectively 0.35V, 3.13mA/cm
-2, be respectively 0.3% and 0.28 through calculating the photoelectric conversion efficiency and the fill factor, curve factor that can obtain device.
In sum, the present invention has prepared to have the simple and good reproducibility of with low cost, technological requirement, can make on a large scale, and has the nanostructure heterojunction of high visible absorptivity.
Claims (1)
1. the preparation method of copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction is characterized in that:
1) Zinc diacetate dihydrate, monoethanol ammonia and deionized water being dissolved in the concentration of making Zinc diacetate dihydrate in the EGME by 1: 1: 0.5 mol ratio is the mixed solution of 0.1-1mol/L, to put into thermostat water bath after the mixed solution sealing again, 60 ℃ of magnetic agitation of constant temperature obtain transparent and uniform colloidal sol;
2) utilize spin coating technology on the FTO sheet glass that rotating speed is cleaning up for the 2000-3000 rev/min of sol deposition that step 1) is prepared, again the substrate after the spin coating is put into 200-275 ℃ of drying box and dried, obtained the zinc oxide inculating crystal layer in 0.5-2 hour 350-500 ℃ of annealing at last;
3) with zinc nitrate hexahydrate and the NaOH growth-promoting media of making soluble in water, the concentration of zinc nitrate hexahydrate is 0.02-0.04mol/L in the growth-promoting media, concentration sodium hydroxide is 0.4-0.8mol/L, the substrate that is coated with the zinc oxide inculating crystal layer is put into growth-promoting media, handled 1-3 hour at 60-80 ℃ of constant temperature, obtain zinc oxide nano-wire array;
4) zinc oxide nano-wire array that obtains being immersed successively caddy ethanol solution and the concentration that concentration is 0.01-0.1mol/L is the vulcanized sodium methanol solution of 0.01-0.1mol/L, soak time was for 30 seconds, repeat this cycling 3-20 time, obtain the zinc oxide nano-wire array that cadmiumsulfide quantum dot coats;
5) with copper chloride or the stannous chloride of 0.5-1.5mmol, 0.5-1.5mmol inidum chloride, the selenium powder of 1-3mmol join in the oleyl amine of 8-12ml mixed solution, copper wherein: indium: the ratio of the amount of element of selenium is 1: 1: 2, then this mixed solution is heated to 60-80 ℃ of insulation 2-3 hour, feed the nitrogen vigorous stirring simultaneously, again the mixed solution that obtains is heated to 210-240 ℃, feed nitrogen simultaneously, and condensing reflux, vigorous stirring, reacted 2-4 hour, in solution, add 10-20 milliliter ethanol afterwards and, remove supernatant and obtain precipitation with the centrifugal 3-5 of the speed of 5000-8000rpm minute;
6) in precipitation, add 5-10ml chloroform and 10-20ml ethanol, and ultrasonic make precipitation all dissolving mix, with the centrifugal 3-5 of the speed of 5000-8000rpm minute, remove supernatant and obtain precipitation, in precipitation, add 5-10ml chloroform and 10-20ml ethanol again, through ultrasonic, centrifugal, go supernatant to precipitate, repeat 3 times, chloroform wherein: ethanol is 1: 2 volume ratio, at last, add the 5-10ml chloroform in precipitation, the ultrasonic precipitation that makes is all dissolved, to remove precipitation in the centrifugal 3-5 of the speed of 5000-8000rpm minute,, obtain suspension and be required copper-indium-selenium nanocrystalline, and be 10 the concentration dilution of copper-indium-selenium nanocrystalline chloroformic solution
-6-10
-7Mol/L;
7) with two anode and negative electrodes that coat the zinc oxide nano-wire array of cadmiumsulfide quantum dot as electrophoresis, two electrodes are immersed in the copper-indium-selenium nanocrystalline chloroformic solution, use the voltage of 50-200V, electrophoresis 30-120 minute, obtain copper-indium-selenium nanocrystalline/cadmiumsulfide quantum dot/zinc oxide nano-wire array nanostructure heterojunction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103779440A (en) * | 2012-10-18 | 2014-05-07 | 台积太阳能股份有限公司 | Method of in-situ fabricating of intrinsic zinc oxide layer and photovoltaic device thereof |
| CN104064628A (en) * | 2014-07-01 | 2014-09-24 | 扬州大学 | Preparation method of CIST nano wire |
| CN104057101A (en) * | 2014-07-01 | 2014-09-24 | 扬州大学 | Method of catalytic preparation of copper-indium-tellurium nanowires |
| CN104465321A (en) * | 2014-11-21 | 2015-03-25 | 河南大学 | Method for preparing photoelectric film |
| CN108318545A (en) * | 2018-03-29 | 2018-07-24 | 上海电机学院 | A kind of the preparation method of Cd doping zinc oxide nanometers stick sensor |
| CN114014277A (en) * | 2021-12-09 | 2022-02-08 | 广东省科学院半导体研究所 | Copper indium selenium nanocrystal, nano film, preparation method of copper indium selenium nanocrystal and preparation method of nano film and electronic device |
| CN114899272A (en) * | 2022-05-20 | 2022-08-12 | 西安交通大学 | Amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector and preparation method thereof |
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| CN101698472A (en) * | 2009-11-03 | 2010-04-28 | 厦门大学 | Method for synthesizing copper-indium-selenium nanocrystalline |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103779440A (en) * | 2012-10-18 | 2014-05-07 | 台积太阳能股份有限公司 | Method of in-situ fabricating of intrinsic zinc oxide layer and photovoltaic device thereof |
| CN104064628A (en) * | 2014-07-01 | 2014-09-24 | 扬州大学 | Preparation method of CIST nano wire |
| CN104057101A (en) * | 2014-07-01 | 2014-09-24 | 扬州大学 | Method of catalytic preparation of copper-indium-tellurium nanowires |
| CN104057101B (en) * | 2014-07-01 | 2015-12-09 | 扬州大学 | The method of copper indium tellurium nano-wire is prepared in a kind of catalysis |
| CN104064628B (en) * | 2014-07-01 | 2016-07-06 | 扬州大学 | A kind of preparation method of CIS tellurium nano-wire |
| CN104465321A (en) * | 2014-11-21 | 2015-03-25 | 河南大学 | Method for preparing photoelectric film |
| CN108318545A (en) * | 2018-03-29 | 2018-07-24 | 上海电机学院 | A kind of the preparation method of Cd doping zinc oxide nanometers stick sensor |
| CN114014277A (en) * | 2021-12-09 | 2022-02-08 | 广东省科学院半导体研究所 | Copper indium selenium nanocrystal, nano film, preparation method of copper indium selenium nanocrystal and preparation method of nano film and electronic device |
| CN114899272A (en) * | 2022-05-20 | 2022-08-12 | 西安交通大学 | Amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector and preparation method thereof |
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