CN101838155B - Method for preparing hexagonal flaky cadmium sulphide membrane in microwave hydrothermal mode - Google Patents
Method for preparing hexagonal flaky cadmium sulphide membrane in microwave hydrothermal mode Download PDFInfo
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- CN101838155B CN101838155B CN2010101820071A CN201010182007A CN101838155B CN 101838155 B CN101838155 B CN 101838155B CN 2010101820071 A CN2010101820071 A CN 2010101820071A CN 201010182007 A CN201010182007 A CN 201010182007A CN 101838155 B CN101838155 B CN 101838155B
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Abstract
The invention relates to a method for preparing a hexagonal flaky cadmium sulphide membrane in a microwave hydrothermal mode. The method comprises the following steps of: mixing cadmium sulphide, oleic acid, deionized water, n-butylamine and sodium sulfide and adjusting the pH value of the mixture to between 3.0 and 11.0 to obtain coating liquid; putting a Si substrate in a hydrothermal reaction kettle and dipping the Si substrate in the coating liquid; sealing the hydrothermal reaction kettle, putting the sealed hydrothermal reaction kettle into a microwave hydrothermal reaction instrument to perform microwave hydrothermal reaction, naturally cooling the reaction product to room temperature after the reaction is finished, taking the Si substrate out, cleaning the Si substrate with distilled water and absolute ethyl alcohol and drying the cleaned Si substrate in a vacuum drying oven to obtain the hexagonal flaky cadmium sulphide membrane on the surface of the substrate. Since a microwave method and a hydrothermal method are combined in the invention, the obtained cadmium sulphide membrane has the advantages of excellent crystallization, complete shape, high repeatability, short reaction period, low reaction temperature, capability of greatly reducing energy consumption and saving cost, simple operation, good repeatability and suitability for mass production.
Description
Technical field
The present invention relates to a kind of preparation method of cadmium sulphide membrane, be specifically related to a kind of method of preparing hexagonal flaky cadmium sulphide membrane in microwave hydrothermal mode.This method can be prepared the good cadmium sulphide membrane of homogeneously crystallized property quickly and easily, and prepared cadmium sulphide membrane is about 100nm by the length of side, and thickness is about the hexagonal flaky cadmium sulphide membrane of 20-50nm.
Background technology
Cadmium Sulfide (CdS) is a kind of wide bandgap semiconductor materials, and band gap width is about 2.42eV.The CdS film is to be a kind of important n type window material in the solar cell, constitutes the pn knot with p section bar material, is the important component part of solar cell.The method for preparing at present cadmium sulphide membrane has vacuum plating, ion sputtering, galvanic deposit, molecular beam epitaxy, elevated temperature heat spraying and electroless plating etc.These filming technologies are comparatively ripe, but need special equipment, and complicated preparation technology and harsh conditions such as vacuum high-temperature make that the cost of preparation cadmium sulphide membrane is too high, are difficult to realize preparing simply fast nano thin-film.Microwave is a kind of special type of heating, can in the space, produce the variation in electric field and magnetic field, make the molecular motion aggravation, thereby acquisition heat energy, microwave method is as a kind of heating means evenly and rapidly, make synthesizing nano-particle become efficiently, simple and repeatability height also is a kind of method for preparing film efficiently.
Summary of the invention
The object of the present invention is to provide a kind of simple to operately, need not protective atmosphere, and the reaction times is short, temperature of reaction is low, the method for the preparing hexagonal flaky cadmium sulphide membrane in microwave hydrothermal mode that energy consumption is little.
For achieving the above object, the technical solution used in the present invention is:
1) gets the analytically pure Cadmium Sulphate (CdSO48/3H of 0.50-10.00g
2O) place beaker, the oleic acid that drips 1-5mL in beaker gets mixture A;
2) in mixture A, add the clear solution B that the deionized water magnetic agitation is mixed with 100mL;
3) add 1-10mL n-Butyl Amine 99 (C4H11N) in solution B, ultrasonic wave 20min gets solution C under the normal temperature;
4) in solution C, add the analytically pure sodium sulphite of 2.00-5.00g (NaS), the normal temperature lower magnetic force stir solution D;
5) the pH value of regulator solution D gets coating liquid to 3.0-11.0;
6) clean substrate: with the Si substrate respectively in water and in the dehydrated alcohol behind the ultrasonic oscillation, be to soak activation treatment in 1: 1 70% nitric acid and 30% the hydrogen peroxide blended activation solution in volume ratio;
7) coating liquid of above-mentioned preparation is poured in the hydrothermal reaction kettle, compactedness is controlled at 50-80%; Then will be Si substrate after the activation treatment be placed in the hydrothermal reaction kettle, and be dipped in the coating liquid; The sealing hydrothermal reaction kettle puts it in the microwave hydrothermal reaction; Hydrothermal temperature is controlled at 120-200 ℃, and pressure-controlling is at 1.0-4.0MPa, and microwave power is controlled at 200-1000w, reaction 10min-30min;
8) reaction naturally cools to room temperature after finishing, and takes out the Si substrate, and after cleaning with distilled water and dehydrated alcohol respectively, the vacuum drying oven inner drying of putting into 100 ℃ promptly obtains hexagonal flaky cadmium sulphide membrane at substrate surface.
Because the present invention combines microwave method and hydrothermal method, the cadmium sulphide membrane well-crystallized of gained, complete shape and appearance, repeatable high, to prepare the length of side and be about 100nm, thickness is about the hexagonal flaky cadmium sulphide membrane of 20-50nm.This method reaction time is short, temperature of reaction is low, greatly reduces energy consumption, has saved cost, and simple to operate, and good reproducibility is fit to scale operation.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the prepared hexagonal flaky cadmium sulphide membrane of embodiment 1.
Fig. 2 is field emission scanning electron microscope (FE-SEM) photo of the prepared hexagonal flaky cadmium sulphide membrane of embodiment 1.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further details.
Embodiment 1:
1) gets the analytically pure Cadmium Sulphate (CdSO48/3H of 1.50g
2O) place beaker, the oleic acid that drips 2mL in beaker gets mixture A;
2) in mixture A, add the clear solution B that the deionized water magnetic agitation is configured to 100mL;
3) add 3mL n-Butyl Amine 99 (C4H11N) in solution B, ultrasonic wave 20min gets solution C under the normal temperature;
4) in solution C, add the analytically pure sodium sulphite of 2.50g (NaS), the normal temperature lower magnetic force stir solution D;
5) the pH value to 4.0 of regulator solution D gets coating liquid;
6) clean substrate:, be to soak activation treatment in 1: 1 70% nitric acid and 30% the hydrogen peroxide blended activation solution in volume ratio with Si substrate ultrasonic oscillation after 20 minutes in water and in the dehydrated alcohol respectively;
7) coating liquid of above-mentioned preparation is poured in the hydrothermal reaction kettle, compactedness is controlled at 70%; Then will be Si substrate after the activation treatment be placed in the hydrothermal reaction kettle, and be dipped in the coating liquid; The sealing hydrothermal reaction kettle puts it in the microwave hydrothermal reaction; Hydrothermal temperature is controlled at 150 ℃, and pressure-controlling is at 2.0MPa, and microwave power is controlled at 500w, reaction 20min;
8) reaction naturally cools to room temperature after finishing, and takes out the Si substrate, and after cleaning with distilled water and dehydrated alcohol respectively, the vacuum drying oven inner drying of putting into 100 ℃ promptly obtains hexagonal flaky cadmium sulphide membrane at substrate surface.
Prepared hexagonal flaky cadmium sulphide membrane is analyzed with Japanese D/max2000PCX-x ray diffractometer x of science, and product is the hexagonal system CdS crystalline substance (Fig. 1) that JCPDS is numbered 41-1049 as can be known.This sample is observed with (Fig. 2) under the JSM-6700F field emission scanning electron microscope, had the hexagonal flake pattern of rule from the prepared as can be seen CdS film of photo.
Embodiment 2:
1) gets the analytically pure Cadmium Sulphate (CdSO48/3H of 4.00g
2O) place beaker, the oleic acid that drips 3mL in beaker gets mixture A;
2) in mixture A, add the clear solution B that the deionized water magnetic agitation is configured to 100mL;
3) add 7mL n-Butyl Amine 99 (C4H11N) in solution B, ultrasonic wave 20min gets solution C under the normal temperature;
4) in solution C, add the analytically pure sodium sulphite of 3.50g (NaS), the normal temperature lower magnetic force stir solution D;
5) the pH value to 6.0 of regulator solution D gets coating liquid;
6) clean substrate:, be to soak activation treatment in 1: 1 70% nitric acid and 30% the hydrogen peroxide blended activation solution in volume ratio with Si substrate ultrasonic oscillation after 20 minutes in water and in the dehydrated alcohol respectively;
7) coating liquid of above-mentioned preparation is poured in the hydrothermal reaction kettle, compactedness is controlled at 67%; Then will be Si substrate after the activation treatment be placed in the hydrothermal reaction kettle, and be dipped in the coating liquid; The sealing hydrothermal reaction kettle puts it in the microwave hydrothermal reaction; Hydrothermal temperature is controlled at 180 ℃, and pressure-controlling is at 3.0MPa, and microwave power is controlled at 600w, reaction 20min;
8) reaction naturally cools to room temperature after finishing, and takes out the Si substrate, and after cleaning with distilled water and dehydrated alcohol respectively, the vacuum drying oven inner drying of putting into 100 ℃ promptly obtains hexagonal flaky cadmium sulphide membrane at substrate surface.
Embodiment 3:
1) gets the analytically pure Cadmium Sulphate (CdSO48/3H of 5.00g
2O) place beaker, the oleic acid that drips 4mL in beaker gets mixture A;
2) in mixture A, add the clear solution B that the deionized water magnetic agitation is configured to 100mL;
3) add 5mL n-Butyl Amine 99 (C4H11N) in solution B, ultrasonic wave 20min gets solution C under the normal temperature;
4) in solution C, add the analytically pure sodium sulphite of 4.50g (NaS), the normal temperature lower magnetic force stir solution D;
5) the pH value to 8.0 of regulator solution D gets coating liquid;
6) clean substrate:, be to soak activation treatment in 1: 1 70% nitric acid and 30% the hydrogen peroxide blended activation solution in volume ratio with Si substrate ultrasonic oscillation after 20 minutes in water and in the dehydrated alcohol respectively;
7) coating liquid of above-mentioned preparation is poured in the hydrothermal reaction kettle, compactedness is controlled at 60%; Then will be Si substrate after the activation treatment be placed in the hydrothermal reaction kettle, and be dipped in the coating liquid; The sealing hydrothermal reaction kettle puts it in the microwave hydrothermal reaction; Hydrothermal temperature is controlled at 120 ℃, and pressure-controlling is at 4.0MPa, and microwave power is controlled at 1000w, reaction 30min;
8) reaction naturally cools to room temperature after finishing, and takes out the Si substrate, and after cleaning with distilled water and dehydrated alcohol respectively, the vacuum drying oven inner drying of putting into 100 ℃ promptly obtains hexagonal flaky cadmium sulphide membrane at substrate surface.
Embodiment 4:
1) gets the analytically pure Cadmium Sulphate (CdSO48/3H of 0.50g
2O) place beaker, the oleic acid that drips 1L in beaker gets mixture A;
2) in mixture A, add the clear solution B that the deionized water magnetic agitation is configured to 100mL;
3) add 1mL n-Butyl Amine 99 (C4H11N) in solution B, ultrasonic wave 20min gets solution C under the normal temperature;
4) in solution C, add the analytically pure sodium sulphite of 2.00g (NaS), the normal temperature lower magnetic force stir solution D;
5) the pH value to 3.0 of regulator solution D gets coating liquid;
6) clean substrate:, be to soak activation treatment in 1: 1 70% nitric acid and 30% the hydrogen peroxide blended activation solution in volume ratio with Si substrate ultrasonic oscillation after 20 minutes in water and in the dehydrated alcohol respectively;
7) coating liquid of above-mentioned preparation is poured in the hydrothermal reaction kettle, compactedness is controlled at 50%; Then will be Si substrate after the activation treatment be placed in the hydrothermal reaction kettle, and be dipped in the coating liquid; The sealing hydrothermal reaction kettle puts it in the microwave hydrothermal reaction; Hydrothermal temperature is controlled at 200 ℃, and pressure-controlling is at 1.0MPa, and microwave power is controlled at 200w, reaction 10min;
8) reaction naturally cools to room temperature after finishing, and takes out the Si substrate, and after cleaning with distilled water and dehydrated alcohol respectively, the vacuum drying oven inner drying of putting into 100 ℃ promptly obtains hexagonal flaky cadmium sulphide membrane at substrate surface.
Embodiment 5:
1) gets the analytically pure Cadmium Sulphate (CdSO48/3H of 10.00g
2O) place beaker, the oleic acid of Dropwise 5 mL gets mixture A in beaker;
2) in mixture A, add the clear solution B that the deionized water magnetic agitation is configured to 100mL;
3) add 10mL n-Butyl Amine 99 (C4H11N) in solution B, ultrasonic wave 20min gets solution C under the normal temperature;
4) in solution C, add the analytically pure sodium sulphite of 5.00g (NaS), the normal temperature lower magnetic force stir solution D;
5) the pH value to 11.0 of regulator solution D gets coating liquid;
6) clean substrate:, be to soak activation treatment in 1: 1 70% nitric acid and 30% the hydrogen peroxide blended activation solution in volume ratio with Si substrate ultrasonic oscillation after 20 minutes in water and in the dehydrated alcohol respectively;
7) coating liquid of above-mentioned preparation is poured in the hydrothermal reaction kettle, compactedness is controlled at 80%; Then will be Si substrate after the activation treatment be placed in the hydrothermal reaction kettle, and be dipped in the coating liquid; The sealing hydrothermal reaction kettle puts it in the microwave hydrothermal reaction; Hydrothermal temperature is controlled at 160 ℃, and pressure-controlling is at 2.0MPa, and microwave power is controlled at 400w, reaction 15min;
8) reaction naturally cools to room temperature after finishing, and takes out the Si substrate, and after cleaning with distilled water and dehydrated alcohol respectively, the vacuum drying oven inner drying of putting into 100 ℃ promptly obtains hexagonal flaky cadmium sulphide membrane at substrate surface.
Beneficial effect of the present invention is embodied in:
1) the hexagonal flake cadmium sulfide crystalline substance that makes of the method, complete shape and appearance, size evenly and can be controlled its length of side and thickness by control reaction temperature and time.
2) hexagonal flake cadmium sulfide of this method preparation is short brilliant reaction time, and energy consumption is low.
3) this method is easy to operate, and raw material is easy to get, and preparation cost is lower.
Claims (1)
1. the method for a preparing hexagonal flaky cadmium sulphide membrane in microwave hydrothermal mode is characterized in that may further comprise the steps:
1) the analytically pure Cadmium Sulphate of getting 0.50-10.00g places beaker, and the oleic acid that drips 1-5mL in beaker gets mixture A;
2) in mixture A, add the clear solution B that the deionized water magnetic agitation is mixed with 100mL;
3) add the 1-10mL n-Butyl Amine 99 in solution B, ultrasonic wave 20min gets solution C under the normal temperature;
4) in solution C, add the analytically pure sodium sulphite of 2.00-5.00g, the normal temperature lower magnetic force stir solution D;
5) the pH value of regulator solution D gets coating liquid to 3.0-11.0;
6) clean substrate: with the Si substrate respectively in water and in the dehydrated alcohol behind the ultrasonic oscillation, be to soak activation treatment in 1: 1 70% nitric acid and 30% the hydrogen peroxide blended activation solution in volume ratio;
7) coating liquid of above-mentioned preparation is poured in the hydrothermal reaction kettle, compactedness is controlled at 50-80%; Then will be Si substrate after the activation treatment be placed in the hydrothermal reaction kettle, and be dipped in the coating liquid; The sealing hydrothermal reaction kettle puts it in the microwave hydrothermal reaction; Hydrothermal temperature is controlled at 120-200 ℃, and pressure-controlling is at 1.0-4.0MPa, and microwave power is controlled at 200-1000w, reaction 10min-30min;
8) reaction naturally cools to room temperature after finishing, and takes out the Si substrate, and after cleaning with distilled water and dehydrated alcohol respectively, the vacuum drying oven inner drying of putting into 100 ℃ promptly obtains hexagonal flaky cadmium sulphide membrane at substrate surface.
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| CN102392306A (en) * | 2011-11-23 | 2012-03-28 | 陕西科技大学 | Microwave hydro-thermal method for preparing SnS film |
| CN102424959A (en) * | 2011-11-23 | 2012-04-25 | 陕西科技大学 | Method for preparing cobalt sulfide thin film on indium tin oxide (ITO) substrate by microwave hydrothermal process |
| CN106698500A (en) * | 2015-11-16 | 2017-05-24 | 天津大学 | Cadmium sulfide ultrathin nanometer flaky material preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396118A (en) * | 2002-04-23 | 2003-02-12 | 中国科学院化学研究所 | Process for preparing nano-class Cds semiconductor material |
| CN101698963A (en) * | 2009-10-30 | 2010-04-28 | 陕西科技大学 | Method for preparing CdS film in microwave hydrothermal mode |
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| JPS6060970A (en) * | 1983-09-14 | 1985-04-08 | アルプス電気株式会社 | Manufacture of cadmium sulfide sintered body |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396118A (en) * | 2002-04-23 | 2003-02-12 | 中国科学院化学研究所 | Process for preparing nano-class Cds semiconductor material |
| CN101698963A (en) * | 2009-10-30 | 2010-04-28 | 陕西科技大学 | Method for preparing CdS film in microwave hydrothermal mode |
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