TWI644865B - Method for preparing cuinx2 compound nano-particles using polyol - Google Patents

Abstract

A method for synthesizing copper indium nitride nanoparticles by using a polyol, comprising: separately preparing a polyol solution of a copper (Cu) element compound, a polyol solution of an indium (In) element compound, and an alcohol solution of an X element compound, wherein The X element is selected from the group consisting of sulfur (S), selenium (Se) or cerium (Te); a polyol solution of a mixed copper element compound, a polyol solution of an indium element compound, and an alcohol solution of an X element compound to form a polyol mixture Heating a polyol mixture containing a copper element, an indium element, and an X element to a temperature higher than a crystallization temperature to obtain a copper indium compound (CuInX ₂ ) nanoparticle; and filtering to obtain a copper indium halide nanoparticle.

Description

Method for synthesizing copper indium nitride nanoparticles by using polyol

The present invention relates to a method for synthesizing copper indium nitride nanoparticles by using a polyol, and more particularly to a liquid using a polyol having a high solubility for an elemental raw material and a boiling point of a polyol higher than a crystallization temperature of a copper indium compound. A method of synthesizing a nanoparticle of copper indium (CuInX ₂ ) or copper indium gallium selenide (CuIn _1-y Ga _y Se ₂ ) by a phase synthesis reaction.

Thin film solar cells have long been recognized as the most popular technology to replace twin solar cells. Because thin film solar cells do not require the use of germanium wafers, they can reduce raw material costs and avoid shortage of raw materials. However, the power generation efficiency of thin film solar cells is not as high as that of single crystal germanium solar cells, but its development potential has been attracting attention. Among them, thin film solar cells use chalcopyrite type semiconductor Cu-III- Composite material of VI ₂ (III = aluminum Al, gallium Ga, indium In; VI = sulfur S, selenium Se, 碲Te), for example, using copper indium sulfide CIS (Cu-In-S), copper indium selenide CISe (Cu- In-Se) or copper indium gallium selenide CIGS (Cu-In-Ga-Se) is used as an absorption layer of a thin film solar cell. Such composite materials are widely used in the semiconductor industry and the solar energy industry, in which copper indium gallium selenide CIGS (Cu-In-Ga-Se) nanoparticles can replace indium (In) elements by gallium (Ga) elements. The power generation efficiency of the copper indium gallium selenide CIGS thin film solar cell can be more than 19% by controlling the change of the band gap at the nanometer scale. Therefore, if a low-cost, high-efficiency copper indium gallium selenide CIGS thin film solar cell can be successfully fabricated on a glass substrate, the estimated price is 6.5 US dollars per square foot. If calculated at 10% efficiency, it can generate 10W of electricity per square foot, and its cost per watt of electricity is 0.65 US dollars. This power generation cost is far cheaper than any type of solar cell in the world.

Because of the potential application value of the chalcopyrite-type semiconductor Cu-III-VI ₂ in photovoltaic systems, the method of synthesizing chalcopyrite composites is extremely important. There are several ways to make such a composite material as an absorbing layer of a thin film solar cell. For example, a material such as copper indium sulphur CIS is generally used as a target in a vacuum environment, and is directly formed on a substrate by evaporation or sputtering. . This vacuum plating method is advantageous for completing a high-efficiency absorption layer. However, it is relatively expensive compared to the required process equipment, and it is necessary to use selenization reaction using a corrosion-toxic hydrogen selenide (H ₂ Se) gas; A precursor of a material such as copper indium sulfide CIS may be applied to the substrate in a vacuum-free environment, and then the precursor may be reduced to a material such as copper indium sulfide CIS by a high temperature heat treatment. This high-temperature heat treatment reduces the cost by reducing the copper indium sulfide CIS, but only a low-efficiency uniform absorption layer having a large particle diameter can be obtained.

Therefore, it is necessary to provide a new method for synthesizing copper indium nitride nanoparticles to solve the problems of the prior art in order to achieve both manufacturing cost and power generation efficiency.

The main object of the present invention is to provide a method for synthesizing copper indium nitride nanoparticles by using a polyol, which dissolves various elemental raw materials by using a polyol under normal pressure, and is heated in a liquid phase environment provided by a polyol to Appropriate crystallization temperature to synthesize the elemental material and crystallize it into copper indium (CuInX ₂ ) or copper indium gallium selenide (CuIn _1-y Ga _y Se ₂ ) nanoparticle, without using expensive process equipment during synthesis Or toxic hydrogen selenide gas, which in turn helps to reduce manufacturing costs and improve process safety.

A secondary object of the present invention is to provide a method for synthesizing copper indium nitride nanoparticles by using a polyol, which is capable of synthesizing a nanometer-sized particle by appropriately controlling parameters such as heating temperature and time of a liquid phase environment of a polyol. Copper indium or copper indium gallium selenide nanoparticle, and using screen printing with rapid thermal annealing or baking to form a copper indium or copper indium gallium selenide absorption layer on the substrate, thereby reducing the material Particle size and improved power generation efficiency.

In order to achieve the above object, the present invention provides a method for synthesizing copper indium nitride nanoparticles by using a polyol, comprising: separately preparing a polyol solution of a copper (Cu) element compound, a polyol solution of an indium (In) element compound, and An alcohol solution of a X element compound, wherein the X element is selected from the group consisting of sulfur (S), selenium (Se) or cerium (Te); a polyol solution of a mixed copper element compound, a polyol solution of an indium element compound, and an alcohol of an X element compound The solution is a polyol mixture; heating the polyol mixture containing copper, indium and X to a temperature higher than a crystallization temperature to obtain copper indium (CuInX ₂ ) nanoparticles; and filtering Nanoparticles of copper indium.

In an embodiment of the invention, the polyol in the polyol solution of the copper element compound is selected from the group consisting of diethylene glycol, triethylene glycol or tetraethylene glycol; or is selected from ethylene glycol or polyethylene glycol.

In an embodiment of the invention, the polyol in the polyol solution of the indium element compound is selected from the group consisting of diethylene glycol, triethylene glycol or tetraethylene glycol; or is selected from ethylene glycol or polyethylene glycol.

In an embodiment of the invention, the alcohol in the alcohol solution of the X element compound is selected from the group consisting of a polyol or a unit alcohol.

In an embodiment of the invention, the polyol is selected from the group consisting of diethylene glycol, triethylene glycol or tetraethylene glycol; or is selected from ethylene glycol or polyethylene glycol. The unit alcohol is selected from the group consisting of ethanol, propanol or butanol.

In an embodiment of the present invention, when the alcohol in the alcohol solution of the X element compound is selected from the group of alcohols, after mixing the polyol mixture, the unit alcohol in the polyol mixture is heated and removed. The temperature of the polyol mixture is then increased to the crystallization temperature.

In an embodiment of the invention, the boiling point of the polyol is higher than the crystallization temperature of the copper indium compound.

In an embodiment of the invention, the copper indium halide nanoparticles have a particle size between 20 and 50 nanometers (nm).

In an embodiment of the present invention, the method further comprises: when formulating the solution, additionally formulating a polyol solution of the gallium element compound; when mixing the solution, adding a polyol solution of the gallium element compound to jointly mix into the polyol mixture. Liquid; when heating the polyol mixture to a temperature higher than a crystallization temperature, obtaining copper indium gallium (CuIn _1-y Ga _y X ₂ ) nanoparticles, wherein y is between 0.3 and 0.6; A copper indium gallium halide nanoparticle is obtained.

In an embodiment of the invention, the X element of the copper indium gallium compound is selected from the group consisting of selenium (Se).

In an embodiment of the present invention, after filtering, the copper indium (or copper indium gallium) nanoparticle is mixed with the organic printing ink filler to form a printing ink; and the printing ink is screen printed to a printing ink. On the surface of the substrate; the organic printing ink filler in the printing ink is removed at a high temperature, leaving only an absorbing layer formed of copper indium (or copper indium gallium) on the substrate.

In an embodiment of the invention, the organic printing ink filler is removed at a high temperature by rapid thermal annealing (RTA) or baking.

In an embodiment of the invention, the substrate is a transparent hard substrate or a transparent flexible flexible substrate.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

Referring to Figures 1, 2, 3 and 4, the present invention provides a method for synthesizing copper indium nitride nanoparticles by using a polyol, which mainly comprises the steps of separately preparing a polyol solution of a copper (Cu) element compound. a polyol solution of an indium (In) element compound and an alcohol solution of an X element compound, wherein the X element is selected from the group consisting of sulfur (S), selenium (Se) or cerium (Te), and an alcohol of an alcohol solution of an X element compound The type may be selected from a polyol or a unit alcohol; a polyol solution in which a copper element compound is mixed, a polyol solution of an indium element compound, and an alcohol solution of an X element compound are used as a polyol mixture; heating contains copper element, indium element, and The polyol mixture of the X element is heated to a temperature higher than a crystallization temperature to obtain a copper indium hydride (CuInX ₂ ) nanoparticle; and the copper indium hydride nanoparticle is obtained by filtration. The invention utilizes the dual characteristics that the polyol has high solubility to various element raw materials and the boiling point of the polyol is higher than the crystallization temperature of the copper indium compound, thereby performing liquid phase synthesis reaction, thereby preparing nano particles of copper indium compound or its derivative ( The particle size is between 20 and 50 nanometers for subsequent use in the manufacture of substrates having semiconductor-characteristic films, such as glass substrates or flexible substrates, for use in the fabrication of various thin film solar cells or other semiconductor electronic components. The present invention will be described in detail below with reference to the first to fourth embodiments and in conjunction with the first to fourth figures.

Referring to Fig. 1, a method for synthesizing copper indium nitride nanoparticles using a polyol according to a first embodiment of the present invention is for synthesizing copper indium sulfide (CuInS ₂ ). As shown in Fig. 1, first, 50 ml (ml) of diethylene glycol (DEG) was prepared as a polyol. Next, 0.2 g (g) of indium chloride InCl _{3 was} heated to 50 ° C and dissolved in 10 ml of diethylene glycol (DEG) to prepare a diethylene glycol solution of the indium (In) element compound for use. Separately, 0.1514 g of thiourea (NH ₂ CSNH ₂ ) was added to 20 ml of diethylene glycol to be dissolved in a three-port reactor equipped with a condenser tube to prepare a diethylene glycol solution of a sulfur (S) element compound for use. Subsequently, another 0.0895 g of copper chloride (CuCl) powder and the remaining diethylene glycol (DEG) solution were prepared to prepare a solution of copper (Cu) elemental compound in diethylene glycol, and it was combined with the indium element compound The alcohol solution is added to a three-port reactor having a condenser tube, and further stirred and mixed with a diethylene glycol solution of a sulfur (S) element compound to form a diethylene glycol mixture. Next, the diethylene glycol mixture is heated and heated to 200 to 240 ° C for 2 hours or more, for example, heating is maintained at 200 ° C for about 2 hours. The above temperature can fully react copper, indium and sulfur, and synthesize copper indium sulfide. Crystallization of (CuInS ₂ ), after sufficient crystallization, the diethylene glycol mixture is lowered to normal temperature, and the crystallized nano particles are filtered by a filter paper, washed with alcohol and centrifuged, and dried to obtain copper indium sulfide. The nanoparticle of (CuInS ₂ ) has a copper:indium:sulfur molar ratio=1:1:2.2, and a particle diameter of between 30 and 40 nanometers (nm).

Referring to Fig. 2, a method for synthesizing copper indium nitride nanoparticles using a polyol according to a second embodiment of the present invention is for synthesizing copper indium selenide (CuInSe ₂ ). As shown in Fig. 2, 50 ml of diethylene glycol (DEG) was first prepared as a polyol. Next, 0.2 g (g) of indium chloride InCl _{3 was} heated to 50 ° C and dissolved in 10 ml of diethylene glycol (DEG) to prepare a diethylene glycol solution of the indium (In) element compound for use. In addition, 0.157 g of selenium (Se) powder, 0.09 g of sodium borohydride (NaBH ₄ ) (the molar number is slightly more than about 10% of the selenium powder) and 10 ml of ethanol (Ethanol, EtOH) are added to the three ports with the condensation tube. The reactor is sealed and stirred at room temperature. When the solution of the selenium powder is completely dissolved, the solution is clear orange-red, that is, a solution of sodium selenide (NaHSe), that is, an ethanol solution of a selenium (Se) element compound. Subsequently, another 0.0895 g of copper chloride (CuCl) powder and the remaining diethylene glycol (DEG) solution were prepared to prepare a solution of copper (Cu) elemental compound in diethylene glycol, and it was combined with the indium element compound The alcohol solution is added to the three-port reactor together, and further stirred and mixed with the ethanol solution of the selenium (Se) element compound to form a mixture of diethylene glycol. Next, the diethylene glycol mixture was heated and heated. At the initial temperature rise to 120 ° C, since the diethylene glycol mixture is mixed with ethanol to lower the boiling point, boiling reflux will begin. At this point, the opening of the three-port reactor was opened to allow the ethanol to evaporate, leaving only diethylene glycol. Then, continue to heat until the temperature is raised to 210 to 240 ° C for more than 2 hours, for example, to maintain heating at 240 ° C for about 4 to 6 hours, the above temperature can fully react copper, indium, selenium elements, and synthesize copper indium selenide ( Crystallization of CuInSe ₂ ). After sufficient crystallization, the diethylene glycol mixture is lowered to normal temperature, and the crystallized nano particles are filtered by a filter paper, washed with alcohol and centrifuged, and dried to obtain a copper indium selenide (CuInSe ₂ ) nanometer. Particles, copper: indium: molar ratio of selenium = 1:1: 2.2, particle size between 35 and 50 nanometers (nm).

Referring to Fig. 3, a method for synthesizing copper indium halide nanoparticles using a polyol according to a third embodiment of the present invention is for synthesizing copper indium telluride (CuInTe ₂ ). As shown in Fig. 3, 70 ml (ml) of tetraethylene glycol (TEG) was first prepared as a polyol. Next, 0.2 g (g) of indium chloride InCl _{3 was} heated to 50 ° C and dissolved in 10 ml of tetraethylene glycol (TEG) to prepare a tetraethylene glycol solution of the indium (In) element compound for use. In addition, 0.2538 g of cerium (Te) powder was added to 20 ml of tetraethylene glycol, heated to 90 ° C and dissolved in a three-port reactor equipped with a condenser and argon gas. After stirring for 10 minutes, 0.7525 g of boron was taken. Sodium hydride (NaBH ₄ ) (more than about 10 times the molar number of strontium) is added to the reactor. After mixing, the color changes from black to dark purple, which forms a solution of sodium hydride (NaHTe), which is 碲 (Te). A tetraethylene glycol solution of the elemental compound. Subsequently, another 0.0895 g of copper chloride (CuCl) powder and the remaining tetraethylene glycol (TEG) solution were taken, and the temperature was raised to 150 ° C to dissolve it, and after being dissolved, it was lowered to normal temperature to prepare a copper (Cu) element compound. The tetraethylene glycol solution is then added to the three-port reactor with the condensing tube together with the tetraethylene glycol solution of the indium element compound to further mix and mix with the tetraethylene glycol solution of the cerium (Te) element compound to form a tetraethylene glycol. Mixture. Next, the tetraethylene glycol mixture is heated and heated to 280 to 310 ° C for 6 hours or more, for example, heating is maintained at 280 ° C for about 6 hours. The above temperature can fully react copper, indium and bismuth elements, and synthesize copper indium telluride. Crystallization of (CuInTe ₂ ). After sufficient crystallization, the tetraethylene glycol mixture is lowered to normal temperature, and the crystallized nano particles are filtered by a filter paper, washed with alcohol and centrifuged, and dried to obtain a copper indium telluride (CuInTe ₂ ) nanometer. Particles, copper: indium: molar ratio of enthalpy = 1:1: 2.2, particle size between 35 and 50 nanometers (nm).

Referring to FIG. 4, a method for synthesizing copper indium nitride nanoparticles using a polyol according to a fourth embodiment of the present invention is for synthesizing copper indium gallium selenide (CuIn _1-y Ga _y Se ₂ ), wherein y Between 0.3 and 0.6. As shown in Fig. 4, 50 ml of tetraethylene glycol (TEG) was first prepared as a polyol. Next, 0.0942 g (g) of indium chloride InCl ₃ and 0.05 g (g) of gallium chloride GaCl ₃ were respectively dissolved in 10 ml of tetraethylene glycol (TEG) to prepare an indium (In) element compound A glycol solution and a tetraethylene glycol solution of a gallium (Ga) element compound are used. In addition, 0.1233 g of selenium (Se) powder, 0.0709 g of sodium borohydride (NaBH ₄ ) (the molar number is slightly more than about 10% of the selenium powder) and 10 ml of ethanol (Ethanol, EtOH) are added to the three with a condenser tube. The reactor is sealed and stirred at room temperature. When the solution of the selenium powder is completely dissolved, the solution is clear orange-red, that is, a solution of sodium selenide (NaHSe), that is, an ethanol solution of a selenium (Se) element compound. Subsequently, another 0.0703 g of copper chloride (CuCl) powder and the remaining tetraethylene glycol (TEG) solution were prepared to prepare a tetraethylene glycol solution of a copper (Cu) element compound, and the indium element compound The alcohol solution was added to the three-port reactor together, and further stirred and mixed with the ethanol solution of the selenium (Se) element compound to form a tetraethylene glycol-based mixture. Next, the tetraethylene glycol mixture was heated and heated. When the initial temperature is raised to 120 ° C, since the tetraethylene glycol mixture is mixed with ethanol to lower the boiling point, boiling reflux is started, and boiling is maintained for 30 minutes. At this point, open the opening of the three-port reactor to allow the ethanol to evaporate. Next, a tetraethylene glycol solution of a gallium compound was further added, and heating was continued to 125 ° C to maintain boiling for 30 minutes, and the ethanol was completely volatilized, leaving only tetraethylene glycol. Then, continue to heat until the temperature rises to 280 to 310 ° C for more than 6 hours, for example, to maintain heating at 280 ° C for about 6 hours, the above temperature can fully react copper, indium, gallium, selenium elements, and synthesize copper indium gallium selenide Crystallization of (CuIn _0.6 Ga _0.4 Se ₂ ). After sufficient crystallization, the tetraethylene glycol mixture is lowered to room temperature, and the crystallized nano particles are filtered by a filter paper, washed with alcohol and centrifuged, and dried to obtain copper indium gallium selenide (CuIn _0.6 Ga _0.4 Se). ₂ ) Nanoparticles having a particle size between 35 and 50 nanometers (nm).

Please refer to FIG. 5, which discloses (a) copper indium sulfide (CuInS ₂ ), (b) copper indium selenide (CuInSe ₂ ) and (c) copper indium synthesized by the first to third embodiments of the present invention. X-ray diffraction pattern of nano particles such as telluride (CuInTe ₂ ). As shown in Fig. 5, the diffraction peaks of the respective nanoparticles are via the Joint Committee of Powder Diffraction Standards (JCPDS) Nos. 27-0159, 40-1487, and 34-1498. The powder standard is fully matched after the comparison. Furthermore, please refer to FIG. 6, which discloses a tunneling electron microscope (TEM) photographic image of a copper indium selenide (CuInSe ₂ ) nanoparticle synthesized by the present invention and an electronic selective area diffraction (SEAD) photographic image. The grain size of each of the nano particles was observed by a tunneling electron microscope (TEM), and the particle size of the three kinds of nano particles was found to be between 35 and 47 nanometers (nm). In the present invention, depending on the type of the nanoparticle to be synthesized, the particle diameter is mostly between 20 and 50 nm. Further, please refer to Figures 7 and 8, which disclose various copper indium gallium selenide synthesized by the present invention (a) CuIn _0.7 Ga _0.3 Se ₂ , (b) CuIn _0.6 Ga _0.4 Se ₂ , (c) CuIn _0.5 Ga X-ray diffraction pattern of _0.5 Se ₂ and (d) CuIn _0.4 Ga _0.6 Se ₂ and other nano particles and a partial enlarged view thereof, wherein various copper indium gallium selenide (CuIn _1-y Ga _y Se ₂ ) nanoparticles The X-ray diffraction results of the composite materials under different gallium (Ga) element substitutions (y=0.3~0.6) can clearly show that the crystal surface peak of the nano particles (as shown in Fig. 8) will follow the gallium. The substitution amount of (Ga) is different to cause a translation phenomenon.

Furthermore, in the present invention, the polyol referred to in the present invention may be a nanoparticle to be synthesized in addition to diethylene glycol (DEG, boiling point 245 ° C) or tetraethylene glycol (TEG, boiling point 327 ° C). The type of crystallization temperature is selected to use other polyols, such as triethylene glycol (boiling point 288 ° C), or may be selected from ethylene glycol (ethylene glycol, boiling point 197 ° C) or polyethylene glycol (poly-ethylene glycol) The molecular weight is 200~6000, and the boiling point depends on the molecular weight, about 250 °C. The boiling point of the above polyol must be higher than the crystallization temperature of the copper indium compound so as not to evaporate excess solvent when the crystallization reaction has not been completed. Further, the alcohol used in the alcohol solution of the X element compound may be selected from a polyhydric alcohol or a unit alcohol, wherein the polyhydric alcohol may be selected from the above species, and the unit alcohol may be selected from C _n H _2n+1 OH. Alcohols, wherein n is a positive integer such as ethanol, propanol or butanol. As shown in FIG. 2 or 4, when the alcohol in the alcohol solution of the X element compound is selected from a unit alcohol (such as ethanol), after mixing into the polyol mixture, it is necessary to initially heat and remove the polyol mixture. The unit alcohol in the liquid is then raised to the crystallization temperature of the nanoparticle. On the other hand, as shown in FIG. 4, in the initial step of formulating the solution, a polyhydric alcohol solution of a gallium element compound may be additionally additionally prepared; and then, in the step of mixing the solution, a polyhydric alcohol of a gallium element compound is further added. a solution to be mixed together to form the polyol mixture; thus, in the step of heating the polyol mixture to a temperature higher than a crystallization temperature, copper indium gallium (CuIn _1-y Ga _y X ₂ ) can be obtained. a nanoparticle, wherein y is between 0.3 and 0.6; and finally, a copper indium gallium nitride nanoparticle is obtained by filtration, wherein the X element of the copper indium gallium compound (CuIn _1-y Ga _y X ₂ ) It is preferably selected from selenium (Se).

After the nanoparticle of a certain copper indium compound or a derivative thereof is prepared according to any one of the first to fourth embodiments of the first to fourth embodiments of the present invention or the like, the present invention may additionally Selectively performing the following steps: first, mixing copper indium (or copper indium gallium) nanoparticle with an organic printing ink filler to form a printing ink; and then printing the printing ink onto a surface of a substrate; Subsequently, the organic printing ink filler in the printing ink is removed by high temperature, leaving only an absorbing layer formed of copper indium (or copper indium gallium) on the substrate, so that the substrate becomes a substrate having a semiconductor characteristic film. And can be applied to the manufacture of various thin film solar cells or other semiconductor electronic components. In the above step of removing the printing ink at a high temperature, the present invention preferably utilizes rapid thermal annealing (RTA) or curing to remove the organic printing ink filler at a high temperature. Furthermore, the substrate may be selected from a transparent hard substrate (such as a glass substrate or the like) or a transparent flexible flexible substrate (such as polymethyl methacrylate PMMA or polycarbonate PC, etc.).

As described above, Cu-III-VI _{2 is} mostly formed on a substrate by vapor deposition or sputtering in a vacuum environment; or the precursor is coated on a substrate in a vacuum-free environment. Then, the precursor is reduced to a material such as copper indium sulfide CIS by a high-temperature heat treatment method, but the above vacuum process has disadvantages such as expensive equipment and necessary use of poisoned hydrogen selenide gas; and the above high-temperature heat treatment process can only obtain large particles. The low-efficiency uniform absorption layer of the diameter, the invention of Figures 1 to 4 dissolves various elemental raw materials by using a polyol under normal pressure, and is heated to a suitable crystallization temperature in a liquid phase environment provided by the polyol. The elemental material is subjected to a synthesis reaction and crystallized into a copper indium (CuInX ₂ ) or copper indium gallium selenide (CuIn _1-y Ga _y Se ₂ ) nanoparticle, which does not require expensive process equipment or is toxic during the synthesis. The selenium gas is hydrogenated, which in turn helps to reduce manufacturing costs and improve process safety. Furthermore, the present invention can further utilize a copper indium compound or a copper indium gallium selenide nanoparticle having a nanometer particle diameter by appropriately controlling parameters such as heating temperature and time of a liquid phase environment of a polyol. Screen printing is combined with rapid thermal annealing or baking to form an absorption layer of copper indium or copper indium gallium selenide on the substrate, which is also advantageous for reducing the particle size of the material and improving the power generation efficiency.

The present invention has been disclosed in its preferred embodiments, and is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Fig. 1 is a flow chart showing the reaction of synthesizing copper indium sulfide (CuInS ₂ ) nanoparticles using diethylene glycol in the first embodiment of the present invention.

Fig. ₂ is a flow chart showing the reaction of synthesizing copper indium selenide (CuInSe ₂ ) nanoparticles using diethylene glycol in the second embodiment of the present invention.

Fig. 3 is a flow chart showing the reaction of synthesizing copper indium telluride (CuInTe ₂ ) nanoparticles using tetraethylene glycol in the third embodiment of the present invention.

Fig. 4 is a flow chart showing the reaction of synthesizing copper indium gallium selenide (CuIn _1-y Ga _y Se ₂ ) nanoparticles using tetraethylene glycol in the fourth embodiment of the present invention.

Figure 5: X- of nanoparticles of (a) copper indium sulfide (CuInS ₂ ), (b) copper indium selenide (CuInSe ₂ ) and (c) copper indium telluride (CuInTe ₂ ) synthesized by the present invention Light diffraction pattern.

Figure 6: Tunneling electron microscope (TEM) photographic image of a copper indium selenide (CuInSe ₂ ) nanoparticle synthesized by the present invention and its electronic selective area diffraction (SEAD) photographic image.

Figure 7: Copper indium gallium selenide synthesized by the present invention (a) CuIn _0.7 Ga _0.3 Se ₂ , (b) CuIn _0.6 Ga _0.4 Se ₂ , (c) CuIn _0.5 Ga _0.5 Se ₂ and (d) CuIn _0.4 Ga _0.6 X-ray diffraction pattern of nano particles such as Se ₂ .

Figure 8 is a partial enlarged X-ray diffraction pattern of Figure 7 of the present invention.

Claims (15)

A method for synthesizing copper indium nitride nanoparticles by using a polyol, comprising: separately preparing a polyol solution of a copper (Cu) element compound, a polyol solution of an indium (In) element compound, and an alcohol solution of an X element compound, wherein The X element is selected from the group consisting of sulfur (S), selenium (Se) or tellurium (Te), wherein when the X element is sulfur (S), the molar concentration of the copper (Cu) element compound polyol solution is 0.045 M, which The molar concentration of the polyol solution of the indium (In) element compound is 0.09 M, and the molar concentration of the alcohol solution of the sulfur (S) element compound is 0.1 M; or when the X element is selenium (Se) and the copper When the Mohr concentration of the polyol solution of the (Cu) element compound is 0.023 M, the molar concentration of the polyol solution of the indium (In) element compound is 0.09 M, and the alcohol solution of the selenium (Se) element compound The Mohr concentration is 0.437 M; or when the X element is selenium (Se) and the Moor concentration of the copper (Cu) element compound polyol solution is 0.018 M, the indium (In) element compound polyol solution is not The concentration is 0.0712M, and the molar concentration of the alcohol solution of the selenium (Se) element compound is 0.343M; or when the X element is 碲 (T e), the molar concentration of the copper (Cu) element compound polyol solution is 0.018 M, the molar concentration of the indium (In) element compound polyol solution is 0.09 M, and the cerium (Te) element compound The alcohol solution has a Mohr concentration of 0.2 M; the polyol solution of the copper element compound, the polyol solution of the indium element compound, and the alcohol solution of the X element compound become a polyol mixture; the heating contains copper element, indium a polyol mixture of an element and an X element to a temperature higher than a crystallization temperature to obtain a copper indium compound (CuInX ₂ ) nanoparticle, wherein the boiling point of the polyol is higher than a crystallization temperature of the copper indium compound, and when X When the element is selected from sulfur (S), the heating temperature is between 200 and 240 degrees, and the heating time is at least 2 hours; when the X element is selected from selenium (Se), the heating temperature is between 210 and 240 degrees. The heating time is between 4 and 6 hours, or the heating temperature is between 280 and 310 degrees, and the heating time is at least 6 hours; when the X element is selected from the group consisting of cerium (Te), the heating temperature is between 280 and 310 degrees. Between and at least 6 hours of heating; and filtration to obtain copper indium nitride Child. The method for synthesizing copper indium nitride nanoparticles by using a polyol according to claim 1, wherein the polyol in the polyol solution of the copper element compound is selected from the group consisting of diethylene glycol, triethylene glycol, tetraethylene glycol, and B. Glycol or polyethylene glycol. The method for synthesizing copper indium nitride nanoparticles by using a polyol according to claim 1, wherein the polyol in the polyol solution of the indium element compound is selected from the group consisting of diethylene glycol, triethylene glycol, tetraethylene glycol, and B. Glycol or polyethylene glycol. The method for synthesizing copper indium nitride nanoparticles by using a polyol according to the first aspect of the invention, wherein the alcohol in the alcohol solution of the X element compound is selected from the group consisting of a polyol or a unit alcohol. The method for synthesizing copper indium nitride nanoparticles by using a polyol according to claim 4, wherein the polyol is selected from the group consisting of diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol or polyethylene glycol; The unit alcohol is selected from the group consisting of ethanol, propanol or butanol. The method for synthesizing copper indium nitride nanoparticles by using a polyol according to claim 1, wherein when the alcohol in the alcohol solution of the X element compound is selected from a unit alcohol, the polyol mixture is mixed. Thereafter, the unit alcohol in the polyol mixture is first heated and then the temperature of the polyol mixture is raised to the crystallization temperature. The method for synthesizing copper indium nitride nanoparticles by using a polyol according to claim 1, wherein the copper indium halide has a particle diameter of between 20 and 50 nm. The method for synthesizing copper indium hydride nanoparticles by using a polyol according to claim 1, wherein after filtering, the copper indium sulphide particles are mixed with an organic printing ink filler to form a printing ink; The printing ink screen is printed onto the surface of a substrate; the organic printing ink filler in the printing ink is removed at a high temperature, leaving only an absorbing layer formed of copper indium compound on the substrate. A method of synthesizing copper indium nitride nanoparticles using a polyol as described in claim 8, wherein the organic printing ink filler is removed at a high temperature by rapid thermal annealing or baking. The method for synthesizing copper indium nitride nanoparticles by using a polyol according to claim 8, wherein the substrate is a transparent hard substrate or Transparent flexible flexible substrate. The method for synthesizing copper indium nitride nanoparticles by using a polyol according to claim 1, further comprising: adjusting a polyol solution of a gallium element compound when preparing the solution; and adding a gallium element when mixing the solution; a polyol solution of the compound to be mixed together to form the polyol mixture; and when the polyol mixture is heated to a temperature higher than a crystallization temperature, a copper indium gallium hydride (CuIn _1-y Ga _y X ₂ ) is obtained. Particles, wherein y is between 0.3 and 0.6; and nanoparticle particles obtained by copper indium gallium hydride are obtained by filtration. The method for synthesizing copper indium nitride nanoparticles using a polyol according to claim 11, wherein the X element of the copper indium gallium compound is selected from the group consisting of selenium (Se). The method for synthesizing copper indium hydride nanoparticles by using a polyol according to claim 11, wherein after filtering, the copper indium sulphide particles are mixed with an organic printing ink filler to form a printing ink; The printing ink screen is printed onto the surface of a substrate; the organic printing ink filler in the printing ink is removed at a high temperature, leaving only an absorbing layer formed of copper indium compound on the substrate. A method of synthesizing copper indium nitride nanoparticles using a polyol as described in claim 13, wherein the organic printing ink filler is removed at a high temperature by rapid thermal annealing or baking. Synthesis of copper indium using polyols as described in claim 13 A method of forming a nanoparticle, wherein the substrate is a transparent hard substrate or a transparent flexible flexible substrate.