KR101874227B1 - Copper chalcogenide absorber and optical film, and method of fabricating the sames - Google Patents

Copper chalcogenide absorber and optical film, and method of fabricating the sames Download PDF

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KR101874227B1
KR101874227B1 KR1020170008619A KR20170008619A KR101874227B1 KR 101874227 B1 KR101874227 B1 KR 101874227B1 KR 1020170008619 A KR1020170008619 A KR 1020170008619A KR 20170008619 A KR20170008619 A KR 20170008619A KR 101874227 B1 KR101874227 B1 KR 101874227B1
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copper
chalcogenide
copper chalcogenide
according
oxide
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KR1020170008619A
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Korean (ko)
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좌용호
권영태
임규담
천지애
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한양대학교 에리카산학협력단
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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/208Filters for use with infra-red or ultraviolet radiation, e.g. for separating visible light from infra-red and/or ultraviolet radiation
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made
    • G02B1/04Optical elements characterised by the material of which they are made made of organic materials, e.g. plastics
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/008Surface plasmon devices
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/22Absorbing filters
    • G02B5/223Absorbing filters containing organic substances, e.g. dyes, inks or pigments

Abstract

A process for producing a copper chalcogenide light absorber is provided. The method of manufacturing the copper chalcogenide light absorber comprises the steps of: preparing a first source solution containing sulfur (S) and selenium (Se), adding a second source solution containing copper (Cu) To form a cooper chalcogenide particle; and coating the copper chalcogenide particle with an oxide to form a copper chalcogenide composite.

Description

Copper chalcogenide light absorbers and light absorbing films, and methods of making them. {Copper chalcogenide absorber and optical film, and method of fabricating the sames}

The present invention relates to a copper-chalcogenide light absorber and a light-absorbing film, and a production method thereof, and relates to a copper-chalcogenide light absorber and a light-absorbing film comprising oxide-coated copper chalcogenide particles, .

In general, conventional ultraviolet and near-infrared region shielding materials include organic dyes, indium tin oxide (ITO), antimony tin oxide (ATO), and cesium-doped tungsten oxide Cs doped tungsten oxide (CsWO 3 )). As a material for the photocatalytic reaction, titania (TiO 2 ) and a titania-metal complex, a titania-metal oxide complex, a vanadium oxide (V 2 O 3 ), a tungsten oxide (WO 3 ) And so on.

Until now, materials for shielding one of ultraviolet or near infrared region have been developed, but now materials for simultaneous shielding of ultraviolet and near infrared region are being developed. First, in order to simultaneously block ultraviolet rays and near-infrared rays, there is a problem in that each substance must be used separately or in combination. In the case of organic dye materials (simple tint film, coloring matter, sputter-coated glass), it has performance limitations such as low visible light transmittance and ultraviolet / near infrared shielding ratio, application limit due to high price, And the like. Indium tin oxide, antimony tin oxide and cesium-doped tungsten oxide have limitations on the cost of the source material, and their synthesis method is very limited.

Accordingly, various techniques for materials capable of simultaneously shielding ultraviolet and near-infrared regions have been developed. For example, JP-A-10-1325728 (Application No. 10-2012-0117579, filed by Nexfil Co., Ltd.), which contains a polybutyl film while absorbing and blocking ultraviolet rays and infrared rays, Provided is a reinforcement film capable of absorbing ultraviolet rays and infrared rays which can be used for security and the like because its rigidity is very high, and a manufacturing method thereof.

In addition, technologies related to materials capable of simultaneously shielding ultraviolet and near-infrared regions are being continuously researched and developed.

Patent Registration No. 10-1325728

Disclosure of Invention Technical Problem [8] The present invention provides a copper-chalcogenide light absorber capable of simultaneously absorbing / blocking ultraviolet rays and near-infrared rays, and a method of manufacturing the same.

It is another object of the present invention to provide a copper-chalcogenide optical absorber capable of adjusting the absorption spectrum of ultraviolet and near-infrared rays, and a method of manufacturing the same.

It is another object of the present invention to provide a copper carbocyanine light absorber which is easy to produce in a large-scale synthesis and a nano-size size, and a method of manufacturing the same.

The technical problem to be solved by the present invention is not limited to the above.

In order to solve the above technical problems, the present invention provides a method of manufacturing a copper chalcogenide light absorber.

According to one embodiment, the method of fabricating the copper chalcogenide light absorber comprises preparing a first source solution comprising sulfur (S) and selenium (Se), adding copper (Cu) to the first source solution And forming a copper chalcogenide particle comprising copper, selenium, and a compound of a sulfur, and coating the copper chalcogenide particle with an oxide to form a copper chalcogenide particle, To form a complex.

According to one embodiment, the copper chalcogenide complex may comprise simultaneously absorbing ultraviolet and near-infrared rays.

According to one embodiment, the ultraviolet light may be absorbed in the band gap region of the copper chalcogenide complex.

According to one embodiment, the near-infrared light may be absorbed by the surface plasmon resonance phenomenon of the copper chalcogenide complex.

According to one embodiment, the second source solution may include a reducing agent for controlling the content of copper contained in the copper chalcogenide particles.

According to an embodiment of the present invention, the step of forming the copper chalcogenide composite comprises: preparing a mixed solution by mixing a solution in which the copper chalcogenide particles are dispersed and a coating solution for coating the copper chalcogenide particles; Adding a pH adjusting agent to the mixed solution, and centrifuging the mixed solution with the pH adjusting agent.

In order to solve the above technical problems, the present invention provides a method for producing a copper chalcogenide light absorbing film.

According to an embodiment of the present invention, there is provided a method of manufacturing a copper chalcogenide light absorbing film, comprising: preparing a copper chalcogenide composite according to the production method of the copper chalcogenide light absorbent; And then coating the copper chalcogenide composite with the binder mixed on the base film.

In order to solve the above technical problems, the present invention provides a copper carbocyanide light absorbing material.

According to one embodiment, the copper chalcogenide light absorber comprises a copper chalcogenide composite comprising copper chalcogenide particles comprising a compound of copper, selenium, and sulfur, and an oxide coating the copper chalcogenide particles, Wherein the copper chalcogenide complex may include ultraviolet light and near infrared light simultaneously.

According to one embodiment, the oxide may include at least one of SiO 2 , Al 2 O 3 , MgO, and Fe 2 O 3 (iron oxide).

According to one embodiment, the copper chalcogenide composite may include a core-shell structure in which the surface of the copper chalcogenide particles is surrounded by the oxide.

According to one embodiment, the copper chalcogenide composite may include a structure in which the copper chalcogenide particles are distributed in the oxide matrix.

In order to solve the above technical problem, the present invention provides a copper chalcogenide light-absorbing film.

According to one embodiment, the copper chalcogenide light absorbing film may comprise a base film, and a copper chalcogenide light absorber according to claim 8 coated on the base film.

The copper chalcogenide light absorber according to an embodiment of the present invention is a copper chalcogenide light absorber comprising copper chalcogenide particles including copper, selenium, and sulfur compounds and an oxide coating the copper chalcogenide particles, .

The copper chalcogenide composite absorbs ultraviolet light in an inherent bandgap region of the copper chalcogenide composite and can absorb near-infrared light by surface plasmon resonance of the copper chalcogenide complex. Accordingly, the copper chalcogenide light absorbing material can simultaneously absorb ultraviolet rays and near-infrared rays.

In addition, the copper chalcogenide light absorber can adjust the absorption spectrum of ultraviolet and near infrared rays by controlling the contents of copper and selenium contained in the copper chalcogenide complex. In addition, the absorption spectra of ultraviolet and near-infrared light can be adjusted depending on the application in which the copper chalcogenide light absorber is used.

In addition, the copper carbocyanine light absorber can be easily mass-synthesized, manufactured to a nanoscale size, and can be produced environmentally, as it is produced by a solution process.

In addition, the copper chalcogenide light absorber can prevent contact with moisture and oxygen as the copper chalcogenide particles are coated with the oxide. Accordingly, the durability of the copper chalcogenide light absorber can be improved and the water permeability can be reduced.

In the above-described embodiments, although the copper chalcogenide particles are described as being coated with an oxide, according to one embodiment, the copper chalcogenide particles not coated with the oxide may be used as a photocatalyst.

1 is a flow chart for explaining a method of manufacturing a copper chalcogenide light absorber according to an embodiment of the present invention.
Figures 2 and 3 are graphs showing X-ray diffraction patterns of copper chalcogenide particles according to embodiments of the present invention.
FIG. 4 is a scanning electron microscope (SEM) image of copper chalcogenide particles according to an embodiment of the present invention.
FIG. 5 and FIG. 6 are transmission electron microscope photographs of copper chalcogenide particles according to the embodiments of the present invention.
7 and 8 are graphs showing light transmittance spectra of copper chalcogenide particles according to embodiments of the present invention.
9 is a photograph of the copper carbocyanide light absorber according to Example 9 of the present invention taken by a transmission electron microscope.
10 is a graph showing the characteristics of the copper carbocyanide particles and the light absorber according to Examples and Comparative Examples of the present invention.
11A to 11C are photographs of a light absorbing film according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical spirit of the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Further, in the drawings, the thicknesses of the films and regions are exaggerated for an effective explanation of the technical content.

Also, while the terms first, second, third, etc. in the various embodiments of the present disclosure are used to describe various components, these components should not be limited by these terms. These terms have only been used to distinguish one component from another. Thus, what is referred to as a first component in any one embodiment may be referred to as a second component in another embodiment. Each embodiment described and exemplified herein also includes its complementary embodiment. Also, in this specification, 'and / or' are used to include at least one of the front and rear components.

The singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. It is also to be understood that the terms such as " comprises "or" having "are intended to specify the presence of stated features, integers, Should not be understood to exclude the presence or addition of one or more other elements, elements, or combinations thereof.

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

1 is a flow chart for explaining a method of manufacturing a copper chalcogenide light absorber according to an embodiment of the present invention.

Referring to FIG. 1, a first source solution including sulfur (S) and selenium (Se) may be prepared (S110). According to one embodiment, the first source solution may be prepared by mixing and stirring distilled water, a sulfur flame, a selenium salt, and a dispersion stabilizer. For example, the first source solution may be prepared by mixing distilled water, 0.015 moles of sulfur flame, 0 to 0.003 moles of selenium salt, and 0.01 mole of a dispersion stabilizer, stirring at a temperature of 70 DEG C at 400 rpm for 30 minutes .

According to one embodiment, the sulfur flame is at least one of thiourea, sodium sulfide (Na 2 S), potassium sulfide (K 2 S), sodium thiosulfate (Na 2 S 2 O 3 ) . ≪ / RTI > According to one embodiment, the selenium salt is at least one selected from the group consisting of selenourea, sodium selenide (Na 2 Se), selenium dioxide (SeO 2 ), sodium selenite (NaSeO 3 ), selenium One can be included. According to one embodiment, the dispersion stabilizer is selected from the group consisting of polyvinylpyrrolidone (PVP), settimulonium bromide (CTAB), polyethylene glycol (PEG), sodium citrate, ethylenediaminetetraacetic acid (EDTA) And may include at least any one of them.

Cooper chalcogenide particles including copper, selenium and sulfur compounds may be formed by mixing the first source solution with a second source solution containing copper (S120).

The step of forming the copper chalcogenide particles may include the step of preparing the second source solution containing copper and the step of dropping the second source solution into the first source solution. According to one embodiment, the step of dispensing the second source solution into the first source solution may be performed with a syringe for a time of 5 minutes at a rate of 1 ml / min to 5 ml / min. Thus, the copper chalcogenide particles can be prevented from aggregating.

According to one embodiment, the second source solution may be a copper precursor solution. According to another embodiment, the second source solution may be prepared by mixing a reducing agent with a copper precursor solution.

The reducing agent can control the content of copper contained in the copper chalcogenide particles. According to one embodiment, the reducing agent is at least one selected from the group consisting of ascorbic acid, sodium sulfate (Na 2 SO 4 ), sodium sulfite (Na 2 SO 3 ), sodium hydroxide (NaOH) One can be included.

When the copper chalcogenide particles are formed without containing the reducing agent, the band gap of the copper chalcogenide particles may be reduced as the proportion of selenium contained in the copper chalcogenide particles increases. Accordingly, the visible light transmittance of the copper chalcogenide particles can be reduced. In addition, the near infrared ray blocking rate of the copper chalcogenide particles may be reduced.

Alternatively, when the copper chalcogenide particles are formed to include the reducing agent, the band gap of the copper chalcogenide particles may increase as the proportion of selenium contained in the copper chalcogenide particles increases. Accordingly, the visible light transmittance of the copper chalcogenide particles can be increased. In addition, the near infrared ray blocking rate of the copper chalcogenide particles may be increased.

According to one embodiment, as the ratio of selenium contained in the copper chalcogenide particles increases, the amount of selenium in the copper chalcogenide lattice is increased, so that the size of the copper chalcogenide particles may increase .

The copper chalcogenide particles may be coated with an oxide to form a copper chalcogenide composite (S130). The step of forming the copper chalcogenide composite may include the steps of: preparing a mixed solution by mixing a solution in which the copper chalcogenide particles are dispersed and a precursor of the oxide; dropping a pH adjusting agent in the mixed solution; and the step of centrifuging the mixed solution in which the pH adjuster is dispensed may be included. Thus, a copper chalcogenide light absorber can be produced.

According to one embodiment, the oxide may include at least one of silica (SiO 2 ), alumina (Al 2 O 3 ), magnesium oxide (MgO), and iron oxide (Fe 2 O 3 ).

According to one embodiment, the solution in which the copper chalcogenide particles are dispersed can be prepared by mixing the copper chalcogenide particles with the dispersion solution. For example, the dispersion solution may be water (H 2 O) or ethanol. According to one embodiment, the precursor of the oxide may be a solution in which tetraethylorthosilicate (TEOS) or aluminum chloride (AlCl 3 ) is mixed with ethanol.

According to one embodiment, the mixed solution may be prepared by mixing a solution in which the copper chalcogenide particles are dispersed and the coating solution at a ratio of 1: 1.

According to one embodiment, the pH adjusting agent may be aqueous ammonia (NH 4 OH). According to one embodiment, the step of dropping the pH adjusting agent in the mixed solution may be performed for 3 hours. The pH of the mixed solution can be adjusted to 9 to 10.

According to one embodiment, the copper chalcogenide composite may be a core-shell structure in which the surface of the copper chalcogenide particles is surrounded by the oxide. According to another embodiment, the copper chalcogenide composite may have a structure in which the copper chalcogenide particles are distributed in the oxide matrix. For example, the copper chalcogenide complex may be in the form of a nano powder.

The copper chalcogenide composite may absorb ultraviolet light in a band gap region inherent to the copper chalcogenide composite. In addition, the copper chalcogenide composite can absorb near-infrared light by surface plasmon resonance (SPR) of the copper chalcogenide complex. Accordingly, the copper chalcogenide composite can simultaneously absorb ultraviolet rays and near-infrared rays.

Unlike the embodiments of the present invention described above, an organic dye other than the copper chalcogenide composite, indium tin oxide (ITO), antimony tin oxide (ATO), cesium-doped tungsten oxide Cesium-doped tungsten oxide (CsWO 3 )), it is necessary to separately use or mix the respective materials in order to absorb only one region of ultraviolet rays or near-infrared rays, or to block ultraviolet rays or near-infrared rays simultaneously have. In addition, the optical absorber containing organic dyes has a problem in that the absorptivity is low, and in the case of the optical absorber including ITO, ATO, CsWO 3, etc., there is a problem that the cost of the source material is high.

However, the copper chalcogenide light absorber according to the embodiment of the present invention is characterized in that the copper chalcogenide light absorber comprises copper chalcogenide particles containing copper, selenium, and a compound of sulfur, and copper chalcogenide containing an oxide coating the copper chalcogenide particles ≪ / RTI > complexes.

The copper chalcogenide composite absorbs ultraviolet light in an inherent bandgap region of the copper chalcogenide composite and can absorb near-infrared light by surface plasmon resonance of the copper chalcogenide complex. Accordingly, the copper chalcogenide light absorbing material can simultaneously absorb ultraviolet rays and near-infrared rays.

In addition, the copper chalcogenide light absorber can adjust the absorption spectrum of ultraviolet and near infrared rays by controlling the contents of copper and selenium contained in the copper chalcogenide complex. In addition, the absorption spectra of ultraviolet and near-infrared light can be adjusted depending on the application in which the copper chalcogenide light absorber is used.

In addition, the copper carbocyanine light absorber can be easily synthesized in large quantities as it is produced by a solution process, can be produced in a nanosize size, and can be produced in an environmentally friendly manner.

In addition, the copper chalcogenide light absorber can prevent contact with moisture and oxygen as the copper chalcogenide particles are coated with the oxide. Accordingly, the durability of the copper chalcogenide light absorber can be improved and the water permeability can be reduced.

The copper chalcogenide composite can be used as a light absorbing film as it simultaneously absorbs ultraviolet rays and near-infrared rays. Hereinafter, a method of manufacturing the light absorbing film will be described.

The method of manufacturing a light absorbing film according to the present invention includes the steps of preparing a copper chalcogenide composite according to the manufacturing method of the copper chalcogenide light absorber described with reference to FIG. 1, mixing the copper chalcogenide composite with a binder , And coating the copper chalcogenide composite with the binder mixed on the base film.

According to one embodiment, the binder includes at least one of polymethylsiloxane (PDMS), polymethyl methacrylate (PMMA), acrylic material, and urethane polymer can do.

According to one embodiment, the base film may be formed of a material selected from the group consisting of polycarbonate (PC), polyethersulfone (PES), triacetyl cellulose (TAC), polyvinyl alcohol (PVA) And may include at least one of polyimide (PI), and cyclic olefin copolymer (COC).

In the above-described embodiments, although the copper chalcogenide particles are described as being coated with an oxide, according to one embodiment, the copper chalcogenide particles not coated with the oxide may be used as a photocatalyst.

Hereinafter, specific experimental production examples and characteristics evaluation results of the light absorber and the light absorbing film according to the above-described embodiment of the present invention will be described.

Copper according to example 1 Chalcogenide  Particle manufacturing

A sulfur / selenium precursor aqueous solution is prepared. The sulfur / selenium precursor aqueous solution was prepared by mixing 0.01 mol of sulfur, a selenium salt and a dispersion stabilizer with distilled water and stirring at a temperature of 70 ° C at 400 rpm for 30 minutes. At this time, the molar ratio of the sulfur flame and the selenium salt was 10: 0.

A 2.5 molar concentration of copper precursor solution was injected into the aqueous solution of sulfur / selenium precursor at a rate of 1 ml / min for 5 minutes and reacted at a temperature of 70 ° C for 1 hour. Thereafter, the particles were centrifuged and washed three times with distilled water to prepare copper chalcogenide particles.

Copper according to example 2 Chalcogenide  Particle manufacturing

Copper chalcogenide particles according to Example 1 were prepared, and the molar ratio of the sulfur flame and the selenium salt was adjusted to 10: 0.5.

Copper according to example 3 Chalcogenide  Particle manufacturing

The copper chalcogenide particles according to Example 1 were prepared, and the molar ratio of the sulfur flame and the selenium salt was prepared at a ratio of 10: 1.

Copper according to example 4 Chalcogenide  Particle manufacturing

The copper chalcogenide particles according to Example 1 were prepared by preparing the sulfur flame and the selenium salt in a molar ratio of 10: 2.

Copper according to example 5 Chalcogenide  Particle manufacturing

The copper chalcogenide particles according to Example 1 were prepared by reacting a solution of the copper precursor solution and a reducing agent in a molar ratio of 2.5: 0.6 in the aqueous solution of sulfur / selenium precursor.

Copper according to example 6 Chalcogenide  Particle manufacturing

The copper-chalcogenide particles according to Example 2 were prepared by reacting the copper / cerium precursor aqueous solution with a mixture of the copper precursor solution and a reducing agent in a molar ratio of 2.5: 0.6.

Copper according to example 7 Chalcogenide  Particle manufacturing

The copper chalcogenide particles according to Example 3 were prepared by reacting a solution of the copper precursor solution and a reducing agent in a molar ratio of 2.5: 0.6 in the aqueous solution of sulfur / selenium precursor.

Copper according to example 8 Chalcogenide  Particle manufacturing

The copper chalcogenide particles according to Example 4 were prepared by reacting the copper precursor solution and the reducing agent in a molar ratio of 2.5: 0.6 in the aqueous sulfur / selenium precursor solution.

The synthesis conditions of the copper chalcogenide particles according to the above-described Examples 1 to 8 are summarized in Table 1 below.

division Copper chalcogenide nanoparticle synthesis conditions Copper precursor solution Sulfur / selenium precursor aqueous solution Copper precursor reducing agent Sulfur flame: selenium salt Example 1 2.5 M - 10: 0 Example 2 2.5 M - 10: 0.5 Example 3 2.5 M - 10: 1 Example 4 2.5 M - 10: 2 Example 5 2.5 M 0.6 M 10: 0 Example 6 2.5 M 0.6 M 10: 0.5 Example 7 2.5 M 0.6 M 10: 1 Example 8 2.5 M 0.6 M 10: 2

Production of a light absorber according to Example 9

A coating solution prepared by mixing copper chalcogenide particles according to Example 7 and ethanol and tetraethylorthosilicate (TEOS) at a ratio of 1: 1 was prepared. The copper chalcogenide particles were dispersed in ethanol, and the coating solution was mixed to prepare a mixed solution. Ammonia water (NH 4 OH) was added to the mixed solution at room temperature (25 ° C) for 3 hours using a syringe pump. Thereafter, the mixed solution was centrifuged and washed with distilled water to prepare a light absorber comprising a copper chalcogenide complex coated with SiO 2 on the copper chalcogenide particles.

The light absorbing film production according to Example 10

The copper chalcogenide particles according to Example 9 described above are prepared. The copper chalcogenide composite and PDMS (Polymethylsiloxane) were mixed and coated on a polycarbonate (PC) to prepare a light absorbing film.

The optical absorber preparation according to Comparative Example 1

A light absorber comprising commercial TiO 2 was prepared.

Figures 2 and 3 are graphs showing X-ray diffraction patterns of copper chalcogenide particles according to embodiments of the present invention.

Referring to FIG. 2, the intensities (a.u.) of the copper chalcogenide particles according to Examples 1 to 4 according to 2 Theta (degrees) were measured. As can be seen from FIG. 2, the copper chalcogenide particles according to Examples 1 and 2 can be confirmed to have an equivalent ratio of copper of 1 and 1.8. It can be confirmed that the copper chalcogenide particles according to Example 3 and Example 4 had an equivalent ratio of copper of 1.8.

In addition, since the copper chalcogenide particles according to Examples 2 to 4 have a larger sphere ion radius than that of the sulphate ion, as the proportion of the selenium salt contained in the copper chalcogenide particles increases, Can be confirmed to be shifted to a lower angle.

Referring to FIG. 3, the intensities (a.u.) of the copper chalcogenide particles according to Examples 5 to 8 were measured according to 2 Theta (degrees). As can be seen from Fig. 3, it was confirmed that the copper chalcogenide particles according to Examples 5 to 8 had an equivalent ratio of copper of 1.8.

In addition, it was confirmed that the peak of the diffraction pattern shifts to a lower angle as the proportion of the selenium salt contained in the copper chalcogenide particles is increased.

FIG. 4 is a scanning electron microscope (SEM) image of copper chalcogenide particles according to an embodiment of the present invention.

Referring to FIG. 4, a scanning electron microscope (SEM) of the copper chalcogenide particles according to Example 7 was performed. As can be seen from FIG. 4, it was confirmed that the copper chalcogenide particles according to Example 7 were produced with a uniform size of 10 nm or less.

FIG. 5 and FIG. 6 are transmission electron microscope photographs of copper chalcogenide particles according to the embodiments of the present invention.

Referring to FIG. 5A, the copper chalcogenide particles according to Example 1 were photographed by transmission electron microscope (TEM). As can be seen from FIG. 5 (a), the interplanar distance of the copper chalcogenide particles according to Example 1 was measured at 0.3119 nm, confirming that the equivalence ratio of copper coincided with the interplanar distance of copper sulfide of 1. In addition, it was confirmed that the copper chalcogenide particles according to Example 1 had a hexagonal system structure.

Referring to FIG. 5 (b), the copper chalcogenide particles according to Example 4 were photographed by TEM. As can be seen from FIG. 5 (b), the interplanar distance of the copper chalcogenide particles according to Example 4 was measured to be 0.3165 nm, which was found to be larger than the interplanar distance of the copper chalcogenide particles according to Example 1 there was. It was also confirmed that the copper chalcogenide particles according to Example 4 had a hexagonal system structure.

Referring to FIG. 6 (c), the copper chalcogenide particles according to Example 5 were photographed by TEM. As can be seen from FIG. 6 (c), the interplanar distance of the copper chalcogenide particles according to Example 5 was measured to be 0.3221 nm, confirming that the equivalence ratio of copper coincided with the interplanar distance of copper sulfide of 1.8. In addition, it was confirmed that the copper chalcogenide particles according to Example 1 had a cubic system structure.

Referring to FIG. 6 (d), the copper chalcogenide particles according to Example 8 were photographed by TEM. As can be seen from FIG. 6 (d), the interplanar distance of the copper chalcogenide particles according to Example 8 was measured at 3.298 nm, which was found to be larger than the interplanar distance of the copper chalcogenide particles according to Example 5 there was. In addition, it was confirmed that the copper chalcogenide particles according to Example 5 had a cubic system structure.

The average particle size value and the particle size value measured by TEM using the X-ray rotation pattern of the copper calcined particles according to Examples 1 to 8 can be summarized in Table 2.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 X-ray average particle size value (nm) 8.70 9.49 9.58 9.77 7.87 7.99 8.20 9.48 TEM particle size value (nm) 7.95 9.08 8.69 9.92

As can be seen from Table 2, it was confirmed that the copper chalcogenide particles according to Examples 1 to 8 had an average particle size of 10 nm or less. Also, as the amount of selenium contained in the copper chalcogenide particles was increased, it was confirmed that the size of the copper chalcogenide particles was increased.

7 and 8 are graphs showing light transmittance spectra of copper chalcogenide particles according to embodiments of the present invention.

Referring to FIG. 7, the light transmittance (%) of the copper chalcogenide particles according to Examples 1 to 4 was measured in the ultraviolet to near infrared region (200 nm to 1400 nm). As can be seen from FIG. 7, the copper chalcogenide particles according to Examples 1 to 4 showed that the peak shifts to a long wavelength in the visible light region as the amount of selenium contained in the copper chalcogenide particles increases I could. In addition, it was confirmed that as the amount of selenium contained in the copper chalcogenide particles increases, the lowest point is shifted to the longer wavelength region in the near infrared region.

(LSPR) peak, ultraviolet (UV) and near-infrared (NIR) blocking rates, visible transmittance (Vis) transmittance, and transmittance were measured using the light transmittance spectra of the copper chalcogenide particles according to Examples 1 to 4 And the results are summarized in Table 3. Wherein the ultraviolet ray blocking rate is a 100% -average transmittance in an ultraviolet region (200 nm to 400 nm), the near-infrared ray blocking rate is a 100%-average transmittance in a near infrared region (800 nm to 1400 nm), and the visible light transmittance is 500 nm The transmittance in the region was shown.

division Example 1 Example 2 Example 3 Example 4 Band gap (eV) 2.63 2.44 2.40 2.35 LSPR peak (nm) 1146 1156 1221 1375 UV cut rate (%) 97.05 93.78 92.88 94.36 Vis Viscosity (%) 61.59 60.67 60.52 53.17 NIR blocking rate (%) 81.81 83.14 81.32 83.49

As can be seen from Table 3, the copper chalcogenide particles according to Examples 1 to 4 exhibited a decrease in band gap as the proportion of selenium contained in the copper chalcogenide particles increased, It was confirmed that the resonance peak moves to the long wavelength region. As a result, it was confirmed that the visible light transmittance decreased and the near infrared ray blocking rate also decreased.

Referring to FIG. 8, the light transmittance (%) of the copper chalcogenide particles according to Examples 5 to 8 was measured in the ultraviolet to near-infrared region (200 nm to 1400 nm). As can be seen from FIG. 7, the copper chalcogenide particles according to Examples 5 to 8 show that the peak shifts to a short wavelength in the visible light region as the amount of selenium contained in the copper chalcogenide particles increases I could. Also, it was confirmed that as the amount of selenium contained in the copper chalcogenide particles increases, the lowest point in the near infrared region shifts to the shorter wavelength region.

(LSPR) peak, ultraviolet (UV) and near-infrared (NIR) blocking rates, visible transmittance (Vis) transmittance, and transmittance were measured using the light transmittance spectra of the copper calcined particles according to Examples 5 to 8, And the results are summarized in Table 4.

division Example 5 Example 6 Example 7 Example 8 Band gap (eV) 2.28 2.44 2.48 2.49 LSPR peak (nm) 1341 1224 1157 1134 UV cut rate (%) 99.61 98.51 97.91 97.73 Vis Viscosity (%) 50.48 58.63 59.48 57.11 NIR blocking rate (%) 80.98 79.81 82.05 81.68

As can be seen from Table 4, the copper-chalcogenide particles according to Examples 5 to 8 have an increased band gap as the proportion of selenium contained in the copper chalcogenide particles increases, It was confirmed that the resonance peak moves to a short wavelength region. As a result, it was confirmed that the visible light transmittance was increased and the near infrared ray blocking rate was also increased.

9 is a photograph of the copper carbocyanide light absorber according to Example 9 of the present invention taken by a transmission electron microscope.

Referring to FIG. 9, the copper-chalcogenide light absorber according to Example 9 was photographed by TEM. As can be seen from FIG. 9, it was confirmed that the copper chalcogenide light absorber according to Example 9 was coated with SiO 2 on the copper chalcogenide particles.

10 is a graph showing the characteristics of the copper carbocyanide particles and the light absorber according to Examples and Comparative Examples of the present invention.

10, the organic dye concentration of the copper chalcogenide particles and the light absorber according to the Comparative Examples 1, 1, 4, 5, 8 and 9 (min) Change (C / C 0 ) was measured. As can be seen from FIG. 10, when the light absorber of Comparative Example 1 was irradiated with light for 30 minutes, it was confirmed that about 72% of the organic dye was decomposed. On the other hand, it was confirmed that the copper chalcogenide particles according to Examples 1, 4, 5 and 8 decomposed up to 96% of the organic dye when light was irradiated for 30 minutes there was.

In addition, it was confirmed that when the copper carbocyanine light absorber according to Example 9 was irradiated with light for 30 minutes, the decomposition of the organic dye did not substantially take place. Thus, in the copper-chalcogenide light absorber according to Example 9, OH radicals are not generated on the surfaces of the copper chalcogenide particles, and SiO 2 coated on the copper chalcogenide particles prevents the photocatalyst phenomenon .

As a result, it is found that when the oxide is coated on the copper chalcogenide particles, the decomposition by light is minimized and the lifetime characteristics are improved. On the contrary, when the oxide is not coated on the copper chalcogenide particles, it is found that the photocatalyst has excellent characteristics. That is, when the oxide is not coated on the copper chalcogenide particles, the copper chalcogenide particles can be used as a photocatalyst.

11A to 11C are photographs of a light absorbing film according to an embodiment of the present invention.

Referring to FIGS. 11A to 11C, the light absorbing film according to Example 10 was manufactured at a thickness of 100 .mu.m, 300 .mu.m, and 500 .mu.m and photographed. As can be seen from FIGS. 11A to 11C, it was confirmed that the workability of the copper chalcogenide particles of the light absorbing film of Example 10 was increased.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the scope of the present invention is not limited to the disclosed exemplary embodiments. It will also be appreciated that many modifications and variations will be apparent to those skilled in the art without departing from the scope of the present invention.

Claims (12)

  1. Preparing a first source solution comprising sulfur (S) and selenium (Se);
    Mixing the first source solution with a second source solution comprising copper (Cu) to form a cooper chalcogenide particle comprising copper, selenium, and a compound of sulfur; And
    The copper chalcogenide particles are coated with an oxide containing at least one of SiO 2 , Al 2 O 3 , MgO, and Fe 2 O 3 , A method of making a copper chalcogenide light absorber comprising forming a co-crystal complex.
  2. The method according to claim 1,
    Wherein the copper chalcogenide composite contains ultraviolet light and near-infrared light at the same time.
  3. 3. The method of claim 2,
    Wherein the ultraviolet light is absorbed in a band gap region of the copper chalcogenide composite.
  4. 3. The method of claim 2,
    Wherein the near infrared rays are absorbed by a surface plasmon resonance phenomenon of the copper chalcogenide complex.
  5. The method according to claim 1,
    Wherein the second source solution comprises a reducing agent for controlling the content of copper contained in the copper chalcogenide particles.
  6. The method according to claim 1,
    The step of forming the copper chalcogenide composite comprises:
    Mixing a solution in which the copper chalcogenide particles are dispersed and a precursor of the oxide to prepare a mixed solution;
    Dripping a pH adjusting agent into the mixed solution; And
    And centrifuging the mixed solution in which the pH adjuster is immersed.
  7. Preparing a copper chalcogenide composite according to the production method of the copper chalcogenide light absorber according to claim 1;
    Mixing the copper chalcogenide complex with a binder; And
    And coating the copper chalcogenide composite with the binder on the base film.
  8. A copper chalcogenide composite comprising copper chalcogenide particles comprising a compound of copper, selenium, and sulfur, and an oxide coating the copper chalcogenide particles,
    Wherein the copper chalcogenide complex comprises simultaneously absorbing ultraviolet and near infrared rays and the oxide is selected from the group consisting of SiO 2 , Al 2 O 3 , MgO, and Fe 2 O 3 iron oxide. < RTI ID = 0.0 > 11. < / RTI >
  9. delete
  10. 9. The method of claim 8,
    Wherein the copper chalcogenide composite comprises a core-shell structure in which the surface of the copper chalcogenide particles is surrounded by the oxide.
  11. 9. The method of claim 8,
    Wherein the copper chalcogenide composite includes a structure in which the copper chalcogenide particles are distributed in an oxide matrix.
  12. A base film; And
    A copper-chalcogenide light-absorbing film comprising a copper-chalcogenide light absorber according to claim 8 coated on said base film.
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JP2006290738A (en) * 2005-04-13 2006-10-26 Corning Inc Chalcogenide glass for use in low viscosity-extrusion molding and -injection molding
KR20120098799A (en) * 2009-11-25 2012-09-05 이 아이 듀폰 디 네모아 앤드 캄파니 Aqueous process for producing crystalline copper chalcogenide nanoparticles, the nanoparticles so-produced, and inks and coated substrates incorporating the nanoparticles
KR101325728B1 (en) 2012-10-23 2013-11-08 주식회사 넥스필 Ultraviolet and infrared absorbable reiforcement film and manufacturing method therefor
JP2014502052A (en) * 2010-12-03 2014-01-23 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Inks and methods for producing sulfided / copper indium gallium selenide coatings and films
KR20160052160A (en) * 2014-11-04 2016-05-12 주식회사 엘지화학 Manufacturing Method of CI(G)S Nano Particle for Preparation of Light Absorbing Layer of Solar Cell and CI(G)S Nano Particle Manufactured thereof
KR20160052140A (en) * 2014-11-04 2016-05-12 주식회사 엘지화학 Copper Calcogenide Nano Particle for Manufacturing Light Absorbing Layer of Solar Cell and Method for Manufacturing the Same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006290738A (en) * 2005-04-13 2006-10-26 Corning Inc Chalcogenide glass for use in low viscosity-extrusion molding and -injection molding
KR20120098799A (en) * 2009-11-25 2012-09-05 이 아이 듀폰 디 네모아 앤드 캄파니 Aqueous process for producing crystalline copper chalcogenide nanoparticles, the nanoparticles so-produced, and inks and coated substrates incorporating the nanoparticles
JP2014502052A (en) * 2010-12-03 2014-01-23 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Inks and methods for producing sulfided / copper indium gallium selenide coatings and films
KR101325728B1 (en) 2012-10-23 2013-11-08 주식회사 넥스필 Ultraviolet and infrared absorbable reiforcement film and manufacturing method therefor
KR20160052160A (en) * 2014-11-04 2016-05-12 주식회사 엘지화학 Manufacturing Method of CI(G)S Nano Particle for Preparation of Light Absorbing Layer of Solar Cell and CI(G)S Nano Particle Manufactured thereof
KR20160052140A (en) * 2014-11-04 2016-05-12 주식회사 엘지화학 Copper Calcogenide Nano Particle for Manufacturing Light Absorbing Layer of Solar Cell and Method for Manufacturing the Same

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