CN-122028536-A - Preparation method of thiourea dioxide-nano selenium sol anion source precursor solution

CN122028536ACN 122028536 ACN122028536 ACN 122028536ACN-122028536-A

Abstract

The invention discloses a preparation method of a thiourea dioxide-nano selenium sol anion source precursor solution, which comprises the steps of adding inorganic salt of selenium and a dispersing agent into deionized water for complete dissolution to prepare a selenium salt solution, gradually adding a reducing solution into the selenium salt solution to prepare nano selenium sol, gradually adding the thiourea dioxide solution into the nano selenium sol, stirring to obtain a TD-Se mixed solution, adding the inorganic salt of indium and the inorganic salt of copper into deionized water for dissolution to prepare an indium copper salt solution, adding a complexing agent into deionized water for preparing a complexing solution, adding the indium copper salt solution into the complexing solution, mixing to obtain an indium copper complex solution, adding the indium copper complex solution into the TD-Se mixed solution, and stirring to obtain the precursor solution.

Inventors

ZHANG ZHI
HU NAIXIANG
JIANG XIN
YI ZICHUAN
YANG JIANJUN
GAO QINGGUO

Assignees

电子科技大学中山学院

Dates

Publication Date: 20260512
Application Date: 20260119

Claims (9)

1. A preparation method of thiourea dioxide-nano selenium sol anion source precursor solution is characterized by comprising the following preparation steps: step 1, weighing inorganic salt of selenium and a dispersing agent, placing the inorganic salt of selenium and the dispersing agent in a beaker, adding deionized water for complete dissolution to prepare a selenium salt solution for standby, adding a reducing agent into the deionized water for dissolution to prepare a reducing solution, and gradually adding the reducing solution into the selenium salt solution under an ultrasonic environment to prepare nano selenium sol; Step 2, thiourea dioxide powder is dissolved in deionized water, thiourea dioxide solution is prepared after complete dissolution, the thiourea dioxide solution is gradually added into nano selenium sol, and TD-Se mixed solution is obtained after stirring; Adding inorganic salt of indium and inorganic salt of copper into deionized water to dissolve to prepare indium copper salt solution, adding deionized water into complexing agent to prepare complexing solution, dropwise adding sodium hydroxide solution into the complexing solution to promote the complexing agent to dissolve, controlling the complexing solution to be alkaline, gradually adding the indium copper salt solution into the complexing solution, stirring while mixing, and completely and uniformly mixing to obtain indium copper complex solution; and step 4, gradually adding the indium-copper complex solution into the TD-Se mixed solution, and stirring to obtain a precursor solution.
2. The method for preparing thiourea dioxide-nano-selenium sol anion source precursor solution according to claim 1, wherein the inorganic salt of selenium is sodium selenite, the inorganic salt of indium is indium chloride tetrahydrate, and the inorganic salt of copper is copper chloride dihydrate.
3. The method for preparing thiourea dioxide-nano-selenium sol anion source precursor solution according to claim 2, wherein the concentration of the selenium salt solution is 0.1mol/L.
4. The method for preparing thiourea dioxide-nano selenium sol anion source precursor solution according to claim 1, wherein the dispersing agent is sodium dodecyl sulfate, and the reducing agent is ascorbic acid.
5. The method for preparing thiourea dioxide-nanoselenium sol anion source precursor solution according to claim 4, wherein the concentration of the reducing solution is 0.1mol/L.
6. The method for preparing thiourea dioxide-nano selenium sol anion source precursor solution according to claim 1, wherein the complexing agent is diethylenetriamine pentaacetic acid.
7. The method for preparing the thiourea dioxide-nano selenium sol anion source precursor solution according to claim 1, wherein the concentration of the thiourea dioxide solution is 0.1mol/L.
8. The method for preparing thiourea dioxide-nano selenium sol anion source precursor solution according to claim 1, wherein sodium hydroxide solution is added dropwise into the complexing solution, and the pH value of the complexing solution is adjusted to 10.
9. The method for preparing thiourea dioxide-nanoselenium sol anion source precursor solution according to claim 1, wherein the reaction temperature of the precursor solution is 55-70 ℃.

Description

Preparation method of thiourea dioxide-nano selenium sol anion source precursor solution Technical Field The invention relates to a copper indium selenium film, in particular to a preparation method of a precursor solution of the copper indium selenium film. Background Among various solar cells, the copper indium selenium thin film solar cell technology is regarded as an important development direction of the photovoltaic field, has higher application potential and commercial value, has the advantages of strong light absorption capacity, good weak light performance, adjustable optical band gap, stable performance and no light attenuation effect, and is regarded as a preparation method of the copper indium selenium thin film solar cell with wide commercial application prospect due to low cost, simple and convenient process and easy mass production when the copper indium selenium thin film solar cell is specifically produced. In the method, the preparation of the copper indium selenium film generally requires high-temperature selenizing treatment of the precursor film in a vacuum environment to realize the conversion from sulfide to selenide. However, the process is not only accompanied by release of highly toxic selenium vapor, difficult to treat and presents environmental and safety risks, but also easily causes volatilization and loss of indium element, affecting the stoichiometric ratio of the film and the final device performance. In order to avoid the problems caused by high-temperature selenization, researchers try to directly provide Se 2− ions in a solution by adopting various selenium sources so as to realize low-temperature liquid-phase synthesis. The currently commonly used selenium sources mainly comprise 1, 1-dimethyl-2-selenourea, H 2 Se gas, sodium selenosulfate and the like. The 1, 1-dimethyl-2-selenourea can decompose and release Se 2− under the heating condition, has the properties similar to thiourea, but is greatly limited in practical application due to high price, H 2 Se gas is introduced into water to prepare hydrogen selenate, and then a certain amount of Se 2− is generated by ionization, however, H 2 Se has extremely high toxicity and low yield of selenium ions in practical reaction, so that the method is gradually eliminated, na 2SeSO3 serving as an unstable compound only exists in an alkaline environment for a short time, and needs to be prepared before each deposition, thereby obviously increasing the complexity of the process and the operation difficulty. The preparation process of Na 2SeSO3 is to add selenium powder into sodium sulfite (Na 2SO3) solution and complete the process through long-time constant-temperature reflux reaction under the protection of nitrogen, and the method has long preparation period and extremely low reaction rate, so that the actual concentration of finally obtained Na 2SeSO3 is difficult to accurately measure, the proportion of each component cannot be accurately regulated when preparing a deposition solution, the stoichiometric ratio and the phase composition of a film are affected, and therefore, the preparation process needs to be improved aiming at the problems existing in the prior precursor solution preparation process. Disclosure of Invention Aiming at the problems, the invention provides a thiourea dioxide-nano selenium sol anion source precursor solution preparation method, which aims at realizing low-temperature, water-phase and environment-friendly synthesis of a copper indium selenium film. The technical scheme adopted for solving the technical problems is as follows: A preparation method of thiourea dioxide-nano selenium sol anion source precursor solution comprises the following preparation steps: step 1, weighing inorganic salt of selenium and a dispersing agent, placing the inorganic salt of selenium and the dispersing agent in a beaker, adding deionized water for complete dissolution to prepare a selenium salt solution for standby, adding a reducing agent into the deionized water for dissolution to prepare a reducing solution, and gradually adding the reducing solution into the selenium salt solution under an ultrasonic environment to prepare nano selenium sol; Step 2, thiourea dioxide powder is dissolved in deionized water, thiourea dioxide solution is prepared after complete dissolution, the thiourea dioxide solution is gradually added into nano selenium sol, and TD-Se mixed solution is obtained after stirring; Adding inorganic salt of indium and inorganic salt of copper into deionized water to dissolve to prepare indium copper salt solution, adding deionized water into complexing agent to prepare complexing solution, dropwise adding sodium hydroxide solution into the complexing solution to promote the complexing agent to dissolve, controlling the complexing solution to be alkaline, gradually adding the indium copper salt solution into the complexing solution, stirring while mixing, and completely and uniformly mixing to obtain indi