TWI386364B - Preparation of copper indium gallium - selenium nanoparticles - Google Patents

Description

Method for preparing copper indium gallium selenide nano particle

The invention relates to a method for preparing copper indium gallium selenide nanoparticles, in particular to a wet bead milling method using zirconium beads.

Nanoparticles generally refer to small particles of less than 100 nm, with special physicochemical properties different from those of general-sized materials, such as special optical properties, thermal properties, magnetic properties, and mechanical properties.

When gold is subdivided into a size smaller than the wavelength of the light wave, it loses its original rich luster and is black, thus exhibiting special optical properties. For example, the original silver-white platinum will turn into black platinum black at the nanometer size, and the original gold-colored metal chrome will turn black chrome black at the nanometer size. In fact, all metals appear black in the nanoparticle state, and the smaller the size, the darker the color. Therefore, the nanoparticle has a lower reflectance and a higher absorbance.

Under the global awareness of energy-saving and carbon-reducing green energy, copper-indium-gallium-selenide thin-film solar cells have no shortage of raw materials due to excessive dependence on silicon wafers, and there is no need for photosensitive sensitized solar cells. The high cost material problem of dyes, in addition, the photoelectric conversion efficiency of copper indium gallium selenide solar cells can reach 20~30%, and the photoelectric conversion rate of soft plastic substrates has reached 14%, so it is a solar energy with considerable development potential. battery.

The copper indium gallium selenide solar cell generally comprises an absorption layer as a P-type layer and a zinc sulfide layer as an n-type layer, wherein the absorption layer is a copper indium gallium diselenide layer, and the light absorption efficiency of the absorption layer directly affects the copper indium gallium selenide layer. Photoelectric conversion efficiency of solar cells.

In recent years, many methods for fabricating copper indium gallium selenide nanoparticles have been proposed for the production of high absorbance absorption layers, including physical preparation methods and chemical preparation methods, wherein physical preparation methods include gas phase condensation method and mechanical ball milling method. , physical pulverization method, thermal decomposition method, supercritical fluid method, and chemical preparation methods include chemical vapor deposition, sol-gel method, micro-emulsion method, polymer grafting method, chemical precipitation method, hydrothermal synthesis method, arc Plasma method, sonochemical method. The mechanical ball milling method has great development potential because of its excellent economic benefits, especially the wet ball milling method, which uses liquid as a medium between the grinding ball and the material to be ground to improve the grinding efficiency.

The disadvantage of the conventional technology is that the wet ball milling method is a high-energy, high-precision nano-grinding device, which is limited by the initial particle size and the characteristics of individual abrasives, and cannot precisely control the particles of the copper indium gallium selenide particles at one time. The size and uniformity of the diameter will also consume more energy. Therefore, there is a need for a multi-stage grinding process in which individual materials are individually ground to produce individual abrasives of a particular size, and the physical properties and surface conditions of the individual abrasives are maintained, and the individual individual abrasives are then held. Mixing and homogenization are carried out, and then the size of the grinding balls is gradually reduced by two-stage grinding to reduce the particle size of the copper indium gallium selenide nanoparticles to a desired range to solve the disadvantages of the above conventional techniques.

The main object of the present invention is to provide a method for preparing copper indium gallium selenide nanoparticles, mainly by wet sanding, including individual grinding treatment, mixed homogenization treatment, primary grinding treatment and advanced grinding treatment, wherein individual grinding treatments will Individual particles or compound particles containing copper, indium, gallium, and/or selenium are ground into individual abrasives of 500 to 600 nanometers, mixed and homogenized to mix all individual abrasives into a mixed homogenate, and the primary grinding process grinds the mixed homogenate A primary abrasive of 100 to 200 nm, advanced grinding treatment to grind the primary abrasive to an advanced abrasive of 50 nm or less, as a copper indium gallium selenide for the formation of an absorption layer of a copper indium gallium selenide solar cell Rice granules.

The embodiments of the present invention will be described in more detail below with reference to the drawings and the <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt;

The method for producing copper indium gallium selenide nanoparticles of the present invention mainly utilizes a wet milling method to form copper indium gallium selenide nanoparticles. Referring to the first figure, a flow chart of a method for producing copper indium gallium selenide particles of the present invention. As shown in the first figure, the method for producing copper indium gallium selenide particles of the present invention is started in step S10, and in step S10, an individual grinding process is performed, using a first grinding medium and a first grinding solvent, respectively. Grinding a plurality of objects to be ground for a period of 4 to 6 hours to form a plurality of individual abrasives, wherein the first grinding medium may be a zirconium bead, as a grinding ball, especially a zirconium bead having a diameter of 1.0 to 2.0 mm The sphere, the first grinding solvent may be at least one of water, alcohols, esters, and ketones, and the object to be polished includes individual particles or compounds containing copper, indium, gallium or/and selenium, such as copper selenide, Indium selenide or gallium selenide. The first grinding medium, the first grinding solvent, and the object to be ground are disposed in the grinder, the first grinding medium having a capacity of 50 to 95%, and the individual grinding materials having a capacity of 5 to 80%.

The driving device of the grinder, generally in a rotating manner, drives the first grinding medium to collide, rotate or move relatively, and generates high energy density collision force, friction force and shear force, thereby interposing between the first grinding medium and The object to be ground of the first grinding solvent is ground into smaller particles having a particle size of 500 to 600 nanometers (nm).

Next, proceeding to step S20, a mixing and homogenization process is performed. The mixed homogenization treatment uses a homogenizer and a mixed homogeneous solvent containing a binder and an interfacing agent, and mixes and homogenizes all of the above individual abrasives, and mixes the homogenization time for 1 to 4 hours to form a mixed homogenate. The homogenizer may be a three-dimensional mixer, and the mixed homogeneous solvent may be at least one of water, alcohols, esters and ketones.

Next, the process proceeds to step S30, where the primary grinding process is performed. The primary grinding treatment utilizes the above-described grinding machine, and the mixed homogeneous substance is ground using a second grinding medium, a second grinding solvent plus a dispersing agent, and the grinding time is 1 to 12 hours to form a primary particle having a particle size of 100 to 200 nm. Abrasive. The second grinding medium may be zirconium beads having a diameter of 0.4 to 1.0 mm, and the second grinding solvent may be at least one of water, alcohols, esters and ketones, and the dispersing agent is divided into a polymer dispersing agent and a nonionic dispersion. The agent may be an alkylbenzenesulfonate, a sulfate, a sulfonated glycerophosphate, an amino acid salt, a phosphorus lipid, a taurate, a phosphate, an alkyl sulfate, a fatty acid, a polyethylene oxide (PEO) At least one of a mercaptan, a sorbic acid oil, and a quaternary ammonium. The second grinding medium has a capacity of 50 to 95% and the mixed homogeneous material has a capacity of 5 to 80%.

Next, the process proceeds to step S40, where the advanced grinding process is performed. The advanced polishing treatment uses the above-mentioned grinder to further grind the primary abrasive using a third polishing medium, a third polishing solvent, and the above dispersing agent, and the polishing time is 1 to 12 hours to form a particle size of 50 nm or less. The advanced abrasive, the advanced abrasive is the copper indium gallium selenide particles.

The third grinding medium may be zirconium beads having a diameter of 0.05 to 0.4 mm, and the third grinding solvent may be at least one of water, alcohols, esters, and ketones. The third grinding media has a capacity of 50 to 95% and the primary abrasive has a capacity of 5 to 80%.

The water in the above grinding solvent may be pure water, deionized water or a mixture thereof, and the alcohol may be methanol, ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol, butanol or a mixture thereof, and the ester may be Ethyl ester, vinyl acetate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl dichloroacetate, methyl crotonate or a mixture thereof, the ketone may be acetone, methyl ethyl ketone or cyclohexanone , 2-pentanone, 3-pentanone or a mixture thereof.

The copper indium gallium selenide nanoparticle produced by the method for preparing the copper indium gallium selenide nanoparticle of the invention can be used for fabricating the absorption layer of the copper indium gallium selenide solar cell to improve the photoelectric conversion efficiency of the copper indium gallium selenide solar cell and reduce production cost.

The above is only a preferred embodiment for explaining the present invention, and is not intended to limit the present invention in any way, and any modifications or alterations to the present invention made in the spirit of the same invention. All should still be included in the scope of the intention of the present invention.

S10. . . Individual grinding

S20. . . Hybrid homogenization

S30. . . Primary grinding

S40. . . Advanced grinding

The first figure is a flow chart of a method for preparing copper indium gallium selenide particles according to the present invention.

S10. . . Individual grinding

S20. . . Hybrid homogenization

S30. . . Primary grinding

S40. . . Advanced grinding

Claims (12)

A method for preparing copper indium gallium selenide nanoparticles for forming copper indium gallium selenide nanoparticles, the method comprising: a grinding treatment, using a grinder, using a first grinding medium and a first grinding solvent, Separating a plurality of objects to be polished to form a plurality of individual abrasives, including individual particles or compounds of copper, indium, gallium or/and selenium, the compounds including copper selenide, indium selenide, and selenization Gallium, and the individual abrasives have a particle size of 500 to 600 nanometers (nm); a homogenizing treatment, using a homogenizer, using a mixed homogeneous solvent comprising a binder and an interfacing agent, the individual abrasives Mixing and homogenizing to form a mixed homogenate; a primary grinding treatment, using the grinder, and using a second grinding medium, a second grinding solvent, and a dispersing agent, grinding the mixed homogeneous material to form a a primary abrasive having a particle size of 100 to 200 nm; and an advanced grinding process using the same, and using a third polishing medium, a third polishing The solvent and the dispersing agent are ground to form an advanced abrasive having a particle size of 50 nm or less, and the advanced abrasive is the copper indium gallium selenide particles. The method of claim 1, wherein the first grinding medium is a zirconium bead having a diameter of 1.0 to 2.0 mm and has a capacity of 50 to 95%, and the grinding time of the individual grinding treatment is 4 Up to 6 hours. The method of claim 1, wherein the individual grinding treatment of the first grinding solvent comprises at least one of water, alcohols, esters, and ketones. The method of claim 1, wherein the individual milled individual abrasives have a capacity of from 5 to 80%. According to the method of claim 1, wherein the mixed homogeneous treatment of the mixed homogeneous solvent comprises at least one of water, alcohols, esters and ketones, and the mixing homogenization treatment has a homogenization time of 1 to 4 hours. . The method according to claim 1, wherein the second grinding medium of the primary grinding treatment is zirconium beads having a diameter of 0.4 to 1.0 mm and having a capacity of 50 to 95%, and the grinding time of the individual grinding treatment is 1 Up to 12 hours. The method of claim 1, wherein the primary ground treated mixed homogeneous material has a capacity of from 5 to 80%. The method of claim 1, wherein the primary grinding solvent comprises at least one of water, alcohols, esters, and ketones. The method of claim 1, wherein the third grinding medium of the advanced grinding treatment is zirconium beads having a diameter of 0.1 to 0.4 mm and having a capacity of 50 to 95%, and the grinding time of the individual grinding treatment is 1 to 12 hours. The method of claim 1, wherein the third grinding solvent of the advanced grinding treatment comprises at least one of water, alcohols, esters, and ketones. The method of claim 1, wherein the advanced ground treatment primary abrasive has a capacity of 5 to 80%. According to the method of claim 1, wherein the dispersing agent is classified into a polymer dispersing agent and a nonionic dispersing agent, and is an alkylbenzenesulfonate, a sulfate, a sulfonated glycerophosphate, an amino acid salt, At least one of a phosphorus lipid, a taurinate, a phosphate, an alkyl sulfate, a fatty acid, a polyethylene oxide (PEO) thiol, a sorbic acid oil, and a quaternary ammonium.