CN101638777A - Method for depositing copper sulphide nano film rapidly in low temperature - Google Patents
Method for depositing copper sulphide nano film rapidly in low temperature Download PDFInfo
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- CN101638777A CN101638777A CN200910088841A CN200910088841A CN101638777A CN 101638777 A CN101638777 A CN 101638777A CN 200910088841 A CN200910088841 A CN 200910088841A CN 200910088841 A CN200910088841 A CN 200910088841A CN 101638777 A CN101638777 A CN 101638777A
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Abstract
The invention relates to a method for depositing copper sulphide nano film rapidly in low temperature, belonging to the technical field of the preparation of functional film materials. The preparationmethod of copper sulphide film in the prior art has high requirement on the deposition conditions, needs high temperature heating, has great limitations for the deposition of substrate, and has longer preparation time and low efficiency, thus being not benefical to the industrial production. In the preparation method of copper sulphide nano film of the invention, the ethylene diamine tetraaceticacid disodium (EDTA-2Na) is used as complexing agent, nano copper sulphide film with an indigo copper ore structure can be obtained on semiconductor substrate and conducting substrate within 40 minutes and in the microwave water-bath environment at the temperature of lower than 100 DEG C, and the crystal particles of the nano copper sulphide film are tiny, uniform, compact and have specific microstructure. The invention has simple technology and low cost, and is suitable for large-scale production and application.
Description
Technical field
The present invention relates to a kind of method of depositing copper sulphide nano film rapidly in low temperature, in lower temperature range, as complexing agent, can deposit in the short period of time and obtain nano level cupric sulfide film with disodium ethylene diamine tetraacetate (EDTA-2Na).The preparing technical field that belongs to film material with function.
Background technology
Cu
xS (x=1-2) is a kind of important photoelectric functional material.1976, D.F.A.Koch, R.J.McIntyre has reported Cu
xS at room temperature exists five kinds of stable compound: CuS, Cu at least
1.75S, Cu
1.8S, Cu
1.95S, Cu
2S.In a very long time from now on, they are widely used in optics and electricity device, as photothermal converter spare, electrical conductivity electrode, microwave protection coating, solar control coating, dye sensitization solar battery, nanotube switch, lithium ion battery anode material and some chemical sensitization devices.In the recent period, CuS is found in the character that has superconduction under the 1.6K temperature again.
Cupric sulfide (CuS) has six side's covellite structures, and spacer is P63/mmc, unit cell parameters
Nowadays, research to preparation CuS film is a lot of relatively, and the existing method for preparing the CuS film is varied, wherein, the method of physics preparation is had relatively high expectations to mode of deposition mostly, needs conditions such as vacuum, high temperature, can inevitably destroy original pattern of film like this, be difficult to the chemical dosage ratio of the composition of the accurate prepared film of control simultaneously, so also can change the optics of film and electrology characteristic and then influence its application in strict conformity with its molecular formula.And for some common chemical preparation process as the reaction of: liquid-liquid interface, chemical vapour deposition, chemical gas phase reaction, electrochemical method, atomic shell absorption reaction continuously, ald, spraying atomic shell gas-phase reaction etc., some needs heat, and some has significant limitation to deposition substrate.So a kind of new preparation method of needs was both simple, can prepare the CuS film of ad hoc structure and pattern again.In recent years, human chemical bath method success such as people such as I.Puspitasari and K.D.Yuan prepare the CuS film, yet preparation time is longer relatively, efficient is lower, is unfavorable for industrial production, this can influence the further application of CuS film.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, propose a kind of quick synthesizing of low temperature to the substrate non-selectivity to have well-crystallized and have the method for the CuS film of strict stoichiometric ratio.Its technology is simple, and is with low cost, is suitable for large-scale production and application.
In order to realize this purpose, the present invention adopts disodium ethylene diamine tetraacetate (EDTA-2Na) as complexing agent, be lower than under 100 ℃ the microwave water-bath environment, within 40 minutes, on substrate, all obtained to have the covellite structure, tiny homogeneous densification of crystal grain and nano-copper sulfide film with specific microtexture.
The method of a kind of depositing copper sulphide nano film rapidly in low temperature provided by the present invention may further comprise the steps:
A) pre-treatment of substrate: substrate after abundant the cleaning, is used deionized water rinsing again, and is immersed in the ethanol standby in ultrasonic cleaning machine with toluene, acetone, ethanol successively;
B) with Cu (Ac)
2Powder dissolution stirs in deionized water, adds and Cu (Ac)
2Deng the complexing agent EDTA-2Na of amount of substance, continue stirred solution, obtain the blue solution A of clear;
C) in solution A, add NaOH solution and HCl solution adjusting pH value to 6～10, obtain solution B;
D) in solution B, slowly add and Cu (Ac)
2Deng the thioacetamide of amount of substance, and stir, obtain the clear solution C;
E) will dry up with nitrogen through pretreated substrate, and put into solution C, and substrate will be inverted be floated on the solution C surface, microwave exposure 20min～40min obtains the CuS film.
Described substrate is conductive substrates or semiconducter substrate.
Described conductive substrates is transparent conducting glass (a FTO glass), and described semiconducter substrate is a silicon 100.
Usefulness of the present invention is: can deposit on conductive substrates and semiconducter substrate and obtain the high cupric sulfide film of crystallinity.The present invention is simple with respect to gas phase legal system film production process, has reduced depositing temperature and has shortened film formation time; With respect to electrochemical method for synthesizing, the present invention does not have particular requirement can adapt to large-scale production application to substrate.Adopt disodium ethylene diamine tetraacetate effectively to avoid initial reaction stage cupric ion and sulfonium ion a large amount of nucleation precipitations in solution as complexing agent.The substrate that swims in the reaction soln surface has effectively avoided the cupric sulfide crystallite of the solution Xiangli generation in the deposition process to be adsorbed onto substrate surface.Adopt the mode of microwave heating, solution is heated evenly, greatly shortened the thin film deposition time.
Description of drawings
Fig. 1 is the comparison of the prepared cupric sulfide film of the present invention with X-ray diffraction (XRD) collection of illustrative plates of FTO substrate, above curve be the XRD figure spectrum of the cupric sulfide film of preparation, below curve be the FTO substrate XRD figure is composed.
Fig. 2 is the stereoscan photograph of the cupric sulfide film of embodiment 1 preparation.
Fig. 3 is the stereoscan photograph of the cupric sulfide film of embodiment 2 preparations.
Fig. 4 is the stereoscan photograph of the cupric sulfide film of embodiment 3 preparations.
Fig. 5 is the stereoscan photograph of the cupric sulfide film of embodiment 4 preparations.
Fig. 6 is the stereoscan photograph of the cupric sulfide film of embodiment 5 preparations.
Embodiment
Below in conjunction with the drawings and specific embodiments, further illustrate substantive distinguishing features of the present invention and remarkable advantage, the present invention only is confined to the embodiment that stated by no means.
In following examples, all adopt the German Bruker Advance D-8X of company ray powder diffraction instrument (Cu K α radiation,
) measure the structure of prepared film; Adopt the microscopic appearance of the prepared film of Hitachi S-3500N determination of electron microscopy.
Embodiment 1:
A) pre-treatment of substrate: transparent conducting glass substrate (FTO glass) respectively after abundant the cleaning, is used deionized water rinsing with toluene, acetone, ethanol successively in ultrasonic cleaning machine, preserve with alcohol immersion, standby.
B) with the Cu (Ac) of 0.1mol/L
2The analytical pure powder dissolution adopts magnetic stirring apparatus to stir in the 100ml beaker in the 10ml deionized water, and disodium ethylene diamine tetraacetate (EDTA-2Na) the solution 10ml that will contain 0.1mol/L then adds clarifying Cu (Ac)
2In the solution, continue stirred solution, obtain the blue solution A of complete clear.
C) adding concentration in solution A is the NaOH solution of 6mol/L, regulates pH value to 10, obtains solution B.
D) in solution B, slowly add the thioacetyl amine aqueous solution 10ml that contains 0.1mol/L, add deionized water to 80ml, and stir, obtain the clear solution C.
E) will dry up with high pure nitrogen through pretreated substrate, put into the beaker that fills solution C, and substrate will be inverted be floated on the solution C surface.Beaker is positioned over reacting by heating 20min under the microwave exposure that power is 119W.Reaction has deposited thin film at substrate surface after finishing, and takes out substrate, dries up with the washed with de-ionized water film surface and under high pure nitrogen, obtains the CuS film.
Prepared as seen from Figure 1 cupric sulfide film is pure covellite structure, and crystallinity is fine.Fig. 2 has shown the microscopic appearance of this film: interlaced hexagon nanometer sheet vertical growth is in substrate surface, and its length of side is about 200～300nm, and thickness is about 20～40nm, and film is dense, grain density: 8.28/μ m
2
Embodiment 2:
A) pre-treatment of substrate: transparent conducting glass substrate (FTO glass) respectively after abundant the cleaning, is used deionized water rinsing with toluene, acetone, ethanol successively in ultrasonic cleaning machine, preserve with alcohol immersion, standby.
B) with a certain amount of 0.1mol/L Cu (Ac)
2The analytical pure powder dissolution adopts magnetic stirring apparatus to stir in the 100ml beaker in the 10ml deionized water, and disodium ethylene diamine tetraacetate (EDTA-2Na) the solution 10ml that will contain 0.1mol/L then adds clarifying Cu (Ac)
2In the solution, continue stirred solution, obtain the blue solution A of complete clear.
C) adding concentration in solution A is the NaOH solution of 6mol/L, regulates pH value to 8, obtains solution B.
D) in solution B, slowly add the thioacetyl amine aqueous solution 10ml that contains 0.1mol/L, add deionized water to 80ml, and stir, obtain the clear solution C.
E) will dry up with high pure nitrogen through pretreated substrate, put into the beaker that fills solution C, and substrate will be inverted be floated on the solution C surface.Beaker is positioned over reacting by heating 25min under the microwave exposure that power is 119W.Reaction has deposited thin film at substrate surface after finishing, and takes out substrate, dries up with the washed with de-ionized water film surface and under high pure nitrogen, obtains the CuS film.
Prepared as seen from Figure 1 cupric sulfide film is pure covellite structure, and crystallinity is fine.Fig. 3 has shown the microscopic appearance of this film: interlaced hexagon nanometer sheet vertical growth is in substrate surface, and its length of side is about 200～300nm, and thickness is about 20～40nm, and film is dense, grain density: 13.81/μ m
2
Embodiment 3:
A) pre-treatment of substrate: transparent conducting glass substrate (FTO glass) respectively after abundant the cleaning, is used deionized water rinsing with toluene, acetone, ethanol successively in ultrasonic cleaning machine, preserve with alcohol immersion, standby.
B) with a certain amount of 0.1mol/L Cu (Ac)
2The analytical pure powder dissolution adopts magnetic stirring apparatus to stir in the 100ml beaker in the 10ml deionized water, and disodium ethylene diamine tetraacetate (EDTA-2Na) the solution 10ml that will contain 0.1mol/L then adds clarifying Cu (Ac)
2In the solution, continue stirred solution, obtain the blue solution A of complete clear.
C) adding concentration in solution A is the HCl solution of 3mol/L, regulates pH value to 6, obtains solution B.
D) in solution B, slowly add the thioacetyl amine aqueous solution 10ml that contains 0.1mol/L, add deionized water to 80ml, and stir, obtain the clear solution C.
E) will dry up with high pure nitrogen through pretreated substrate, put into the beaker that fills solution C, and substrate will be inverted be floated on the solution C surface.Beaker is positioned over reacting by heating 30min under the microwave exposure that power is 119W.Reaction has deposited thin film at substrate surface after finishing, and takes out substrate, dries up with the washed with de-ionized water film surface and under high pure nitrogen, obtains the CuS film.
Prepared as seen from Figure 1 cupric sulfide film is pure covellite structure, and crystallinity is fine.Fig. 2 has shown the microscopic appearance of this film: interlaced hexagon nanometer sheet vertical growth is in substrate surface, and its length of side is about 200～300nm, and thickness is about 20～40nm, and film is dense, grain density: 19.33/μ m
2
Embodiment 4:
A) pre-treatment of substrate: silicon (100) substrate respectively after abundant the cleaning, is used deionized water rinsing with toluene, acetone, ethanol successively in ultrasonic cleaning machine, preserve with alcohol immersion, standby.
B) with a certain amount of 0.1mol/L Cu (Ac)
2The analytical pure powder dissolution adopts magnetic stirring apparatus to stir in the 100ml beaker in the 10ml deionized water, and disodium ethylene diamine tetraacetate (EDTA-2Na) the solution 10ml that will contain 0.1mol/L then adds clarifying Cu (Ac)
2In the solution, continue stirred solution, obtain the blue solution A of complete clear.
C) adding concentration in solution A is the NaOH solution of 6mol/L, regulates pH value to 8, obtains solution B.
D) in solution B, slowly add the thioacetyl amine aqueous solution 10ml that contains 0.1mol/L, add deionized water to 80ml, and stir, obtain the clear solution C.
E) will dry up with high pure nitrogen through pretreated substrate, put into the beaker that fills solution C, and substrate will be inverted be floated on the solution C surface.Beaker is positioned over reacting by heating 35min under the microwave exposure that power is 119W.Reaction has deposited thin film at substrate surface after finishing, and takes out substrate, dries up with the washed with de-ionized water film surface and under high pure nitrogen, obtains the CuS film.
Prepared as seen from Figure 1 cupric sulfide film is pure covellite structure, and crystallinity is fine.Fig. 2 has shown the microscopic appearance of this film: interlaced hexagon nanometer sheet vertical growth is in substrate surface, and its length of side is about 200～300nm, and thickness is about 20～40nm, and film is dense, grain density: 24.85/μ m
2
Embodiment 5:
A) pre-treatment of substrate: silicon (100) substrate respectively after abundant the cleaning, is used deionized water rinsing with toluene, acetone, ethanol successively in ultrasonic cleaning machine, preserve with alcohol immersion, standby.
B) with a certain amount of 0.1mol/L Cu (Ac)
2The analytical pure powder dissolution adopts magnetic stirring apparatus to stir in the 100ml beaker in the 10ml deionized water, and disodium ethylene diamine tetraacetate (EDTA-2Na) the solution 10ml that will contain 0.1mol/L then adds clarifying Cu (Ac)
2In the solution, continue stirred solution, obtain the blue solution A of complete clear.
C) adding concentration in solution A is the NaOH solution of 6mol/L, regulates pH value to 10, obtains solution B.
D) in solution B, slowly add the thioacetyl amine aqueous solution 10ml that contains 0.1mol/L, add deionized water to 80ml, and stir, obtain the clear solution C.
E) will dry up with high pure nitrogen through pretreated substrate, put into the beaker that fills solution C, and substrate will be inverted be floated on the solution C surface.Beaker is positioned over reacting by heating 40min under the microwave exposure that power is 119W.Reaction has deposited thin film at substrate surface after finishing, and takes out substrate, dries up with the washed with de-ionized water film surface and under high pure nitrogen, obtains the CuS film.
Prepared as seen from Figure 1 cupric sulfide film is pure covellite structure, and crystallinity is fine.Fig. 2 has shown the microscopic appearance of this film: interlaced hexagon nanometer sheet vertical growth is in substrate surface, and its length of side is about 200～300nm, and thickness is about 20～40nm, and film is dense, grain density: 33.14/μ m
2
Claims (3)
1, a kind of method of depositing copper sulphide nano film rapidly in low temperature is characterized in that, may further comprise the steps:
A) pre-treatment of substrate: substrate after abundant the cleaning, is used deionized water rinsing again, and is immersed in the ethanol standby in ultrasonic cleaning machine with toluene, acetone, ethanol successively;
B) with Cu (Ac)
2Powder dissolution stirs in deionized water, adds and Cu (Ac)
2Deng the complexing agent EDTA-2Na of amount of substance, continue stirred solution, obtain the blue solution A of clear;
C) in solution A, add NaOH solution and HCl solution adjusting pH value to 6～10, obtain solution B;
D) in solution B, slowly add and Cu (Ac)
2Deng the thioacetamide of amount of substance, and stir, obtain the clear solution C;
E) will dry up with nitrogen through pretreated substrate, and put into solution C, and substrate will be inverted be floated on the solution C surface, microwave exposure 20min～40min obtains the CuS film.
2, the method for a kind of depositing copper sulphide nano film rapidly in low temperature according to claim 1 is characterized in that, described substrate is conductive substrates or semiconducter substrate.
3, the method for a kind of depositing copper sulphide nano film rapidly in low temperature according to claim 2 is characterized in that, described conductive substrates is transparent conducting glass (a FTO glass), and described semiconducter substrate is a silicon 100.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153288A (en) * | 2010-12-02 | 2011-08-17 | 山东建筑大学 | Method for preparing copper disulfide thin film with preferred orientation |
| CN102560674A (en) * | 2011-11-23 | 2012-07-11 | 陕西科技大学 | Preparation method of copper sulfide thin film with x-shaped-flaky crystal crossing structure |
| CN102560677A (en) * | 2011-12-19 | 2012-07-11 | 陕西科技大学 | Method for preparing self-assembling copper sulfide film with flake crystalline grains |
| CN106219997A (en) * | 2016-07-26 | 2016-12-14 | 北京航空航天大学 | A kind of technique preparing copper sulfide film on electro-conductive glass |
| CN106823469A (en) * | 2017-01-10 | 2017-06-13 | 华南理工大学 | Super-hydrophobic super-oleophylic copper mesh without low-surface energy substance modification and preparation method thereof |
| CN107365981A (en) * | 2017-08-11 | 2017-11-21 | 陕西科技大学 | A kind of Al doping CuS/ graphene complex films and preparation method thereof |
| CN108069393A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院上海硅酸盐研究所 | A kind of hydrogenation Copper thin film and preparation method thereof |
-
2009
- 2009-07-20 CN CN2009100888411A patent/CN101638777B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153288A (en) * | 2010-12-02 | 2011-08-17 | 山东建筑大学 | Method for preparing copper disulfide thin film with preferred orientation |
| CN102560674A (en) * | 2011-11-23 | 2012-07-11 | 陕西科技大学 | Preparation method of copper sulfide thin film with x-shaped-flaky crystal crossing structure |
| CN102560674B (en) * | 2011-11-23 | 2014-08-27 | 陕西科技大学 | Preparation method of copper sulfide thin film with x-shaped-flaky crystal crossing structure |
| CN102560677A (en) * | 2011-12-19 | 2012-07-11 | 陕西科技大学 | Method for preparing self-assembling copper sulfide film with flake crystalline grains |
| CN106219997A (en) * | 2016-07-26 | 2016-12-14 | 北京航空航天大学 | A kind of technique preparing copper sulfide film on electro-conductive glass |
| CN108069393A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院上海硅酸盐研究所 | A kind of hydrogenation Copper thin film and preparation method thereof |
| CN106823469A (en) * | 2017-01-10 | 2017-06-13 | 华南理工大学 | Super-hydrophobic super-oleophylic copper mesh without low-surface energy substance modification and preparation method thereof |
| CN107365981A (en) * | 2017-08-11 | 2017-11-21 | 陕西科技大学 | A kind of Al doping CuS/ graphene complex films and preparation method thereof |
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