CN103709821A - Copper-zinc-tin-sulfur/selenium ink and preparation method thereof - Google Patents
Copper-zinc-tin-sulfur/selenium ink and preparation method thereof Download PDFInfo
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- CN103709821A CN103709821A CN201310691608.9A CN201310691608A CN103709821A CN 103709821 A CN103709821 A CN 103709821A CN 201310691608 A CN201310691608 A CN 201310691608A CN 103709821 A CN103709821 A CN 103709821A
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Abstract
The invention discloses copper-zinc-tin-sulfur/selenium ink and a preparation method thereof. The ink is prepared from metal source liquor and non-metal source liquor, wherein the metal source liquor consists of copper source liquor, zinc source liquor and tin source liquor; the non-metal source liquor is composed of more than one of the sulfur source liquor and the selenium source liquor. The ink is prepared by virtue of the following steps: (1), respectively dissolving a copper source, a zinc source and a tin source into a solvent by taking monoethanolamine aqueous liquor as the solvent, mixing, and then carrying out thermal treatment so as to obtain the copper-zinc-tin source liquor; (2), dissolving a non-metal source into the solvent so as to obtain the non-metal source liquor by taking monoethanolamine or monoethanolamine aqueous liquor as the solvent; (3), mixing for reacting to obtain the copper-zinc-tin-sulfur/selenium ink. The method disclosed by the invention has the advantages that the metal sources do not contain chlorine ions or other acid radial impurity ions which are difficult to degrade and remove, and the solvent is gentle in characteristic, environment-friendly, single and easy to decompose, and the adverse effect of impurity ions on the performance of a battery film can be avoided.
Description
Technical field
The present invention relates to technical field of thin-film solar, be specifically related to a kind of ink for the preparation of copper-zinc-tin-sulfur/selenium absorbing layer of thin film solar cell and preparation method thereof.
Background technology
Copper-zinc-tin-sulfur/selenium has higher photoabsorption coefficient and suitable direct optical band gap, and enrich and environmental friendliness in its component source, is a kind of novel thin film solar battery obsorbing layer material that has potentiality, and its technology of preparing is also more and more concerned.Adopt the preparation of raw material of low cost, safety non-toxic or low toxicity to go out copper-zinc-tin-sulfur/selenium ink, then be the main trend of thin film solar cell technologies development from now in conjunction with the simple good copper-zinc-tin-sulfur/selenium film of technique big area processability.
It is raw material that the preparation of copper-zinc-tin-sulfur/selenium ink at present can adopt copper, zinc, tin, sulphur simple substance or respective metal sulfide and selenide, adds organic dispersing agent and fully after grinding, obtains copper-zinc-tin-sulfur/selenium slurry ink.This method is very simple and easy, but owing to being particle after grinding, particle size is larger, causes the element skewness in ink, and film easily forms other dephasign, is unfavorable for the raising of film performance.
The homogeneity distributing in order to improve element, need to adopt hydrazine to obtain the dispersed solution ink of molecular level level as dissolution with solvents metallic sulfide, but hydrazine belongs to inflammable and explosive highly toxic substance, to the big area of copper-zinc-tin-sulfur/selenium film, prepare safely and brought obstacle.In order to overcome this obstacle, various complicated organism are used as solvent to replace hydrazine, but due to the deliquescent restriction of source metal, current non-hydrazine solution legal system is limited to metal chloride or acetate mostly for the source metal of copper-zinc-tin-sulfur/selenium ink, the chlorion comprising in these source metal or acid group foreign ion are difficult for decomposing to be removed, and the residual raising that is unfavorable for film performance of foreign ion.The present invention is directed to now methodical deficiency, propose a kind of ink and compound method thereof for the preparation of copper-zinc-tin-sulfur/selenium absorbing layer of thin film solar cell.
Summary of the invention
The object of the present invention is to provide a kind of copper-zinc-tin-sulfur/selenium ink and preparation method thereof, ink of the present invention is prepared from by source metal solution and nonmetal source solution, wherein source metal solution is by copper source solution, zinc source solution and the three provenance solution compositions of tin source solution, more than one source solution compositions in sulphur source solution and selenium source solution of nonmetal source solution;
It is source metal that metal hydroxides or subcarbonate are take in the present invention, and monoethanolamine or the monoethanolamine aqueous solution are solvent, are equipped with suitable sulphur source or selenium source and prepare copper-zinc-tin-sulfur/selenium ink.
For realizing above object, the present invention by the following technical solutions:
(1) take the monoethanolamine aqueous solution that concentration is 7 ~ 10mol/L is solvent, respectively copper source, He Xi source, zinc source are dissolved in described solvent, obtain copper source solution, zinc source solution and tin source solution, after being mixed, copper source solution, zinc source solution and tin source solution heat-treats, obtain copper zinc-tin source solution, i.e. source metal solution; Described heat treated temperature is 100 ~ 150 ℃, and the time is 30 ~ 50 minutes;
(2) take the monoethanolamine aqueous solution that monoethanolamine or concentration is 7 ~ 10mol/L is solvent, and nonmetal source is dissolved in and in described solvent, obtains nonmetal source solution;
(3) source metal solution and nonmetal source solution are mixed and fully reacts and obtain copper-zinc-tin-sulfur/selenium ink.
In aforesaid method, the source metal in described ink is provided by metal hydroxides or subcarbonate, and described copper source is copper hydroxide or ventilation breather, and zinc source is zinc hydroxide or zinc subcarbonate, and Xi Yuan is stannic hydroxide, and wherein stannic hydroxide is also referred to as stannic acid.
In aforesaid method, in described ink, nonmetal source comprises more than one in sulphur source and selenium source, and described sulphur source comprises any one in sulphur simple substance, thiocarbamide, thioacetamide, ammonium sulfide, mercaptan or dimethyl sulfoxide (DMSO); Described selenium source is selenium simple substance or selenol.
In aforesaid method, when nonmetal source solution is sulphur source solution, sulphur source solution is dissolved in monoethanolamine and is obtained by sulphur source, for moisture sulphur source, need to heat-treat and boil off moisture sulphur source solution; When nonmetal source solution is selenium source solution, selenium source solution is dissolved in altogether in the monoethanolamine aqueous solution and after heat-treating and is obtained by selenium simple substance and Tetramethylammonium hydroxide, or is dissolved in monoethanolamine and after heat-treating and is obtained by selenol; When nonmetal source solution is sulphur selenium source solution, sulphur selenium source solution is directly dissolved in the solution of above-mentioned sulphur source and is obtained by selenium simple substance, or is dissolved in the solution of above-mentioned sulphur source and after heat-treating and is obtained by selenol; Described heat treated temperature is 90 ~ 100 ℃, and the time is 30 ~ 40 minutes.
In aforesaid method, in step (3), when copper zinc-tin source solution mixes with sulphur source solution and fully obtains copper-zinc-tin-sulfur ink after reaction, when copper zinc-tin source solution mixes with selenium source solution and fully obtains copper-zinc-tin-selenium ink after reaction, when copper zinc-tin source solution mixes with sulphur selenium source solution and fully obtains copper zinc tin sulfur selenium ink after reaction.
Compared with prior art, advantage of the present invention is:
(1) it is source metal that the ink of preparing has adopted metal hydroxides or subcarbonate.Different from the source metal such as metal chloride or acetate, the source metal that the present invention proposes does not decompose containing being difficult to chlorion and the acid group foreign ion of removing, and invented ink is more suitable in the preparation of copper-zinc-tin-sulfur/selenium film.
(2) it is solvent that the ink of preparing has adopted monoethanolamine or the monoethanolamine aqueous solution.Compare to the danger of the inflammable and explosive severe toxicity of hydrazine, monoethanolamine characteristic gentleness is safety low-poison, is conducive to the production in enormous quantities of ink.As the single solvent of ink, monoethanolamine and sulphur source, selenium source compatibility are good, and low temperature easily decomposes, and make invented ink have environmental protection outstanding advantages cheaply.
Accompanying drawing explanation
fig. 1 is the X ray diffracting spectrum of embodiment 1.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
Compound concentration is the monoethanolamine aqueous solution of 7.2mol/L.Get copper hydroxide, zinc hydroxide, stannic hydroxide and sulphur simple substance that mol ratio is 1.8:1.2:1:5, three kinds of source metal of described ratio are dissolved in respectively in the monoethanolamine aqueous solution, and obtaining source metal concentration is copper source solution, zinc source solution and the tin source solution of 0.3mol/L.It is 150 ℃ that three kinds of source metal solution are fully mixed to the trip temperature of going forward side by side, and the time is to obtain copper zinc-tin source solution after the thermal treatment of 30 minutes.Got sulphur simple substance is dissolved in and in monoethanolamine, obtains the sulphur source solution that concentration is 2mol/L.Copper zinc-tin source solution and sulphur source solution are mixed and fully reacts and obtain copper-zinc-tin-sulfur ink.
Adopt the mode of spin coating that prepared copper-zinc-tin-sulfur ink is directly spin-coated on clean slide glass, and annealing obtains copper-zinc-tin-sulfur film body under nitrogen protection, wherein annealing temperature is 420 ℃, and annealing time is 40 minutes.X-ray diffractogram (Fig. 1) shows that invented ink can be used for preparing single-phase copper-zinc-tin-sulfur.
Embodiment 2
Compound concentration is the monoethanolamine aqueous solution of 8.2mol/L.Get ventilation breather, zinc hydroxide, stannic hydroxide, selenium simple substance and Tetramethylammonium hydroxide that mol ratio is 0.9:1.2:1:4.5:8, three kinds of source metal are dissolved in respectively in the monoethanolamine aqueous solution, and obtaining source metal concentration is copper source solution, zinc source solution and the tin source solution of 0.35mol/L.It is 130 ℃ that three kinds of source metal solution are fully mixed to the trip temperature of going forward side by side, and the time is to obtain copper zinc-tin source solution after the thermal treatment of 40 minutes.Got selenium simple substance and Tetramethylammonium hydroxide are dissolved in the monoethanolamine aqueous solution altogether, obtain the mixing solutions that selenium concentration is 0.5mol/L, it is 90 ℃ that this mixing solutions is carried out to temperature, and the time is that the thermal treatment of 40 minutes obtains selenium source solution.Copper zinc-tin source solution and selenium source solution are mixed and fully reacts and obtain copper-zinc-tin-selenium ink.
Embodiment 3
Compound concentration is the monoethanolamine aqueous solution of 9.7mol/L.Get ventilation breather, zinc subcarbonate, stannic hydroxide, sulphur simple substance and selenium simple substance that mol ratio is 0.9:0.4:1:1.8:2.5, three kinds of source metal of described ratio are dissolved in respectively in the monoethanolamine aqueous solution, and obtaining source metal concentration is copper source solution, zinc source solution and the tin source solution of 0.3mol/L.It is 100 ℃ that three kinds of source metal solution are fully mixed to the trip temperature of going forward side by side, and the time is to obtain copper zinc-tin source solution after the thermal treatment of 50 minutes.Got sulphur simple substance is dissolved in and in monoethanolamine, obtains the sulphur source solution that concentration is 1mol/L.Got selenium simple substance is directly dissolved in to sulphur source solution and obtains sulphur selenium source solution.Copper zinc-tin source solution and sulphur selenium source solution are mixed and fully reacts and obtain copper zinc tin sulfur selenium ink.
The present invention proposes take metal hydroxides or subcarbonate is source metal, and monoethanolamine is that single solvent is prepared copper-zinc-tin-sulfur ink.Wherein metal hydroxides or subcarbonate not chloride ion-containing or other be difficult to the acid group foreign ion decomposing, can avoid the disadvantageous effect of foreign ion to battery thin film performance.Employing monoethanolamine is single solvent, and low temperature easily decomposes, and the carbon that can reduce in film is residual.Aspect sulphur source and selenium source selection, can select elemental sulfur, thiocarbamide, thioacetamide, ammonium sulfide, mercaptan or dimethyl sulfoxide (DMSO) is sulphur source, and selecting simple substance selenium or selenol is selenium source.The ink system of inventing forms simple, advantages of nontoxic raw materials or low toxicity, and element ratio is easy to control, and preparation flow is simple and easy, good with sulphur source, selenium source compatibility.The ink of inventing, except spin coating, is also applicable to the big area coating process such as blade coating, spraying, roller coat.
Claims (6)
1. the preparation method of copper-zinc-tin-sulfur/selenium ink, it is characterized in that, described ink is prepared from by source metal solution and nonmetal source solution, wherein source metal solution is by copper source solution, zinc source solution and the three provenance solution compositions of tin source solution, more than one source solution compositions in sulphur source solution and selenium source solution of nonmetal source solution; Described ink is prepared from by following steps:
(1) take the monoethanolamine aqueous solution that concentration is 7 ~ 10mol/L is solvent, respectively copper source, He Xi source, zinc source are dissolved in described solvent, obtain copper source solution, zinc source solution and tin source solution, after being mixed, copper source solution, zinc source solution and tin source solution heat-treats, obtain copper zinc-tin source solution, i.e. source metal solution; Described heat treated temperature is 100 ~ 150 ℃, and the time is 30 ~ 50 minutes;
(2) take the monoethanolamine aqueous solution that monoethanolamine or concentration is 7 ~ 10mol/L is solvent, and nonmetal source is dissolved in and in described solvent, obtains nonmetal source solution;
(3) source metal solution and nonmetal source solution are mixed and fully reacts and obtain copper-zinc-tin-sulfur/selenium ink.
2. a kind of copper-zinc-tin-sulfur/selenium ink claimed in claim 1 and preparation method thereof, it is characterized in that, source metal in described ink is provided by metal hydroxides or subcarbonate, described copper source is copper hydroxide or ventilation breather, zinc source is zinc hydroxide or zinc subcarbonate, Xi Yuan is stannic hydroxide, and wherein stannic hydroxide is also referred to as stannic acid.
3. a kind of copper-zinc-tin-sulfur/selenium ink according to claim 1 and preparation method thereof, it is characterized in that, in described ink, nonmetal source comprises more than one in sulphur source and selenium source, and described sulphur source comprises any one in sulphur simple substance, thiocarbamide, thioacetamide, ammonium sulfide, mercaptan or dimethyl sulfoxide (DMSO); Described selenium source is selenium simple substance or selenol.
4. according to a kind of copper-zinc-tin-sulfur/selenium ink described in claim 1 or 3 and preparation method thereof, it is characterized in that, when nonmetal source solution is sulphur source solution, sulphur source solution is dissolved in monoethanolamine and is obtained by sulphur source, for moisture sulphur source, need to heat-treat and boil off moisture sulphur source solution; When nonmetal source solution is selenium source solution, selenium source solution is dissolved in altogether in the monoethanolamine aqueous solution and after heat-treating and is obtained by selenium simple substance and Tetramethylammonium hydroxide, or is dissolved in monoethanolamine and after heat-treating and is obtained by selenol; When nonmetal source solution is sulphur selenium source solution, sulphur selenium source solution is directly dissolved in the solution of above-mentioned sulphur source and is obtained by selenium simple substance, or is dissolved in the solution of above-mentioned sulphur source and after heat-treating and is obtained by selenol; Described heat treated temperature is 90 ~ 100 ℃, and the time is 30 ~ 40 minutes.
5. a kind of copper-zinc-tin-sulfur/selenium ink according to claim 1 and preparation method thereof, it is characterized in that, in step (3), when copper zinc-tin source solution mixes with sulphur source solution and fully obtains copper-zinc-tin-sulfur ink after reaction, when copper zinc-tin source solution mixes with selenium source solution and fully obtains copper-zinc-tin-selenium ink after reaction, when copper zinc-tin source solution mixes with sulphur selenium source solution and fully obtains copper zinc tin sulfur selenium ink after reaction.
6. by the arbitrary described method of claim 1-5, prepare a kind of copper-zinc-tin-sulfur/selenium ink.
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| CN201310691608.9A CN103709821B (en) | 2013-12-17 | 2013-12-17 | A kind of Copper-zinc-tin-sulfinkselenium inkselenium and preparation method thereof |
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| US9997655B1 (en) | 2017-06-27 | 2018-06-12 | International Business Machines Corporation | Solution process for silver-containing chalcogenide layer deposition |
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| US10396221B2 (en) | 2017-06-27 | 2019-08-27 | International Business Machines Corporation | Solution process for silver-containing chalcogenide layer deposition |
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