DOWN-SHIFTING NANOPHOSPHORS, METHOD FOR PREPARING THE SAME, AND LUMINESCENT SOLAR CONCENTRATOR USING THE SAME

Abstract

The present disclosure relates to down-shifting nanophosphors, a method for preparing the same, and a luminescent solar concentrator (LSC) using the same. The down-shifting nanophosphors according to an embodiment of the present disclosure include a core including NaYF.sub.4 nanocrystals doped with neodymium (Nd) and ytterbium (Yb), and further include a neodymium (Nd)-doped crystalline shell surrounding the core, or further include a NaYF.sub.4 crystalline shell surrounding the crystalline shell. Therefore, the down-shifting nanophosphors efficiently absorb near infrared rays with a wavelength range of 700-900 nm and efficiently emit near infrared rays with a wavelength range of 950-1050 nm. In addition, the down-shifting nanophosphors according to an embodiment of the present disclosure has a size of 60 nm or less, and thus can be applied to manufacture transparent LSC films with ease and can realize transparent solar cell modules having high near infrared ray shifting efficiency.

Claims

1. Down-shifting nanophosphors comprising a core containing Nd.sup.3+- and Yb.sup.3+-doped fluoride-based nanoparticles represented by the following Chemical Formula 1:
NaY.sub.1-x-yF.sub.4: Nd.sup.3+.sub.x,Yb.sup.3+.sub.y   [Chemical Formula 1] wherein x is a real number satisfying 0.05≤x≤0.9, and y is a real number satisfying 0<y≤0.5, with the proviso that x and y are selected within such a range that they satisfy 0.05<x+y≤1.

2. The down-shifting nanophosphors according to claim 1, which further comprise an active shell containing a Nd.sup.3+-doped fluoride-based crystalline compound represented by the following Chemical Formula 2, and have a core-shell structure in which the active shell surrounds the core:
NaY.sub.1-pF.sub.4:Nd.sup.3+.sub.p   [Chemical Formula 2] wherein p is a real number satisfying 0<p≤0.5.

3. The down-shifting nanophosphors according to claim 2, which further comprise an inactive shell containing NaYF.sub.4 nanocrystals, and have a core-shell-shell structure in which the inactive shell surrounds the active shell.

4. The down-shifting nanophosphors according to claim 1, wherein the core has a size of 1-30 nm.

5. The down-shifting nanophosphors according to claim 1, wherein the core has a structure of hexagonal system.

6. The down-shifting nanophosphors according to claim 3, wherein the nanophosphors having a core-shell-shell structure has a size of 2-60 nm.

7. The down-shifting nanophosphors according to claim 1, which have a structure of hexagonal system.

8. The down-shifting nanophosphors according to claim 1, which have down-shifting light emission properties of absorbing near infrared rays with a wavelength range of 700-900 nm and emitting near infrared rays with a wavelength range of 950-1050 nm.

9. The down-shifting nanophosphors according to claim 8, wherein Nd.sup.3+ absorbs near infrared rays with a wavelength range of 700-900 nm, and Yb.sup.3+ emits near infrared rays with a wavelength range of 950-1050 nm.

10. A transparent polymer composite comprising the down-shifting nanophosphors as defined in claim 1.

11. A luminescent solar concentrator (LSC) comprising the down-shifting nanophosphors as defined in claim 1.

12. The luminescent solar concentrator according to claim 11, which is provided in the form of a transparent film.

13. A method for preparing down-shifting nanophosphors for a transparent luminescent solar concentrator (TLSC), comprising the steps of: (1) mixing an yttrium (Y) compound, neodymium (Nd) compound, ytterbium (Yb) compound, oleic acid and 1-octadecene, followed by heating, to form a first mixed solution containing a lanthanoid complex; (2) mixing the first mixed solution with a mixed solution of a sodium (Na) compound, fluorine (F) compound and an alcohol to form a first reaction solution; and (3) removing the alcohol from the first reaction solution and carrying out heat treatment to form Nd.sup.3+- and Yb.sup.3+-doped fluoride-based nanoparticles having a structure of hexagonal system represented by the following Chemical Formula 1:
NaY.sub.1-x-yF.sub.4: Nd.sup.3+.sub.x,Yb.sup.3+.sub.y   [Chemical Formula 1] wherein x is a real number satisfying 0.05≤x≤0.9, and y is a real number satisfying 0<y≤0.5, with the proviso that x and y are selected within such a range that they satisfy 0.05<x+y≤1.

14. The method for preparing down-shifting nanophosphors for a transparent luminescent solar concentrator (TLSC) according to claim 13, further comprising the steps of: (4) mixing an yttrium compound, neodymium compound, oleic acid and 1-octadecene, followed by heating, to form a second mixed solution containing a lanthanoid complex; (5) mixing the second mixed solution with the solution containing the nanoparticles represented by Chemical Formula 1, obtained from step (3), and with a mixed solution of a sodium compound, fluorine compound and an alcohol to form a second reaction solution; and (6) removing the alcohol from the second reaction solution and carrying out heat treatment to form active shells containing a Nd.sup.3+-doped fluoride-based crystalline compound represented by the following Chemical Formula 2 on the surfaces of the cores including the nanoparticles represented by Chemical Formula 1, thereby providing nanophosphors having a core-shell structure:
NaY.sub.1-pF.sub.4:Nd.sup.3+.sub.p   [Chemical Formula 2] wherein p is a real number satisfying 0<p≤0.5.

15. The method for preparing down-shifting nanophosphors for a transparent luminescent solar concentrator (TLSC) according to claim 14, further comprising the steps of: (7) mixing an yttrium compound, oleic acid and 1-octadecene, followed by heating, to form a third mixed solution; (8) mixing the third mixed solution with the solution containing the cores and the active shells, obtained from step (6), and with a mixed solution of a sodium compound, fluorine compound and an alcohol to form a third reaction solution; and (9) removing the alcohol from the third reaction solution and carrying out heat treatment to form inactive shells containing NaYF.sub.4 nanocrystals on the surfaces of the active shells, thereby providing nanophosphors having a core-shell-shell structure.

16. The method for preparing down-shifting nanophosphors for a transparent luminescent solar concentrator (TLSC) according to claim 13, wherein the ytterbium compound is any one selected from the group consisting of ytterbium chloride hexahydrate (YbCl.sub.3.6H.sub.2O), ytterbium acetate (Yb(CH.sub.3COO).sub.3), ytterbium chloride (YbCl.sub.3) and a combination thereof; the neodymium compound is any one selected from the group consisting of neodymium chloride hexahydrate (NdCl.sub.3.6H.sub.2O), neodymium acetate (Nd(CH.sub.3COO).sub.3), neodymium chloride (NdCl.sub.3) and a combination thereof; the yttrium compound is any one selected from the group consisting of yttrium chloride hexahydrate (YCl.sub.3.6H.sub.2O), yttrium acetate (Y(CH.sub.3COO).sub.3), yttrium chloride (YCl.sub.3) and a combination thereof; and the alcohol is any one selected from C1-C4 lower alcohols.

17. The method for preparing down-shifting nanophosphors for a transparent luminescent solar concentrator (TLSC) according to claim 14, wherein the neodymium compound is any one selected from the group consisting of neodymium chloride hexahydrate (NdCl.sub.3.6H.sub.2O), neodymium acetate (Nd(CH.sub.3COO).sub.3), neodymium chloride (NdCl.sub.3) and a combination thereof; the yttrium compound is any one selected from the group consisting of yttrium chloride hexahydrate (YCl.sub.3.6H.sub.2O), yttrium acetate (Y(CH.sub.3COO).sub.3), yttrium chloride (YCl.sub.3) and a combination thereof; and the alcohol is any one selected from C1-C4 lower alcohols.

18. The method for preparing down-shifting nanophosphors for a transparent luminescent solar concentrator (TLSC) according to claim 15, wherein the yttrium compound is any one selected from the group consisting of yttrium chloride hexahydrate (YCl.sub.3.6H.sub.2O), yttrium acetate (Y(CH.sub.3COO).sub.3), yttrium chloride (YCl.sub.3) and a combination thereof, and the alcohol is any one selected from C1-C4 lower alcohols.

19. The method for preparing down-shifting nanophosphors for a transparent luminescent solar concentrator (TLSC) according to claim 13, wherein the heat treatment in step (3) is carried out at a temperature of 200-400° C. for 10-200 minutes.

20. The method for preparing down-shifting nanophosphors for a transparent luminescent solar concentrator (TLSC) according to claim 15, wherein the heat treatment in steps (6) and (9) is carried out at a temperature of 200-400° C. for 10-200 minutes.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0013] FIG. 1 illustrates a transmission electron microscopic image of the core nanophosphors according to an embodiment of the present disclosure.

[0014] FIG. 2 illustrates an X-ray diffraction pattern of the core nanophosphors according to an embodiment of the present disclosure.

[0015] FIG. 3 illustrates a photoluminescence (PL) spectrum of the core nanophosphors according to an embodiment of the present disclosure.

[0016] FIG. 4 illustrates a transmission electron microscopic image of the nanophosphors having a core-shell structure according to an embodiment of the present disclosure.

[0017] FIG. 5 illustrates an X-ray diffraction pattern of the nanophosphors having a core-shell structure according to an embodiment of the present disclosure.

[0018] FIG. 6 illustrates a PL spectrum of the nanophosphors having a core-shell structure according to an embodiment of the present disclosure.

[0019] FIG. 7 illustrates a transmission electron microscopic image of the nanophosphors having a core-shell-shell structure according to an embodiment of the present disclosure.

[0020] FIG. 8 illustrates an X-ray diffraction pattern of the nanophosphors having a core-shell-shell structure according to an embodiment of the present disclosure.

[0021] FIG. 9 illustrates a PL spectrum of the nanophosphors having a core-shell-shell structure according to an embodiment of the present disclosure.

[0022] FIG. 10 is a schematic view illustrating a transparent solar cell module using a luminescent solar concentrator (LSC) film including the nanophosphors having a core-shell-shell structure according to an embodiment of the present disclosure and a solar cell.

[0023] FIG. 11 illustrates a photographic image of a transparent polymer film (LSC film) obtained by using the nanophosphors having a core-shell-shell structure according to an embodiment of the present disclosure.

[0024] FIG. 12 illustrates a transmittance spectrum of a transparent polymer film (LSC film) obtained by using the nanophosphors having a core-shell-shell structure according to an embodiment of the present disclosure.

[0025] FIG. 13 is a voltage-current density graph of a solar cell determined by using a transparent polymer film (LSC film) obtained by using the nanophosphors having a core-shell-shell structure according to an embodiment of the present disclosure.

DETAILED DESCRIPTION

[0026] Hereinafter, a detailed description of the present disclosure is given.

[0027] In one aspect of the present disclosure, there are provided down-shifting nanophosphors including a core containing Nd.sup.3+- and Yb.sup.3+-doped fluoride-based nanoparticles represented by the following Chemical Formula 1:

NaY.sub.1-x-yF.sub.4:Nd.sup.3+.sub.x, Yb.sup.3+.sub.y   [Chemical Formula 1]

[0028] wherein x is a real number satisfying 0.05≤x≤0.9, and y is a real number satisfying 0<y≤0.5, with the proviso that x and y are selected within such a range that they satisfy 0.05<x+y≤1.

[0029] According to an embodiment, the down-shifting nanophosphors may further include an active shell containing a Nd.sup.3+-doped fluoride-based crystalline compound represented by the following Chemical Formula 2, wherein the down-shifting nanophosphors may have a core-shell structure in which the active shell surrounds the core:

NaY.sub.1-pF.sub.4:Nd.sup.3+.sub.p   [Chemical Formula 2]

[0030] wherein p is a real number satisfying 0<p≤0.5.

[0031] According to another embodiment, the down-shifting nanophosphors may further include an inactive shell containing NaYF.sub.4 nanocrystals, wherein the down-shifting nanophosphors may have a core-shell-shell structure in which the inactive shell surrounds the active shell.

[0032] The down-shifting nanophosphors according to an embodiment of the present disclosure use NaYF.sub.4 crystals as cores and are doped suitably with a specific activator and coactivator, and thus can selectively absorb and emit near infrared rays with a specific wavelength range.

[0033] According to an embodiment, the core may have a size of 1-30 nm. More particularly, the core may have a particle size of 1 nm or more, 2 nm or more, 3 nm or more, 4 nm or more, 5 nm or more, 6 nm or more, 7 nm or more, 8 nm or more, 9 nm or more, 10 nm or more, 12 nm or more, 14 nm or more, 16 nm or more, 18 nm or more, 20 nm or more, 22 nm or more, 24 nm or more, 26 nm or more, or 28 nm or more. In addition, the core may have a particle size of 30 nm or less, 28 nm or less, 26 nm or less, 24 nm or less, 22 nm or less, 20 nm or less, 18 nm or less, 16 nm or less, 14 nm or less, 12 nm or less, 10 nm or less, 9 nm or less, 8 nm or less, 7 nm or less, 6 nm or less, 5 nm or less, 4 nm or less, 3 nm or less, or 2 nm or less.

[0034] According to an embodiment, the core may have a structure of hexagonal system, and the nanophosphors having a core-shell structure and the nanophosphors having a core-shell-shell structure may also have a structure of hexagonal system.

[0035] The nanophosphors having a core-shell-shell structure may have a size of 2-60 nm. More particularly, the nanophosphors having a core-shell-shell structure may have a particle size of 2 nm or more, 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 32 nm or more, 34 nm or more, 36 nm or more, 38 nm or more, 40 nm or more, 42 nm or more, 44 nm or more, 46 nm or more, 48 nm or more, 50 nm or more, 52 nm or more, 54 nm or more, 56 nm or more, or 58 nm or more. In addition, the nanophosphors having a core-shell-shell structure may have a particle size of 60 nm or less, 58 nm or less, 56 nm or less, 54 nm or less, 52 nm or less, 50 nm or less, 48 nm or less, 46 nm or less, 44 nm or less, 42 nm or less, 40 nm or less, 38 nm or less, 36 nm or less, 34 nm or less, 32 nm or less, 30 nm or less, 27 nm or less, 25 nm or less, 22 nm or less, 18 nm or less, 15 nm or less, 12 nm or less, 8 nm or less, 5 nm or less, or 3 nm or less.

[0036] As mentioned above, the nanophosphors according to an embodiment of the present disclosure has a significantly small size of 60 nm or less, and thus can be used to prepare a transparent polymer composite with ease and can be applied with ease to manufacture a luminescent solar concentrator in the form of a transparent film.

[0037] According to an embodiment, the down-shifting nanophosphors may absorb near infrared rays with a wavelength range of 700-900 nm and emit near infrared rays with a wavelength range of 950-1050 nm.

[0038] According to an embodiment, Nd.sup.3+ may absorb near infrared rays with a wavelength range of 700-900 nm and Yb.sup.3+ may emit near infrared rays with a wavelength range of 950-1050 nm.

[0039] In other words, Nd.sup.3+ may be doped as a coactivator for absorbing near infrared rays with a wavelength range of 700-900 nm, and Yb.sup.3+ may be doped as an activator for receiving the absorbed energy of near infrared rays and emitting near infrared rays with a wavelength range of 950-1050 nm.

[0040] In another aspect of the present disclosure, there is provided a transparent polymer composite including the down-shifting nanophosphors. Since the down-shifting nanophosphors have a uniform and small size, it is possible to obtain a significantly transparent polymer composite.

[0041] In still another aspect of the present disclosure, there is provided a luminescent solar concentrator (LSC) including the down-shifting nanophosphors.

[0042] According to an embodiment, the luminescent solar concentrator may be provided in the form of a transparent film. Since the down-shifting nanophosphors have a uniform and small size, it is possible to obtain an LSC in the form of a transparent film. In addition, since the down-shifting nanophosphors have high near infrared ray-emitting efficiency, they may be easily applied to a transparent LSC to be used for a transparent solar cell module.

[0043] In yet another aspect of the present disclosure, there is provided a method for preparing down-shifting nanophosphors for a transparent luminescent solar concentrator (TLSC), including the steps of: (1) mixing an yttrium (Y) compound, neodymium (Nd) compound, ytterbium (Yb) compound, oleic acid and 1-octadecene, followed by heating, to form a first mixed solution containing a lanthanoid complex; (2) mixing the first mixed solution with a mixed solution of a sodium (Na) compound, fluorine (F) compound and an alcohol to form a first reaction solution; and (3) removing the alcohol from the first reaction solution and carrying out heat treatment to form Nd.sup.3+- and Yb.sup.3+-doped fluoride-based nanoparticles represented by the above Chemical Formula 1.

[0044] According to an embodiment, the method for preparing down-shifting nanophosphors for TLSC may further include the steps of: (4) mixing an yttrium compound, neodymium compound, oleic acid and 1-octadecene, followed by heating, to form a second mixed solution containing a lanthanoid complex; (5) mixing the second mixed solution with the solution containing the nanoparticles represented by Chemical Formula 1, obtained from step (3), and with a mixed solution of a sodium compound, fluorine compound and an alcohol to form a second reaction solution; and (6) removing the alcohol from the second reaction solution and carrying out heat treatment to form active shells containing a Nd.sup.3+-doped fluoride-based crystalline compound represented by the above Chemical Formula 2 on the surfaces of the cores including the nanoparticles represented by Chemical Formula 1, thereby providing nanophosphors having a core-shell structure.

[0045] According to an embodiment, the method for preparing down-shifting nanophosphors for TLSC may further include the steps of: (7) mixing an yttrium compound, oleic acid and 1-octadecene, followed by heating, to form a third mixed solution; (8) mixing the third mixed solution with the solution containing the cores and the active shells, obtained from step (6), and with a mixed solution of a sodium compound, fluorine compound and an alcohol to form a third reaction solution; and (9) removing the alcohol from the third reaction solution and carrying out heat treatment to form inactive shells containing NaYF.sub.4 nanocrystals on the surfaces of the active shells, thereby providing nanophosphors having a core-shell-shell structure.

[0046] According to an embodiment, the ytterbium compound in step (1) may be any one selected from the group consisting of ytterbium chloride hydrate (YbCl.sub.3.6H.sub.2O), ytterbium acetate (Yb(CH.sub.3COO).sub.3), ytterbium chloride (YbCl.sub.3) and a combination thereof.

[0047] According to an embodiment, the neodymium compound in steps (1) and (4) may be any one selected from the group consisting of neodymium chloride hydrate (NdCl.sub.3.6H.sub.2O), neodymium acetate (Nd(CH.sub.3COO).sub.3), neodymium chloride (NdCl.sub.3) and a combination thereof.

[0048] According to an embodiment, the yttrium compound in steps (1), (4) and (7) may be any one selected from the group consisting of yttrium chloride hydrate (YCl.sub.3.6H.sub.2O), yttrium acetate (Y(CH.sub.3COO).sub.3), yttrium chloride (YCl.sub.3) and a combination thereof.

[0049] According to an embodiment, the alcohol may be any one selected from C1-C4 lower alcohols, preferably methanol.

[0050] According to an embodiment, the sodium compound may be sodium hydroxide, and the fluorine compound may be ammonium fluoride.

[0051] According to an embodiment, the heating in steps (1), (4) and (7) may be carried out at a temperature of 100-200° C. More particularly, the heating in steps (1), (4) and (7) may be carried out at a temperature of 100° C. or higher, 110° C. or higher, 120° C. or higher, 130° C. or higher, 140° C. or higher, 150° C. or higher, 160° C. or higher, 170° C. or higher, 180° C. or higher, or 190° C. or higher. In addition, the heating in steps (1), (4) and (7) may be carried out at a temperature of 200° C. or lower, 190° C. or lower, 180° C. or lower, 170° C. or lower, 160° C. or lower, 150° C. or lower, 140° C. or lower, 130° C. or lower, 120° C. or lower, or 110° C. or lower.

[0052] According to an embodiment, the heat treatment in steps (3), (6) and (9) may be carried out at 200-400° C. for 10-200 minutes.

[0053] According to another embodiment, the heat treatment in steps (3), (6) and (9) may be carried out at a temperature of 200° C. or higher, 220° C. or higher, 240° C. or higher, 260° C. or higher, 280° C. or higher, 300° C. or higher, 320° C. or higher, 340° C. or higher, 360° C. or higher, or 380° C. or higher. In addition, the heat treatment in steps (3), (6) and (9) may be carried out at a temperature of 400° C. or lower, 380° C. or lower, 360° C. or lower, 340° C. or lower, 320° C. or lower, 300° C. or lower, 280° C. or lower, 260° C. or lower, 240° C. or lower, or 220° C. or lower.

[0054] According to still another embodiment, the heat treatment in steps (3), (6) and (9) may be carried out for 10 minutes or more, 20 minutes or more, 30 minutes or more, 40 minutes or more, 50 minutes or more, 60 minutes or more, 70 minutes or more, 80 minutes or more, 90 minutes or more, 100 minutes or more, 120 minutes or more, 140 minutes or more, 160 minutes or more, or 180 minutes or more. In addition, the heat treatment in steps (3), (6) and (9) may be carried out for 200 minutes or less, 180 minutes or less, 160 minutes or less, 140 minutes or less, 120 minutes or less, 100 minutes or less, 90 minutes or less, 80 minutes or less, 70 minutes or less, 60 minutes or less, 50 minutes or less, 40 minutes or less, 30 minutes or less, or 20 minutes or less.

[0055] Hereinafter, the present disclosure will be described in detail with reference to examples and test examples. However, it will be apparent to those skilled in the art that these examples and test examples are provided for illustrative purposes only and the following examples are not intended to limit the scope of the present disclosure. It should be understood that various modifications, substitutions and additions known to those skilled in the art could be made thereto without departing from the scope of the disclosure.

<Example 1> Synthesis of NaY.SUB.0.85.F.SUB.4.:Nd.SUP.3+..SUB.0.05.,Yb.SUP.3+..SUB.0.1 .Core Nanophosphors

[0056] Core nanophosphors having a core represented by the chemical formula of NaY.sub.0.85F.sub.4:Nd.sup.3+.sub.0.05,Yb.sup.3+.sub.0.1 were synthesized through the following steps.

[0057] 1. Step of preparing first mixed solution: 0.85 mmol of yttrium chloride hydrate (YCl.sub.3.6H.sub.2O), 0.05 mmol of neodymium chloride hydrate (NdCl.sub.3.6H.sub.2O) and 0.1 mmol of ytterbium chloride hydrate (YbCl.sub.3.6H.sub.2O) were mixed with 6 mL of oleic acid and 15 mL of 1-octadecene as a solvent, and heated to 150° C. to prepare a first mixed solution including a lanthanoid complex.

[0058] 2. Step of preparing first reaction solution: 10 mL of methanol solution containing 2.5 mmol of sodium hydroxide and 4 mmol of ammonium fluoride was mixed with the first mixed solution including the lanthanoid complex to prepare a first reaction solution.

[0059] 3. Step of forming nanoparticles: Methanol was removed from the first reaction solution and the resultant product was heat treated at a temperature of 320° C. under argon (Ar) gas atmosphere for 60 minutes. During the heat treatment, beta (β)-NaY.sub.0.85F.sub.4:Nd.sup.3+.sub.0.05,Yb.sup.3+.sub.0.1 nanoparticles having a structure of hexagonal system were formed. The resultant nanoparticles were washed with ethanol, dispersed in a non-polar solvent, such as hexane, toluene or chloroform, and stored.

<Example 2> Synthesis of NaY.SUB.0.8.F.SUB.4.:Nd.SUP.3+..SUB.0.1.,Yb.SUP.3+..SUB.0.1 .Core Nanoparticles

[0060] Beta (β)-NaY.sub.0.8F.sub.4:Nd.sup.3+.sub.0.1,Yb.sup.3+.sub.0.1 nanoparticles having a structure of hexagonal system were synthesized in the same manner as Example 1, except that 0.8 mmol of yttrium chloride hydrate (YCl.sub.3.6H.sub.2O) and 0.1 mmol of neodymium chloride hydrate (NdCl.sub.3.6H.sub.2O) were used. The resultant nanoparticles were washed with ethanol, dispersed in a non-polar solvent, such as hexane, toluene or chloroform, and stored.

<Example 3> Synthesis of NaY.SUB.0.75.F.SUB.4.:Nd.SUP.3+..SUB.0.15.,Yb.SUP.3+..SUB.0.1 .Core Nanoparticles

[0061] Beta (β)-NaY.sub.0.75F.sub.4:Nd.sup.3+.sub.0.15,Yb.sup.3+.sub.0.1 nanoparticles having a structure of hexagonal system were synthesized in the same manner as Example 1, except that 0.75 mmol of yttrium chloride hydrate (YCl.sub.3.6H.sub.2O) and 0.15 mmol of neodymium chloride hydrate (NdCl.sub.3.6H.sub.2O) were used. The resultant nanoparticles were washed with ethanol, dispersed in a non-polar solvent, such as hexane, toluene or chloroform, and stored.

<Example 4> Synthesis of NaY.SUB.0.7.F.SUB.4.:Nd.SUP.3+..SUB.0.2.,Yb.SUP.3+..SUB.0.1 .Core Nanoparticles

[0062] Beta (β)-NaY.sub.0.7F.sub.4:Nd.sup.3+.sub.0.2,Yb.sup.3+.sub.0.1 nanoparticles having a structure of hexagonal system were synthesized in the same manner as Example 1, except that 0.7 mmol of yttrium chloride hydrate (YCl.sub.3.6H.sub.2O) and 0.2 mmol of neodymium chloride hydrate (NdCl.sub.3.6H.sub.2O) were used. The resultant nanoparticles were washed with ethanol, dispersed in a non-polar solvent, such as hexane, toluene or chloroform, and stored.

<Example 5> Synthesis of NaY.SUB.0.65.F.SUB.4.:Nd.SUP.3+..SUB.0.25.,Yb.SUP.3+..SUB.0.1 .Core Nanoparticles

[0063] Beta (β)-NaY.sub.0.65F.sub.4:Nd.sup.3+.sub.0.25,Yb.sup.3+.sub.0.1 nanoparticles having a structure of hexagonal system were synthesized in the same manner as Example 1, except that 0.65 mmol of yttrium chloride hydrate (YCl.sub.3.6H.sub.2O) and 0.25 mmol of neodymium chloride hydrate (NdCl.sub.3.6H.sub.2O) were used. The resultant nanoparticles were washed with ethanol, dispersed in a non-polar solvent, such as hexane, toluene or chloroform, and stored.

<Example 6> Synthesis of NaY.SUB.0.6.F.SUB.4.:Nd.SUP.3+..SUB.0.3.,Yb.SUP.3+..SUB.0.1 .Core Nanoparticles

[0064] Beta (β)-NaY.sub.0.6F.sub.4:Nd.sup.3+.sub.0.3,Yb.sup.3+.sub.0.1 nanoparticles having a structure of hexagonal system were synthesized in the same manner as Example 1, except that 0.6 mmol of yttrium chloride hydrate (YCl.sub.3.6H.sub.2O) and 0.3 mmol of neodymium chloride hydrate (NdCl.sub.3.6H.sub.2O) were used. The resultant nanoparticles were washed with ethanol, dispersed in a non-polar solvent, such as hexane, toluene or chloroform, and stored.

<Example 7> Synthesis of NaY.SUB.0.5.F.SUB.4.:Nd.SUP.3+..SUB.0.4.,Yb.SUP.3+..SUB.0.1 .Core Nanoparticles

[0065] Beta (β6)-NaY.sub.0.5F.sub.4:Nd.sup.3+.sub.0.4,Yb.sup.3+.sub.0.1 nanoparticles having a structure of hexagonal system were synthesized in the same manner as Example 1, except that 0.5 mmol of yttrium chloride hydrate (YCl.sub.3.6H.sub.2O) and 0.4 mmol of neodymium chloride hydrate (NdCl.sub.3.6H.sub.2O) were used. The resultant nanoparticles were washed with ethanol, dispersed in a non-polar solvent, such as hexane, toluene or chloroform, and stored.

<Example 8> Synthesis of NaY.SUB.0.4.F.SUB.4.:Nd.SUP.3+..SUB.0.5.,Yb.SUP.3+..SUB.0.1 .Core Nanoparticles

[0066] Beta (β)-NaY.sub.0.4F.sub.4:Nd.sup.3+.sub.0.5,Yb.sup.3+.sub.0.1 nanoparticles having a structure of hexagonal system were synthesized in the same manner as Example 1, except that 0.4 mmol of yttrium chloride hydrate (YCl.sub.3.6H.sub.2O) and 0.5 mmol of neodymium chloride hydrate (NdCl.sub.3.6H.sub.2O) were used. The resultant to nanoparticles were washed with ethanol, dispersed in a non-polar solvent, such as hexane, toluene or chloroform, and stored.

[0067] Each of the core nanophosphors according to Examples 1-8 was observed by using a transmission electron microscope (TEM) (Model: Tecnai F20, FEI). The TEM image is shown in FIG. 1. As shown in FIG. 1, it can be seen that the core nanophosphors according to an embodiment of the present disclosure show a uniform size of 30 nm or less.

[0068] Each of the core nanophosphors according to Examples 1-8 was analyzed by X-ray diffractometry using D8-Advance (Bruker). The results are shown in FIG. 2. As shown in FIG. 2, it can be seen that the core nanophosphors according to Examples 18 show a diffraction pattern conformed to the diffraction pattern of NaYF.sub.4 crystals (reference) having a structure of hexagonal system, and thus are present in a single hexagonal crystal phase free from impurities.

[0069] Each of the core nanophosphors according to Examples 1-8 was analyzed by photoluminescence (PL) spectrometry using a spectrophotometer (F-7000, Hitachi). The results are shown in FIG. 3. As shown in FIG. 3, it can be seen that the core nanophosphors according to Examples 1-8 show a broad near infrared ray emission band in a range of 950-1050 nm around a center of about 977 nm. Particularly, it can be seen that the core nanophosphors according to Example 6 show the highest light emission intensity.

<Example 9> Synthesis of Nanophosphors Having Core-Shell Structure Including NaY.SUB.0.6.F.SUB.4.:Nd.SUP.3+..SUB.0.3.,Yb.SUP.3+..SUB.0.1 .(Core)-NaYF.SUB.4 .(Shell)

[0070] Nanophosphors having a core-shell structure including the nanophosphors according to Example 6 as cores surrounded with NaYF.sub.4 crystalline shells were synthesized through the following steps.

[0071] 1. Step of preparing second mixed solution: 1 mmol of yttrium chloride hydrate (YCl.sub.3.6H.sub.2O) was mixed with 6 mL of oleic acid and 15 mL of 1-octadecene as a solvent and heated to 150° C. to prepare a second mixed solution including a lanthanoid complex.

[0072] 2. Step of preparing second reaction solution: 10 mL of the core nanophosphor solution synthesized according to Example 6 was introduced to the second mixed solution including a lanthanoid complex, and the resultant mixture was mixed with 10 mL of methanol solution containing 2.5 mmol of sodium hydroxide and 4 mmol of ammonium fluoride to prepare a second reaction solution.

[0073] 3. Step of forming nanoparticles: Methanol was removed from the second reaction solution and heat treated at a temperature of 320° C. under argon gas atmosphere for 60 minutes. During the heat treatment, beta (β)-NaY.sub.0.6F.sub.4:Nd.sup.3+.sub.0.3,Yb.sup.3+.sub.0.1 (core)-NaYF.sub.4 (shell) nanoparticles were formed. The resultant core-shell nanoparticles were washed with ethanol, dispersed in a non-polar solvent, such as hexane, toluene or chloroform, and stored.

<Example 10> Synthesis of Nanophosphors Having Core-Shell Structure Including NaY.SUB.0.6.F.SUB.4.:Nd.SUP.3+..SUB.0.3.,Yb.SUP.3+..SUB.0.1 .(Core)-NaY.SUB.0.9.F.SUB.4.:Nd.SUP.3+..SUB.0.1 .(Shell)

[0074] Beta ((β)-NaY.sub.0.6F.sub.4:Nd.sup.3+.sub.0.3,Yb.sup.3+.sub.0.1 (core)-NaY.sub.0.9F.sub.4:Nd.sup.3+.sub.0.1 (shell) nanoparticles were synthesized in the same manner as Example 9, except that 0.9 mmol of yttrium chloride hydrate (YCl.sub.3.6H.sub.2O) and 0.1 mmol of neodymium chloride hydrate (NdCl.sub.3.6H.sub.2O) were mixed with 6 mL of oleic acid and 15 mL of 1-octadecene in the step of forming a second mixed solution. The resultant core-shell nanoparticles were washed with ethanol, dispersed in a non-polar solvent, such as hexane, toluene or chloroform, and stored.

<Example 11> Synthesis of Nanophosphors Having Core-Shell Structure Including NaY.SUB.0.6.F.SUB.4.:Nd.SUP.3+..SUB.0.3.,Yb.SUP.3+..SUB.0.1 .(Core)-NaY.SUB.0.8.F.SUB.4.:Nd.SUP.3+..SUB.0.2 .(Shell)

[0075] Beta (β)-NaY.sub.0.6F.sub.4:Nd.sup.3+.sub.0.3,Yb.sup.3+.sub.0.1 (core)-NaY.sub.0.8F.sub.4:Nd.sup.3+.sub.0.2 (shell) nanoparticles were synthesized in the same manner as Example 9, except that 0.8 mmol of yttrium chloride hydrate (YCl.sub.3.6H.sub.2O) and 0.2 mmol of neodymium chloride hydrate (NdCl.sub.3.6H.sub.2O) were mixed with 6 mL of oleic acid and 15 mL of 1-octadecene in the step of forming a second mixed solution. The resultant core-shell nanoparticles were washed with ethanol, dispersed in a non-polar solvent, such as hexane, toluene or chloroform, and stored.

[0076] Each of the core-shell nanophosphors according to Examples 9-11 was observed by using a transmission electron microscope (TEM) (Model: Tecnai F20, FEI). The TEM image is shown in FIG. 4. When comparing FIG. 4 to FIG. 1, it can be seen that the particles have an increased size, since the shells surrounding the cores are formed.

[0077] Each of the core-shell nanophosphors according to Examples 9-11 was analyzed by X-ray diffractometry using D8-Advance (Bruker). The results are shown in FIG. 5. As shown in FIG. 5, it can be seen that the core-shell nanophosphors according to Examples 9-11 show a diffraction pattern conformed to the diffraction pattern of NaYF.sub.4 crystals (reference) having a structure of hexagonal system, and thus are present in a single hexagonal crystal phase free from impurities.

[0078] Each of the core nanophosphors according to Example 6 and the core-shell nanophosphors according to Examples 9-11 was analyzed by photoluminescence (PL) spectrometry using a spectrophotometer (F-7000, Hitachi). The results are shown in FIG. 6. As shown in FIG. 6, it can be seen that the core-shell nanophosphors according to Examples 9-11 show significantly high light emission intensity corresponding to twice or more of the light emission intensity of the core nanophosphors due to the formation of the shells surrounding the cores. It can be also seen that Examples 10 and 11 including NaYF.sub.4 crystals doped with neodymium show significantly higher light emission intensity as compared to Example 9 including shells, not doped with neodymium, and show a light emission intensity about 2.3 times of the light emission intensity of the core nanophosphors according to Example 6. Particularly, it can be seen that the nanophosphors including shells doped with 10% of neodymium according to Example 10 show the highest light emission intensity.

<Example 12> Synthesis of Nanophosphors Having Core-Shell-Shell Structure Including NaY.SUB.0.6.F.SUB.4.:Nd.SUP.3+..SUB.0.3.,Yb.SUP.3+..SUB.0.1 .(Core)-NaY.SUB.0.9.F.SUB.4.:Nd.SUP.3+..SUB.0.1 .(Shell)-NaYF.SUB.4 .(Shell)

[0079] Nanophosphors having a core-shell-shell structure including the nanophosphors having a core-shell structure according to Example 10 surrounded with NaYF.sub.4 crystalline inactive shells were synthesized through the following steps.

[0080] 1. Step of preparing third mixed solution: 1 mmol of yttrium chloride hydrate (YCl.sub.3.6H.sub.2O) was mixed with 6 mL of oleic acid and 15 mL of 1-octadecene as a solvent and heated to 150° C. to prepare a third mixed solution.

[0081] 2. Step of preparing third reaction solution: 10 mL of the core-shell nanophosphor solution synthesized according to Example 10 was introduced to the third mixed solution, and the resultant mixture was mixed with 10 mL of methanol solution containing 2.5 mmol of sodium hydroxide and 4 mmol of ammonium fluoride to prepare a third reaction solution.

[0082] 3. Step of forming nanoparticles: Methanol was removed from the third reaction solution and heat treated at a temperature of 320° C. under argon gas atmosphere for 60 minutes. During the heat treatment, beta (β)-NaY.sub.0.6F.sub.4:Nd.sup.3+.sub.0.3,Yb.sup.3+.sub.0.1 (core)-NaY.sub.0.9F.sub.4:Nd.sup.3+.sub.0.1 (Shell)-NaYF.sub.4 (shell) nanoparticles were formed. The resultant core-shell-shell nanoparticles were washed with ethanol, dispersed in a non-polar solvent, such as hexane, toluene or chloroform, and stored.

[0083] The core-shell-shell nanophosphors according to Example 12 were observed by using a transmission electron microscope (TEM) (Model: Tecnai F20, FEI). The TEM image is shown in FIG. 7. When comparing FIG. 7 to FIG. 4, it can be seen that the particles have an increased size, since the crystalline shells were further formed on the core-shell structures.

[0084] The core-shell-shell nanophosphors according to Example 12 were analyzed by X-ray diffractometry using D8-Advance (Bruker). The results are shown in FIG. 8. As shown in FIG. 8, it can be seen that the core-shell-shell nanophosphors according to Example 12 show a diffraction pattern conformed to the diffraction pattern of NaYF.sub.4 crystals (reference) having a structure of hexagonal system, and thus hexagonal-system shells are further formed uniformly around the core-shell structure of hexagonal-system with no impurities.

[0085] Each of the core nanophosphors according to Example 6, the core-shell nanophosphors according to Example 10 and the core-shell-shell nanophosphors according to Example 12 was analyzed by photoluminescence (PL) spectrometry using a spectrophotometer (F-7000, Hitachi). The results are shown in FIG. 9. As shown in FIG. 9, it can be seen that the core-shell nanophosphors according to Example 10 and the core-shell-shell nanophosphors according to Example 12 show significantly high light emission intensity corresponding to twice or more of the light emission intensity of the core nanophosphors. It can be also seen that the core-shell-shell nanophosphors further including the second shells show higher light emission intensity as compared to the core-shell nanophosphors. Particularly, the core-shell-shell nanophosphors show a light emission intensity about 2.6 times of the light emission intensity of the core nanophosphors according to Example 6.

<Example 13> Manufacture of Transparent Polymer Film Including Nanophosphors Having Core-Shell-Shell Structure Including NaY.SUB.0.6.F.SUB.4.:Nd.SUP.3+..SUB.0.3.,Yb.SUP.3+..SUB.0.1 .(Core)-NaY.SUB.0.9.F.SUB.4.:Nd.SUP.3+..SUB.0.1 .(Shell)-NaYF.SUB.4 .(Shell)

[0086] First, 0.5 mL of the core-shell-shell nanophosphors obtained from Example 12 were mixed with 10 mL of polydimethylsiloxane (PDMS) polymer and 1 mL of SYLGARD 184 as a curing agent to obtain a polymer mixture including the core-shell-shell nanophosphors. The polymer mixture was allowed to stand at 80° C. for 1 hour and cooled to room temperature to obtain a transparent polymer film including nanophosphors.

[0087] The resultant transparent polymer film may be applied to a luminescent solar concentrator (LSC). FIG. 10 is a schematic view illustrating a transparent solar cell module using the transparent polymer film including the nanophosphors according to an embodiment of the present disclosure and a solar cell.

[0088] As shown in FIG. 10, a transparent solar cell module may be obtained by applying the transparent polymer film including the core-shell-shell nanophosphors 105 according to an embodiment of the present disclosure to an LSC film 103 and applying solar cells 101 to both sides thereof.

[0089] FIG. 11 illustrates a photographic image of a transparent polymer film including the nanophosphors having a core-shell-shell structure according to Example 13. As shown in FIG. 11, it can be seen that the polymer film including the nanophosphors according to an embodiment of the present disclosure is significantly transparent.

[0090] The transparent polymer film including the nanophosphors having a core-shell-shell structure according to Example 13 was analyzed by Lambda25 spectrometer (Perkin-Elmer) to obtain a transmittance spectrum. FIG. 12 illustrates the transmittance spectrum. It can be seen from the result of FIG. 12 that the transparent polymer film including the nanophosphors having a core-shell-shell structure according to an embodiment of the present disclosure shows a high transmittance of 78.7% or more in the visible light region.

[0091] In addition, a solar cell was obtained by using the transparent polymer film including the nanophosphors having a core-shell-shell structure according to Example 13 as an LSC and determined for voltage and electric current by using AM 1.5 G (100 mWcm.sup.−2) light source of XES 301S solar simulator available from SAN-EI ELECTRIC Co. and 2400 source meter available from Keithley Co. The result is shown in FIG. 13. It can be seen from the result of FIG. 13 that when using the transparent polymer film including the core-shell-shell nanophosphors showing near infrared ray emission according to an embodiment of the present disclosure, as an LSC film, it is possible to obtain an efficiency of about 0.7%.

Description of Drawing Numerals

[0092] 101: Solar cell

[0093] 103: Luminescent solar concentrator film (LSC film)

[0094] 105: Core-shell-shell down-shifting nanophosphors