CN106219997A - A kind of technique preparing copper sulfide film on electro-conductive glass - Google Patents

A kind of technique preparing copper sulfide film on electro-conductive glass Download PDF

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Publication number
CN106219997A
CN106219997A CN201610594502.0A CN201610594502A CN106219997A CN 106219997 A CN106219997 A CN 106219997A CN 201610594502 A CN201610594502 A CN 201610594502A CN 106219997 A CN106219997 A CN 106219997A
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solution
copper sulfide
deionized water
electro
conductive glass
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CN201610594502.0A
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Chinese (zh)
Inventor
于美
孟燕兵
刘建华
章锦丹
李松梅
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Beihang University
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Beihang University
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3464—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide
    • C03C17/347—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide comprising a sulfide or oxysulfide
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/114—Deposition methods from solutions or suspensions by brushing, pouring or doctorblading
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment

Abstract

The invention discloses a kind of method preparing copper sulfide film on electro-conductive glass, first analytically pure soluble copper salt is joined in deionized water, be subsequently added a certain amount of triethanolamine and obtain solution A；In solution A, add ammonia and sodium hydroxide obtains solution B；Continue in solution B add thiourea and at a certain temperature react a period of time obtain copper sulfide；It is prepared as slurry to be coated on electro-conductive glass and obtain uniform thin film.It is characteristic of the invention that preparation technology is simple, preparation condition is gentle, and environmental friendliness, with low cost, the film layer prepared is homogeneous, fine and close.

Description

A kind of technique preparing copper sulfide film on electro-conductive glass
Technical field
The invention belongs to technical field of inorganic nanometer material, be specifically related to the preparation of a kind of loose porous copper sulfide film Method.
Background technology
Copper sulfide is a kind of inorganic material with good electric conductivity, chemosensitivity and photoelectric properties.There is nanometer The copper sulfide of structure is especially because having special character, so being widely used at numerous areas.
The preparation of copper sulfide has a diversified method, solvent thermal reaction [Gorai S., Ganguli D., Chaudhuri S.Morphological control in solvothermal synthesis of copper sulphides on copper foil[J].Materials Research Bulletin,2007,42(2):345-353； Shamraiz U.,Hussain R.A.,Badshah A.Fabrication and applications of copper sulfide(CuS)nanostructures[J].Journal of Solid State Chemistry,2016,238,25- 40], continuous particle layer absorption with reaction method [Ali Yildirim M.,A.,Astam A.Annealing and light effect on structural,optical and electrical properties of CuS,CuZnS and ZnS thin films grown by the SILAR method[J].Physica E:Low-dimensional Systems and Nanostructures, 2009,41 (8): 1365-1372] and chemical bath deposition [Nien Y.-T., Chen I.-G.Rapid thermal annealing of chemical bath-deposited CuxS films and their Characterization [J] .Journal of Alloys and Compounds, 2009,471 (1-2): 553-556] Method.But these methods typically require special condition and control with strict experimentation, and preparation cost is high, is not suitable for big The production of amount.Therefore, a kind of simple preparation method practical again is current desired.
Summary of the invention
The invention provides the preparation method of the copper sulfide film of a kind of even porous, preparation technology is simple, preparation condition Gentleness, environmental friendliness, with low cost, the even film layer prepared is loose porous.
For obtaining above-mentioned thin film, the technical solution used in the present invention is:
1) analytically pure soluble copper salt is added in 100ml deionized water, be prepared as Cu2+Concentration is 0.05-0.1mol/ The clear solution of L, adds the triethanolamine solution of 3-5ml in solution so that solution becomes suspension, and gained solution is designated as molten Liquid A；
2) add in solution A 5-15ml 25% ammonia, strong stirring 10min, obtain limpid bright blueness Solution, with adding NaOH in this mixed solution backward so that its concentration is 00.1-0.2mol/l, obtains solution B；
3) using thiourea as sulfur source, in solution B, a certain amount of thiourea is added so that its concentration is 0.05-0.1mol/ L, and at 30-40 DEG C, react 3-5h；
4) copper sulfide deionized water obtained above is washed, and be dried with freezer dryer；
5) by conducting glass substrate difference ultrasonic vibration 10-30min in acetone, ethanol, deionized water, then moisten with ethanol Wash, and dry up, place standby；
6) take a certain amount of ethylene glycol and above-mentioned copper sulfide powder is prepared as slurry, and scratch on FTO electro-conductive glass, warp 150-180 DEG C of sintering 30-60min, prepares fine and close homogeneous copper sulfide film.
Above-mentioned soluble copper salt refers to copper chloride and Schweinfurt green.
The copper sulfide film that the method is prepared uniformly loosens, porous, and preparation technology is simple, and preparation condition is gentle, environment Close friend, with low cost.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the copper sulfide film prepared by present example 1；
Fig. 2 is the SEM image of the copper sulfide film prepared by present example 1.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1
Employing dosage ratio is
1) analytically pure copper chloride is added in 100ml deionized water, be prepared as Cu2+Concentration is the transparent of 0.05mol/L Solution, adds the triethanolamine solution of 4ml in solution so that solution becomes suspension, and gained solution is designated as solution A；
2) add in solution A 10ml 25% ammonia, strong stirring 10min, obtain limpid bright blueness molten Liquid, with adding NaOH in this mixed solution backward so that its concentration is 0.1mol/l, obtains solution B；
3) using thiourea as sulfur source, in solution B, a certain amount of thiourea is added so that its concentration is 0.05mol/l, and 4h is reacted at 35 DEG C；
4) copper sulfide deionized water obtained above is washed, and be dried with freezer dryer；
5) by conducting glass substrate difference ultrasonic vibration 15min in acetone, ethanol, deionized water, then ethanol rinse is used, And dry up, place standby；
6) take a certain amount of ethylene glycol and above-mentioned copper sulfide powder is prepared as slurry, and scratch on FTO electro-conductive glass, warp 180 DEG C of sintering 30min, prepare fine and close homogeneous copper sulfide film.
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of prepared copper sulfide film, it can be seen that use the method The composition of the thin film prepared is really for copper sulfide, the diffraction maximum at its 27.7,29.3,31.8,47.9,52.7, and 59.3 ° Corresponding with (101) of covellite CuS, (102), (103), (110), (108), and (116) crystal face, and three big main peak intensity are relatively Height, therefore its structure is the copper sulfide of covellite.
Fig. 2 is the SEM image of copper sulfide film, characterizes its surface optical pattern, it can be seen that can from figure To find out, this film surface is uniform, for loose porous structure.
Embodiment 2
1) analytically pure copper chloride is added in 100ml deionized water, be prepared as Cu2+Concentration is the transparent molten of 0.1mol/L Liquid, adds the triethanolamine solution of 3ml in solution so that solution becomes suspension, and gained solution is designated as solution A；
2) add in solution A 10ml 25% ammonia, strong stirring 10min, obtain limpid bright blueness molten Liquid, with adding NaOH in this mixed solution backward so that its concentration is 0.1mol/l, obtains solution B；
3) using thiourea as sulfur source, in solution B, a certain amount of thiourea is added so that its concentration is 0.05mol/l, and 5h is reacted at 35 DEG C；
4) copper sulfide deionized water obtained above is washed, and be dried with freezer dryer；
5) by conducting glass substrate difference ultrasonic vibration 10min in acetone, ethanol, deionized water, then ethanol rinse is used, And dry up, place standby；
6) take a certain amount of ethylene glycol and above-mentioned copper sulfide powder is prepared as slurry, and scratch on FTO electro-conductive glass, warp 180 DEG C of sintering 30min, prepare fine and close homogeneous copper sulfide film.
Its degree of crystallinity of thin film using the method to prepare does not has the height in example one, and some of which peak is at XRD figure picture In do not show, and its pattern is not as fine and close homogeneous in example 1, mostly is loose aperture above.
Embodiment 3
1) analytically pure Schweinfurt green is added in 100ml deionized water, be prepared as Cu2+Concentration is the transparent of 0.05mol/L Solution, adds the triethanolamine solution of 4ml in solution so that solution becomes suspension, and gained solution is designated as solution A；
2) add in solution A 15ml 25% ammonia, strong stirring 10min, obtain limpid bright blueness molten Liquid, with adding NaOH in this mixed solution backward so that its concentration is 0.1mol/l, obtains solution B；
3) using thiourea as sulfur source, in solution B, a certain amount of thiourea is added so that its concentration is 0.1mol/l, and 5h is reacted at 40 DEG C；
4) copper sulfide deionized water obtained above is washed, and be dried with freezer dryer；
5) by conducting glass substrate difference ultrasonic vibration 15min in acetone, ethanol, deionized water, then ethanol rinse is used, And dry up, place standby；
6) take a certain amount of ethylene glycol and above-mentioned copper sulfide powder is prepared as slurry, and scratch on FTO electro-conductive glass, warp 180 DEG C of sintering 60min, prepare fine and close homogeneous copper sulfide film.
Embodiment 4
1) analytically pure Schweinfurt green is added in 100ml deionized water, be prepared as Cu2+Concentration is the transparent molten of 0.1mol/L Liquid, adds the triethanolamine solution of 3ml in solution so that solution becomes suspension, and gained solution is designated as solution A；
2) add in solution A 5ml 25% ammonia, strong stirring 10min, obtain limpid bright blueness molten Liquid, with adding NaOH in this mixed solution backward so that its concentration is 0.2mol/l, obtains solution B；
3) using thiourea as sulfur source, in solution B, a certain amount of thiourea is added so that its concentration is 0.05mol/l, and 4h is reacted at 30 DEG C；
4) copper sulfide deionized water obtained above is washed, and be dried with freezer dryer；
5) by conducting glass substrate difference ultrasonic vibration 15min in acetone, ethanol, deionized water, then ethanol rinse is used, And dry up, place standby；
6) take a certain amount of ethylene glycol and above-mentioned copper sulfide powder is prepared as slurry, and scratch on FTO electro-conductive glass, warp 150 DEG C of sintering 60min, prepare fine and close homogeneous copper sulfide film.

Claims (2)

1. the preparation method of the copper sulfide film of uniform compact on an electro-conductive glass, it is characterised in that:
1) analytically pure soluble copper salt is added in 100ml deionized water, be prepared as Cu2+Concentration is 0.05-0.1mol/L's Clear solution, adds the triethanolamine solution of 3-5ml in solution so that solution becomes suspension, and gained solution is designated as solution A；
2) add in solution A 5-15ml 25% ammonia, strong stirring 10min, obtain limpid bright blue solution, With this mixed solution backward adds NaOH so that its concentration is 00.1-0.2mol/l, obtains solution B；
3) using thiourea as sulfur source, in solution B, a certain amount of thiourea is added so that its concentration is 0.05-0.1mol/l, and 3-5h is reacted at 30-40 DEG C；
4) copper sulfide deionized water obtained above is washed, and be dried with freezer dryer；
5) by conducting glass substrate difference ultrasonic vibration 10-30min in acetone, ethanol, deionized water, then ethanol rinse is used, And dry up, place standby；
6) take a certain amount of ethylene glycol and above-mentioned copper sulfide powder is prepared as slurry, and scratch on FTO electro-conductive glass, through 150- 180 DEG C of sintering 30-60min, prepare fine and close homogeneous copper sulfide film.
The preparation method of the copper sulfide film of uniform compact the most according to claim 1, it is characterised in that described is solvable My copper chloride or Schweinfurt green of property mantoquita.
CN201610594502.0A 2016-07-26 2016-07-26 A kind of technique preparing copper sulfide film on electro-conductive glass Pending CN106219997A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111524712A (en) * 2020-04-13 2020-08-11 昆明理工大学 Preparation method of three-dimensional porous structure dye-sensitized solar cell counter electrode
CN113499483A (en) * 2021-06-28 2021-10-15 福州大学 Nano copper sulfide coating modified memory alloy esophageal stent and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1949546A (en) * 2006-11-10 2007-04-18 中国科学院上海硅酸盐研究所 Method for preparing p type copper sulfide transparent conducting film
CN101638777A (en) * 2009-07-20 2010-02-03 北京工业大学 Method for depositing copper sulphide nano film rapidly in low temperature
CN104332315A (en) * 2014-10-29 2015-02-04 北京科技大学 Preparation method of porous nanocrystalline Cu2S counter electrode of quantum-dot-sensitized solar cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1949546A (en) * 2006-11-10 2007-04-18 中国科学院上海硅酸盐研究所 Method for preparing p type copper sulfide transparent conducting film
CN101638777A (en) * 2009-07-20 2010-02-03 北京工业大学 Method for depositing copper sulphide nano film rapidly in low temperature
CN104332315A (en) * 2014-10-29 2015-02-04 北京科技大学 Preparation method of porous nanocrystalline Cu2S counter electrode of quantum-dot-sensitized solar cell

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111524712A (en) * 2020-04-13 2020-08-11 昆明理工大学 Preparation method of three-dimensional porous structure dye-sensitized solar cell counter electrode
CN111524712B (en) * 2020-04-13 2022-07-05 昆明理工大学 Preparation method of three-dimensional porous structure dye-sensitized solar cell counter electrode
CN113499483A (en) * 2021-06-28 2021-10-15 福州大学 Nano copper sulfide coating modified memory alloy esophageal stent and preparation method thereof
CN113499483B (en) * 2021-06-28 2022-05-24 福州大学 Nano copper sulfide coating modified memory alloy esophageal stent and preparation method thereof

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