CN101853901B - Method for preparing cadmium sulfide nanometer membrane by self assembly - Google Patents

Method for preparing cadmium sulfide nanometer membrane by self assembly Download PDF

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CN101853901B
CN101853901B CN201010181991XA CN201010181991A CN101853901B CN 101853901 B CN101853901 B CN 101853901B CN 201010181991X A CN201010181991X A CN 201010181991XA CN 201010181991 A CN201010181991 A CN 201010181991A CN 101853901 B CN101853901 B CN 101853901B
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cadmium sulfide
ito substrate
membrane
self assembly
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CN101853901A (en
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黄剑锋
张钦峰
胡宝云
曹丽云
吴建鹏
熊信柏
曾燮榕
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Shaanxi University of Science and Technology
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Abstract

The invention provides a method for preparing a cadmium sulfide nanometer membrane by self assembly. The method comprises the following steps of: mixing cadmium carbonate and trimethylamine to obtain A, and adding deionized water into A to obtain B; adding PVP into the B, performing magnetic stirring to obtain C, adding thioacetamide into the C, and uniformly stirring the mixture to obtain D; adjusting a pH value of the solution D to 4.0 to 10.0 to obtain precursor solution; soaking a clean ITO base plate in benzene solution of CTAB at room temperature, taking the base plate out, and drying the base plate in an argon protective atmosphere; placing the dried ITO base plate in the precursor solution for deposition at room temperature for 5 to 40 hours to prepare a cadmium sulfide membrane; and drying the prepared cadmium sulfide membrane in a vacuum dry box to obtain the cadmium sulfide nanometer membrane. Because the method of the invention adopts the self assembly, the cadmium sulfide nanometer membrane prepared by the method has a complete shape and uniform size; and the thickness of the membrane and the size of crystal grains can be controlled by controlling the concentration and pH value of the reaction precursor solution and the deposition time. The cadmium sulfide nanometer membrane prepared by the method has the advantages of high repeatability and easy formation of large-area membranes; and the method has the advantages of easy operation, readily available raw materials and low preparation cost.

Description

A kind of method of preparing cadmium sulfide nanometer membrane by self assembly
Technical field
The present invention relates to a kind of preparation method of cadmium sulfide nano-film, be specifically related to a kind ofly can prepare evenly smooth cadmium sulfide nano-film, the method for the preparing cadmium sulfide nanometer membrane by self assembly of the crystallite dimension of film about 30nm quickly and easily.
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.Up to the present, the method for preparing cadmium sulphide membrane has vacuum coating, ion sputtering, electro-deposition, molecular beam epitaxy, elevated temperature heat spraying and chemical deposition 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.Self-assembled monolayer (Self-assembled monolayers) technology (being called for short the SAMs technology), it is a kind of new technology for preparing nano thin-film, by the chemisorption between surfactant and the substrate, self assembly forms and arranges orderly molecule rete on baseplate material.Method is simple to be self-assembled into membrane technology, do not need special installation, and the film defects of preparation is few, adhesion is strong, and good crystallinity does not need the later stage crystallization and thermal treatment.
Summary of the invention
The object of the present invention is to provide a kind of simple to operately, need not protective atmosphere, the reaction condition mild temperature is low, and energy consumption is little, and the cadmium sulphide membrane perfect crystalline of gained is repeatable high, need not the method for heat treated preparing cadmium sulfide nanometer membrane by self assembly of later stage.About prepared cadmium sulfide nano-film crystallite dimension 30nm.
For achieving the above object, the technical solution used in the present invention is:
1) gets the analytically pure cadmium carbonate (CdCO of 1.00-10.00g 3) placing beaker, the trimethylamine (C3H9N) that drips 2-8mL in beaker gets mixture A;
2) the adding deionized water and stirring is even in mixture A, is configured to the clear solution B of 200mL;
3) in solution B, add the PVP (polyvinylpyrrolidone) of 1.00-20.00g, the normal temperature lower magnetic force stir solution C;
4) in solution C, add the analytically pure thioacetamide of 1.00-6.00g (TAA, molecular formula is: CH3CSNH2) stir solution D;
5) the pH value of regulator solution D gets precursor liquid E to 4.0-10.0;
6) getting the ito substrate that cleans up, to place volumetric concentration be that the benzole soln of 2% CTAB (softex kw) at room temperature soaks 30min, take out the back under the argon gas atmosphere protection in 100 ℃ of dryings;
7) dried ito substrate is placed precursor liquid E, at room temperature deposit 5-40h and prepare cadmium sulphide membrane, the film for preparing is placed the dry cadmium sulfide nano-film that gets of vacuum drying chamber.
The cleaning of ito substrate of the present invention is earlier ito substrate to be placed solution F ultrasonic waves for cleaning 15min, remove the lip-deep acidic materials of ito substrate, again ito substrate is placed solution G ultrasonic waves for cleaning 15min, use absolute ethyl alcohol and deionized water wash respectively behind the removal alkaline matter;
Said solution F is H 2O: NH 4OH: H 2O 2=6: the mixed solution of 2: 1 volume ratios;
Said solution G is H 2O: HCl: H 2O 2=6: the mixed solution of 2: 1 volume ratios.
The baking temperature of said vacuum drying chamber is 80 ℃.
Because the present invention adopts the liquid phase self-assembling method, the cadmium sulfide nano-film that makes, complete shape and appearance, size is even, and can control film thickness and grain size by control reaction precursor liquid concentration, pH value and sedimentation time.The cadmium sulfide nano-film repeatability of this method preparation is high, is easy to large tracts of land system film.And easy to operate, raw material is easy to get, and preparation cost is lower.
Description of drawings
Fig. 1 is field emission scanning electron microscope (FE-SEM) photo of the prepared cadmium sulfide nano-film of embodiment 1.
Fig. 2 is the partial enlarged drawing of Fig. 1.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Embodiment 1:
1) gets the analytically pure cadmium carbonate (CdCO of 2.00g 3) placing beaker, the trimethylamine (C3H9N) that drips 3mL in beaker gets mixture A;
2) the adding deionized water and stirring is even in mixture A, is configured to the clear solution B of 200mL;
3) in solution B, add the PVP (polyvinylpyrrolidone) of 2.00g, the normal temperature lower magnetic force stir solution C.
4) in solution C, add the analytically pure thioacetamide of 3.00g (TAA, molecular formula is: CH3CSNH2) stir solution D;
5) the pH value to 4.5 with regulator solution D gets precursor liquid E;
6) get ito substrate and earlier ito substrate is placed solution F ultrasonic waves for cleaning 15min, remove the lip-deep acidic materials of ito substrate, again ito substrate is placed solution G ultrasonic waves for cleaning 15min, use absolute ethyl alcohol and deionized water wash respectively behind the removal alkaline matter;
Said solution F is H 2O: NH 4OH: H 2O 2=6: the mixed solution of 2: 1 volume ratios;
Said solution G is H 2O: HCl: H 2O 2=6: the mixed solution of 2: 1 volume ratios.
7) getting the ito substrate that cleans up, to place volumetric concentration be that the benzole soln of 2% CTAB (softex kw) at room temperature soaks 30min, take out the back under the argon gas atmosphere protection in 100 ℃ of dryings;
8) dried ito substrate is placed precursor liquid E, at room temperature deposit 6h and prepare cadmium sulphide membrane, place vacuum drying chamber at 80 ℃ of dry cadmium sulfide nano-films that get the film for preparing.
The cadmium sulphide membrane under the JSM-6700F field emission scanning electron microscope (Fig. 1, Fig. 2) of this embodiment preparation is observed, better from the CdS nano thin-film crystallization that photo is prepared as can be seen, uniformity is better, and the crystallite dimension of film is about 30nm as can be seen from Figure 2.
Embodiment 2:
1) gets the analytically pure cadmium carbonate (CdCO of 5.00g 3) place beaker, the trimethylamine C3H9N of Dropwise 5 mL in beaker) and mixture A;
2) the adding deionized water and stirring is even in mixture A, is configured to the clear solution B of 200mL;
3) in solution B, add the PVP (polyvinylpyrrolidone) of 3.00g, the normal temperature lower magnetic force stir solution C.
4) in solution C, add the analytically pure thioacetamide of 4.00g (TAA, molecular formula is: CH3CSNH2) stir solution D;
5) the pH value to 6.0 with regulator solution D gets precursor liquid E;
6) get ito substrate and earlier ito substrate is placed solution F ultrasonic waves for cleaning 15min, remove the lip-deep acidic materials of ito substrate, again ito substrate is placed solution G ultrasonic waves for cleaning 15min, use absolute ethyl alcohol and deionized water wash respectively behind the removal alkaline matter;
Said solution F is H 2O: NH 4OH: H 2O 2=6: the mixed solution of 2: 1 volume ratios;
Said solution G is H 2O: HCl: H 2O 2=6: the mixed solution of 2: 1 volume ratios.
7) getting the ito substrate that cleans up, to place volumetric concentration be that the benzole soln of 2% CTAB (softex kw) at room temperature soaks 30min, take out the back under the argon gas atmosphere protection in 100 ℃ of dryings;
8) dried ito substrate is placed precursor liquid E, at room temperature deposit 10h and prepare cadmium sulphide membrane, place vacuum drying chamber at 80 ℃ of dry cadmium sulfide nano-films that get the film for preparing.
Embodiment 3:
1) gets the analytically pure cadmium carbonate (CdCO of 6.00g 3) placing beaker, the trimethylamine (C3H9N) that drips 6mL in beaker gets mixture A;
2) the adding deionized water and stirring is even in mixture A, is configured to the clear solution B of 200mL;
3) in solution B, add the PVP (polyvinylpyrrolidone) of 6.00g, the normal temperature lower magnetic force stir solution C.
4) in solution C, add the analytically pure thioacetamide of 5.5g (TAA, molecular formula is: CH3CSNH2) stir solution D;
5) the pH value to 8.0 with regulator solution D gets precursor liquid E;
6) get ito substrate and earlier ito substrate is placed solution F ultrasonic waves for cleaning 15min, remove the lip-deep acidic materials of ito substrate, again ito substrate is placed solution G ultrasonic waves for cleaning 15min, use absolute ethyl alcohol and deionized water wash respectively behind the removal alkaline matter;
Said solution F is H 2O: NH 4OH: H 2O 2=6: the mixed solution of 2: 1 volume ratios;
Said solution G is H 2O: HCl: H 2O 2=6: the mixed solution of 2: 1 volume ratios.
7) getting the ito substrate that cleans up, to place volumetric concentration be that the benzole soln of 2% CTAB (softex kw) at room temperature soaks 30min, take out the back under the argon gas atmosphere protection in 100 ℃ of dryings;
8) dried ito substrate is placed precursor liquid E, at room temperature deposit 15h and prepare cadmium sulphide membrane, place vacuum drying chamber at 80 ℃ of dry cadmium sulfide nano-films that get the film for preparing.
Embodiment 4:
1) gets the analytically pure cadmium carbonate (CdCO of 1.00g 3) placing beaker, the trimethylamine (C3H9N) that drips 2mL in beaker gets mixture A;
2) the adding deionized water and stirring is even in mixture A, is configured to the clear solution B of 200mL;
3) in solution B, add the PVP (polyvinylpyrrolidone) of 1.00g, the normal temperature lower magnetic force stir solution C.
4) in solution C, add the analytically pure thioacetamide of 1.00g (TAA, molecular formula is: CH3CSNH2) stir solution D;
5) the pH value to 4.0 with regulator solution D gets precursor liquid E;
6) get ito substrate and earlier ito substrate is placed solution F ultrasonic waves for cleaning 15min, remove the lip-deep acidic materials of ito substrate, again ito substrate is placed solution G ultrasonic waves for cleaning 15min, use absolute ethyl alcohol and deionized water wash respectively behind the removal alkaline matter;
Said solution F is H 2O: NH 4OH: H 2O 2=6: the mixed solution of 2: 1 volume ratios;
Said solution G is H 2O: HCl: H 2O 2=6: the mixed solution of 2: 1 volume ratios.
7) getting the ito substrate that cleans up, to place volumetric concentration be that the benzole soln of 2% CTAB (softex kw) at room temperature soaks 30min, take out the back under the argon gas atmosphere protection in the 100C drying;
8) dried ito substrate is placed precursor liquid E, at room temperature deposit 30h and prepare cadmium sulphide membrane, place vacuum drying chamber at 80 ℃ of dry cadmium sulfide nano-films that get the film for preparing.
Embodiment 5:
1) gets the analytically pure cadmium carbonate (CdCO of 10.00g 3) placing beaker, the trimethylamine (C3H9N) that drips 8mL in beaker gets mixture A;
2) the adding deionized water and stirring is even in mixture A, is configured to the clear solution B of 200mL;
3) in solution B, add the PVP (polyvinylpyrrolidone) of 20.00g, the normal temperature lower magnetic force stir solution C.
4) in solution C, add the analytically pure thioacetamide of 6.00g (TAA, molecular formula is: CH3CSNH2) stir solution D;
5) the pH value to 10.0 with regulator solution D gets precursor liquid E;
6) get ito substrate and earlier ito substrate is placed solution F ultrasonic waves for cleaning 15min, remove the lip-deep acidic materials of ito substrate, again ito substrate is placed solution G ultrasonic waves for cleaning 15min, use absolute ethyl alcohol and deionized water wash respectively behind the removal alkaline matter;
Said solution F is H 2O: NH 4OH: H 2O 2=6: the mixed solution of 2: 1 volume ratios;
Said solution G is H 2O: HCl: H 2O 2=6: the mixed solution of 2: 1 volume ratios.
7) getting the ito substrate that cleans up, to place volumetric concentration be that the benzole soln of 2% CTAB (softex kw) at room temperature soaks 30min, take out the back under the argon gas atmosphere protection in 100 ℃ of dryings;
8) dried ito substrate is placed precursor liquid E, at room temperature deposit 4h and prepare cadmium sulphide membrane, place vacuum drying chamber at 80 ℃ of dry cadmium sulfide nano-films that get the film for preparing.
Embodiment 6:
1) gets the analytically pure cadmium carbonate (CdCO of 8.00g 3) placing beaker, the trimethylamine (C3H9N) that drips 7mL in beaker gets mixture A;
2) the adding deionized water and stirring is even in mixture A, is configured to the clear solution B of 200mL;
3) in solution B, add the PVP (polyvinylpyrrolidone) of 15.00g, the normal temperature lower magnetic force stir solution C.
4) in solution C, add the analytically pure thioacetamide of 5.00g (TAA, molecular formula is: CH3CSNH2) stir solution D;
5) the pH value to 9.0 with regulator solution D gets precursor liquid E;
6) get ito substrate and earlier ito substrate is placed solution F ultrasonic waves for cleaning 15min, remove the lip-deep acidic materials of ito substrate, again ito substrate is placed solution G ultrasonic waves for cleaning 15min, use absolute ethyl alcohol and deionized water wash respectively behind the removal alkaline matter;
Said solution F is H 2O: NH 4OH: H 2O 2=6: the mixed solution of 2: 1 volume ratios;
Said solution G is H 2O: HCl: H 2O 2=6: the mixed solution of 2: 1 volume ratios.
7) getting the ito substrate that cleans up, to place volumetric concentration be that the benzole soln of 2% CTAB (softex kw) at room temperature soaks 30min, take out the back under the argon gas atmosphere protection in 100 ℃ of dryings;
8) dried ito substrate is placed precursor liquid E, at room temperature deposit 40h and prepare cadmium sulphide membrane, place vacuum drying chamber at 80 ℃ of dry cadmium sulfide nano-films that get the film for preparing.

Claims (3)

1. the method for a preparing cadmium sulfide nanometer membrane by self assembly is characterized in that may further comprise the steps:
1) the analytically pure cadmium carbonate of getting 1.00-10.00g places beaker, and the trimethylamine that drips 2-8mL in beaker gets mixture A;
2) the adding deionized water and stirring is even in mixture A, is configured to the clear solution B of 200mL;
3) in solution B, add the polyvinylpyrrolidone of 1.00-20.00g, the normal temperature lower magnetic force stir solution C;
4) in solution C, add the analytically pure thioacetamide of 1.00-6.00g stir solution D;
5) the pH value of regulator solution D gets precursor liquid E to 4.0-10.0;
6) getting the ito substrate that cleans up, to place volumetric concentration be that the benzole soln of 2% softex kw at room temperature soaks 30min, take out the back under the argon gas atmosphere protection in 100 ℃ of dryings;
7) dried ito substrate is placed precursor liquid E, at room temperature deposit 5-40h and prepare cadmium sulphide membrane, the film for preparing is placed the dry cadmium sulfide nano-film that gets of vacuum drying chamber.
2. the method for preparing cadmium sulfide nanometer membrane by self assembly according to claim 1, it is characterized in that: the cleaning of said ito substrate is earlier ito substrate to be placed solution F ultrasonic waves for cleaning 15min, remove the lip-deep acidic materials of ito substrate, again ito substrate is placed solution G ultrasonic waves for cleaning 15min, use absolute ethyl alcohol and deionized water wash respectively behind the removal alkaline matter;
Said solution F is H 2O: NH 4OH: H 2O 2=6: the mixed solution of 2: 1 volume ratios;
Said solution G is H 2O: HCl: H 2O 2=6: the mixed solution of 2: 1 volume ratios.
3. the method for preparing cadmium sulfide nanometer membrane by self assembly according to claim 1, it is characterized in that: the baking temperature of said vacuum drying chamber is 80 ℃.
CN201010181991XA 2010-05-25 2010-05-25 Method for preparing cadmium sulfide nanometer membrane by self assembly Expired - Fee Related CN101853901B (en)

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CN1645559A (en) * 2004-12-03 2005-07-27 中国科学院长春应用化学研究所 Method for synthesizing cadmium selenide and quantum point with cadmium selenide cadmium sulfide nucleocapsid structure

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1645559A (en) * 2004-12-03 2005-07-27 中国科学院长春应用化学研究所 Method for synthesizing cadmium selenide and quantum point with cadmium selenide cadmium sulfide nucleocapsid structure

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