KR20190048646A - Multicolor tunable upconversion nanophosphors under various excitation wavelengths and method of fabricating the same - Google Patents

Abstract

The present invention relates to an up-conversion nano-phosphor capable of the excitation of multi-wavelength and light-emitting of multi-color which exhibits strong visible light emission under the excitation of not only at 980 nm infrared light but also at 800 nm infrared light by doping a shell with an activator using the nano-phosphor having a hexagonal core and shell structure, and is capable of light-emitting various colors ranging from blue to yellow and light green through composition control.

Description

TECHNICAL FIELD [0001] The present invention relates to an up-converting nanophosphor and a method for fabricating the same,

The present invention relates to an up-converted nanophosphor and a method of manufacturing the same, and more particularly, to an up-converted nanophosphor capable of emitting multi-wavelength excitation light and a method of manufacturing the same.

 Up-converting nano-phosphors are phosphors that emit light with high energy such as visible light by absorbing low-energy light such as infrared rays, and have a very small size of 100 nm or less. [Chem. Rev. vol. 104. vol. 104, 139-174 (2004)] At this time, according to the lanthanide element doped, the nanophosphores emit intrinsic color, blue when doped with Tm, and green when doped with Er. Since the luminescence of the upconverted nanophosphor appears by the transition of 4f-4f due to the transition of 4f electrons of Tm and Er ions, even if the type of the host changes or the size or shape of nanoparticles changes, . Therefore, the conventional up-converting nano-phosphors emit light of a few fixed colors such as blue, green or red, and it is difficult to obtain a different luminescent color other than the unique color emitted by each element.

In addition, most of the up-converting nano-phosphors are excited by near-infrared rays in the 980 nm wavelength band to emit visible light, and when excited to other wavelengths, it is difficult to obtain a desired luminescent color. In order to realize a transparent 3D volumetry display device, it is preferable to use an invisible infrared ray as an excitation source (Science 1999). In this case, various excitation light sources are used to emit various colors which are difficult to realize as an excitation light source A full color display can be realized. Therefore, it is expected that a transparent 3D volumetry display can be realized by applying up-converting nano-phosphors capable of emitting light of various colors while being excited by near-infrared rays of various wavelength bands while being capable of controlling emission color.

Disclosure of Invention Technical Problem [8] The present invention has been conceived to solve the problems of the prior art as described above, and it is an object of the present invention to provide a Yb activator capable of absorbing near infrared rays of 980 nm capable of converting infrared rays into visible light, Tm, Er is doped into the core, Nd capable of absorbing 800 nm of near infrared rays is doped with an activator, and the absorbed energy is transferred to the core, and the hexagonal system of the core / shell structure doped with Yb into the shell is raised The present invention also provides a nanophosphor having a core / shell structure capable of realizing various luminescent colors only by changing the composition ratio of the active agent doped into the core.

In one embodiment of the present invention, the multi-wavelength excited multicolor light-emitting up-converting nanophosphor is a compound of the formula (1) wherein Yb ³⁺ is doped and at least one selected from Tm ³⁺ and Er ³⁺ is doped A core comprising fluoride-based nanoparticles; And a fluoride-based compound doped with Nd ³⁺ and Yb ³⁺ , represented by the following formula (2), and surrounding at least a part of the core.

[Chemical Formula 1]

NaY _1-xyzw L _w F ₄ : Yb ³⁺ _x , Tm ³⁺ _y , Er ³⁺ _z

(Wherein x is a real number of 0 < x? 0.7, y is a real number of 0? Y? 0.1, z is a real number of 0? Z? 0.2, and w is 0? W Ce, Pr, Pm, Sm, Eu, and Z are real numbers satisfying 0 < x + y + z + w & Tb, Dy, Ho, and Lu.

(2)

NaY _1-pqr N _p F ₄ : Nd ³⁺ _q , Yb ³⁺ _r

P is a real number of 0? P? 1, q is a real number of 0? Q? 1, r is a real number of 0? R <1, 0 <p + q + and N is at least one selected from the group consisting of La, Ce, Pr, Pm, Sm, Eu, Tb, Dy, Ho, Er and Lu.

In the above multi-wavelength excited multicolor light-upturnable ^nanophosphor , Yb ³⁺ is an activator capable of absorbing near infrared rays in a 980 nm wavelength band, and Tm ³⁺ and Er ³⁺ in the formula (1) In the formula (2), Nd ³⁺ is an activator capable of absorbing near infrared rays in a wavelength band of 800 nm, and Yb ³⁺ in the formula (2) is an activator capable of absorbing energy absorbed from near- ^{Lt; RTI ID = 0.0} &gt; Tm &lt; / RTI &gt; ³⁺ and Er ³⁺ of the core.

In the multiwavelength excited multicolor light emitting uplink nanophosphor, the core has a single hexagonal crystal structure, and the nanophosphor having the core and the shell may have a single hexagonal crystal structure.

The display device according to another aspect of the present invention may include the nano-fluorescent substance described above.

The fluorescent contrast agent according to another aspect of the present invention may include the above-described nano-fluorescent substance.

A solar cell according to another aspect of the present invention may include the above-mentioned nanophosphor.

The anti-falsification code according to another aspect of the present invention may include the above-mentioned nano-fluorescent substance.

According to one aspect of the present invention, there is provided a method for producing a multi-wavelength excited multicolor light emission up-converting nano-phosphor, comprising the steps of: i) preparing a yttrium precursor; Ytterbium precursor; At least one precursor selected from a thulium precursor and an erbium precursor; Oleic acid; And 1-octadisene; a first mixed solution preparation step of forming a first mixed solution including a first mixed solution containing 1-octadecene; ii) heating the first mixed solution to form a solution containing the first lanthanide complex; iii) a reaction solution preparation step of mixing a second mixed solution containing a sodium precursor, a fluorine precursor and methanol with a solution containing the first lanthanide complex to prepare a first reaction solution; And iv) removing nanoparticles from the first reaction solution and forming nanoparticles by heat treatment. The nanoparticles are fluoride-based nanoparticles doped with Yb ³⁺ and doped with at least one selected from Tm ³⁺ and Er ³⁺ represented by the following formula (1).

[Chemical Formula 1]

NaY _1-xyzw L _w F ₄ : Yb ³⁺ _x , Tm ³⁺ _y , Er ³⁺ _z

(Wherein x is a real number of 0 < x? 0.7, y is a real number of 0? Y? 0.1, z is a real number of 0? Z? 0.2, and w is 0? W Ce, Pr, Pm, Sm, Eu, and Z are real numbers satisfying 0 < x + y + z + w & Tb, Dy, Ho, and Lu.

Wherein the yttrium precursor is at least one selected from the group consisting of yttrium chloride hydrate (YCl ₃ .6H ₂ O), yttrium acetate (Y (CH ₃ COO) ₃ ), yttrium chloride (YCl ₃ ) (YbCl ₃ .6H ₂ O), ytterbium acetate (Yb (CH ₃ COO) ₃ ), ytterbium chloride (YbCl ₃ ), and combinations thereof. The ytterbium precursor may be selected from the group consisting of ytterbium chloride ) and it is one selected from the group consisting of one, the thulium precursor chloride thulium hydrate _{(TmCl 3 · 6H 2 O)} , thulium acetate _{(Tm (CH 3 COO) 3} ), chloride, thulium (TmCl ₃₎ and these (ErCl ₃ .6H ₂ O), erbium acetate (Er (CH ₃ COO) ₃ ), erbium chloride (ErCl ₃ ), and combinations thereof. The erbium precursor may be selected from the group consisting of May be any one selected from the group consisting of

In the method for producing the multi-wavelength excited multicolor light emission up-converting nanophosphor, the heat treatment in the nanoparticle formation step may be performed at 250 ° C to 370 ° C for 10 minutes to 4 hours.

The method for producing the multiwavelength excited multicolor light emission uplink nanophosphor is a method for producing a nanoparticle comprising the steps of: v) forming a third mixed solution containing a yttrium precursor, a neodymium precursor, an ytterbium precursor, oleic acid and 1-octadisene, A third mixed solution preparing step of forming the third mixed solution; vi) heating the third mixed solution to form a solution containing the second lanthanide complex; vii) a fourth mixed solution preparation step of mixing a solution containing the nanoparticles formed in the nanoparticle formation step with a solution containing the second lanthanide complex to form a fourth mixed solution; viii) preparing a second reaction solution by mixing the fourth mixed solution with a fifth mixed solution including a sodium precursor, a fluorine precursor, and methanol to prepare a second reaction solution; And ix) removing the methanol from the second reaction solution and subjecting it to heat treatment to form a shell surrounding at least a part of the core. The shell may include a fluoride-based compound doped with Nd ³⁺ and Yb ³⁺ represented by the following formula (2).

(2)

NaY _1-pqr N _p F ₄ : Nd ³⁺ _q , Yb ³⁺ _r

P is a real number of 0? P? 1, q is a real number of 0? Q? 1, r is a real number of 0? R <1, 0 <p + q + and N is at least one selected from the group consisting of La, Ce, Pr, Pm, Sm, Eu, Tb, Dy, Ho, Er and Lu.

Wherein the yttrium precursor is at least one selected from the group consisting of yttrium chloride hydrate (YCl ₃ .6H ₂ O), yttrium acetate (Y (CH ₃ COO) ₃ ), yttrium chloride (YCl ₃ ) (YbCl ₃ .6H ₂ O), ytterbium acetate (Yb (CH ₃ COO) ₃ ), ytterbium chloride (YbCl ₃ ), and combinations thereof. The ytterbium precursor may be selected from the group consisting of ytterbium chloride ) And a combination thereof. The neodymium precursor is at least one selected from the group consisting of neodymium chloride hydrate (NdCl ₃ .6H ₂ O), neodymium acetate (Nd (CH ₃ COO) ₃ ), neodymium chloride (NdCl ₃ ) Or a combination thereof.

In the method for producing the multi-wavelength excitation multi-color light emission up-converting nano-phosphor, the heat treatment in the shell-making step may be performed at 250 ° C to 370 ° C for 10 minutes to 4 hours.

According to another aspect of the present invention, the up-converted nanophosphor is a core and shell-structured up-converted nanophosphor having a hexagonal crystal structure, and can be excited by infrared rays of 980 nm and 800 nm to exhibit multi- It is an up-conversion nanophosphor that can emit multi-wavelength light with multiple wavelengths.

As described in detail above, according to the present invention, an inorganic nano-fluorescent substance excited by a single wavelength ultraviolet ray to exhibit strong green light emission and emitting various colors such as blue, sky blue, cyan, and green is obtained, Since it uses light emission by transition, there is no flickering phenomenon, and light stability is excellent. Therefore, it can be used as a transparent display device. In addition, since it is possible to use infrared rays in a wavelength band having low harmfulness to the living body and a low degree of absorption of cells as an excitation source, it can be used as a contrast medium for bioimaging. However, these effects are exemplary and do not limit the scope of the present invention.

1 is a transmission electron microscope photograph of a core up-converting nano-phosphor according to a preferred embodiment of the present invention.
2 is an X-ray diffraction pattern of a core up-converting nano-phosphor according to a preferred embodiment of the present invention.
3 is a schematic view of a multicolor luminescent up-conversion nano-phosphor of a core / shell structure according to an embodiment of the present invention.
4 is a transmission electron micrograph of a core / shell structure up-converting nanophosphor according to a preferred embodiment of the present invention.
5 is an X-ray diffraction pattern of a core / shell structure up-converting nano-phosphor according to a preferred embodiment of the present invention.
FIG. 6 is a light emission spectrum of nano-phosphors having core and core / shell structures excited by 980 nm infrared rays according to a preferred embodiment of the present invention.
FIG. 7 is a light emission spectrum of a nano-fluorescent material having a core / shell structure according to a preferred embodiment of the present invention when it is excited by 980 nm infrared rays.
FIG. 8 is a photoluminescence image of a core / shell structure nano-phosphor according to a preferred embodiment of the present invention when it is excited by 980 nm infrared rays.
FIG. 9 is an emission spectrum of nano-phosphors having a core and a core / shell structure according to a preferred embodiment of the present invention excited by 800 nm infrared rays.
FIG. 10 is an emission spectrum of a nano-phosphor having a core / shell structure according to a preferred embodiment of the present invention when it is excited by 800 nm infrared rays.
11 is a photograph of a nano-fluorescent material having a core / shell structure according to a preferred embodiment of the present invention excited by 800 nm infrared rays.

Hereinafter, a description will be made of an up-converted nano-phosphor capable of emitting various colors under 980 nm and 800 nm infrared ray excitation according to a preferred embodiment of the present invention, with reference to the accompanying drawings. The up-converted nano-phosphors of the present invention are characterized in that an activator capable of absorbing 980 nm infrared light and an activator capable of emitting visible light are doped into the core, and an activator capable of absorbing 800 nm infrared light, Is doped into the shell to form a core / shell structure. However, the present invention is not limited to the embodiments shown in the drawings, and other embodiments may be easily suggested by adding, replacing, etc. components.

However, the embodiments of the present invention described above and shown in the drawings should not be construed as limiting the technical idea of the present invention, and the embodiments of the present invention are provided to more fully describe the present invention.

The present invention relates to a nanofluorescent material applicable to security fields such as a fluorescent contrast agent, a light emitting portion of a transparent display device, a wavelength conversion portion of a solar cell, and anti-counterfeiting, and a method of synthesizing the same. More specifically, the present invention relates to a core / shell structure up-converting nano-phosphor capable of converting invisible near-infrared rays into visible light, which is excited by near-infrared rays of two wavelengths of 980 nm and 800 nm, To a nano-fluorescent substance which emits visible light of color. In other words, the present invention is a nano-fluorescent material having a hexagonal core / shell structure and exhibits strong visible light emission not only at 980 nm infrared but also at 800 nm infrared ray excitation by doping the shell with an activator. Discloses an up-converted nanophosphor capable of emitting a multi-wavelength excited multicolor light capable of emitting light of a color.

Hereinafter, a specific embodiment of a method of manufacturing a multicolor light emission up-conversion nano-phosphor according to the technical idea of the present invention will be described.

&Lt; Example 1 > ³⁺  And Tm ³⁺  Manufacture of Upgraded Core Nano Phosphor

0.74 mmol of yttrium chloride hydrate (YCl ₃揃 6H ₂ O) as a yttrium precursor, 0.25 mmol of ytterbium chloride hydrate (YbCl ₃揃 6H ₂ O) as a ytterbium precursor, thulium chloride hydrate (TmCl ₃揃 6H ₂ O) 0.01 mmol is mixed with a solution containing oleic acid and 1-octadecene to form a first mixed solution (first mixed solution preparation step). The first mixed solution is heat-treated at 150 ° C for 30 minutes to form a mixed solution containing the first lanthanide complex (complex compound forming step).

2.5 mmol of sodium hydroxide as a sodium precursor and 10 ml of a methanol solution containing 4 mmol of ammonium fluoride as a fluorine precursor were mixed into the first mixed solution to prepare a second mixed solution ). Thereafter, the second mixed solution is mixed with the mixed solution containing the first lanthanide complex to form a first reaction solution (first reaction solution preparation step).

After the first reaction solution was sufficiently mixed, methanol was removed and heat treatment was performed in an inert gas atmosphere. At this time, when the heat treatment temperature is lower than 250 ° C, a single hexagonal crystal is not completely formed, and thus the phosphor does not exhibit strong luminescence. If the temperature is higher than 370 ° C, aggregation of particles occurs due to excessive reaction, resulting in a very large particle size, a uniform distribution of the size, and a disadvantage that the luminance is lowered. Therefore, it is preferable that the heat treatment temperature is 250 to 370 ° C and the heat treatment time is 10 minutes to 4 hours (nanoparticle formation step). After the heat treatment is completed, the nanopowder is cooled to room temperature and a colloidal nanoporous phosphor having a diameter of 1 to 50 nm is obtained. The nano-phosphors thus prepared were washed with acetone or ethanol and dispersed in a non-polar solvent such as hexane, toluene or chloroform. The nanoparticles prepared in Example 1 were NaY _0.74 F ₄ : Yb ³⁺ _0.25 and Tm ³⁺ _0.01 .

&Lt; Example 2 > Yb ³⁺  And Tm ³⁺ And 0.1% Er ³⁺  Manufacture of Upgraded Core Nano Phosphor

0.739 mmol of yttrium chloride hydrate (YCl ₃揃 6H ₂ O) as a yttrium precursor, 0.25 mmol of ytterbium chloride hydrate (YbCl ₃揃 6H ₂ O) as an ytterbium precursor, thulium chloride hydrate (TmCl ₃揃 6H ₂ O) 0.01 mmol, and 0.001 mmol of erbium chloride hydrate (ErCl ₃ .6H ₂ O) as an erbium precursor were mixed with a solution containing oleic acid and 1-octadecene to form a first mixed solution (first mixed solution preparation step). The first mixed solution is heat-treated at 150 ° C for 30 minutes to form a mixed solution containing the first lanthanide complex (complex compound forming step).

2.5 mmol of sodium hydroxide as a sodium precursor and 10 ml of a methanol solution containing 4 mmol of ammonium fluoride as a fluorine precursor were mixed into the first mixed solution to prepare a second mixed solution ). Thereafter, the second mixed solution is mixed with the mixed solution containing the first lanthanide complex to form a first reaction solution (first reaction solution preparation step).

After the first reaction solution was sufficiently mixed, methanol was removed and heat treatment was performed in an inert gas atmosphere. At this time, when the heat treatment temperature is lower than 250 ° C, a single hexagonal crystal is not completely formed, and thus the phosphor does not exhibit strong luminescence. If the temperature is higher than 370 ° C, aggregation of particles occurs due to excessive reaction, resulting in a very large particle size, a uniform distribution of the size, and a disadvantage that the luminance is lowered. Therefore, it is preferable that the heat treatment temperature is 250 to 370 ° C and the heat treatment time is 10 minutes to 4 hours (nanoparticle formation step). After the heat treatment is completed, the nanopowder is cooled to room temperature and a colloidal nanoporous phosphor having a diameter of 1 to 50 nm is obtained. The nano-phosphors thus prepared were washed with acetone or ethanol and dispersed in a non-polar solvent such as hexane, toluene or chloroform. The nanoparticles prepared in Example 2 were NaY _0.739 F ₄ : Yb ³⁺ _0.25 , Tm ³⁺ _0.01 , and Er ³⁺ _0.001 .

&Lt; Example 3 > ³⁺  And Tm ³⁺ And 0.2% Er ³⁺  Manufacture of Upgraded Core Nano Phosphor

0.738 mmol of yttrium chloride hydrate (YCl ₃揃 6H ₂ O) as a yttrium precursor, 0.25 mmol of ytterbium chloride hydrate (YbCl ₃揃 6H ₂ O) as an ytterbium precursor, 13.0 g of thulium chloride hydrate (TmCl ₃揃 6H ₂ O) 0.01 mmol, and 0.002 mmol of erbium chloride hydrate (ErCl ₃ .6H ₂ O) as an erbium precursor are mixed with a solution containing oleic acid and 1-octadecene to form a first mixed solution (first mixed solution preparation step). The first mixed solution is heat-treated at 150 ° C for 30 minutes to form a mixed solution containing the first lanthanide complex (complex compound forming step).

2.5 mmol of sodium hydroxide as a sodium precursor and 10 ml of a methanol solution containing 4 mmol of ammonium fluoride as a fluorine precursor were mixed into the first mixed solution to prepare a second mixed solution ). Thereafter, the second mixed solution is mixed with the mixed solution containing the first lanthanide complex to form a first reaction solution (first reaction solution preparation step).

After the first reaction solution was sufficiently mixed, methanol was removed and heat treatment was performed in an inert gas atmosphere. At this time, when the heat treatment temperature is lower than 250 ° C, a single hexagonal crystal is not completely formed, and thus the phosphor does not exhibit strong luminescence. If the temperature is higher than 370 ° C, aggregation of particles occurs due to excessive reaction, resulting in a very large particle size, a uniform distribution of the size, and a disadvantage that the luminance is lowered. Therefore, it is preferable that the heat treatment temperature is 250 to 370 ° C and the heat treatment time is 10 minutes to 4 hours (nanoparticle formation step). After the heat treatment is completed, the nanopowder is cooled to room temperature and a colloidal nanoporous phosphor having a diameter of 1 to 50 nm is obtained. The nano-phosphors thus prepared were washed with acetone or ethanol and dispersed in a non-polar solvent such as hexane, toluene or chloroform. The nanoparticles prepared in Example 3 were NaY _0.738 F ₄ : Yb ³⁺ _0.25 , Tm ³⁺ _0.01 , and Er ³⁺ _0.002 .

&Lt; Example 4 > ³⁺  And Tm ³⁺ And 0.3% Er ³⁺  Manufacture of Upgraded Core Nano Phosphor

0.737 mmol of yttrium chloride hydrate (YCl ₃揃 6H ₂ O) as a yttrium precursor, 0.25 mmol of ytterbium chloride hydrate (YbCl ₃揃 6H ₂ O) as an ytterbium precursor, thulium chloride hydrate (TmCl ₃揃 6H ₂ O) 0.01 mmol, and 0.003 mmol of erbium chloride hydrate (ErCl ₃ .6H ₂ O) as an erbium precursor were mixed with a solution containing oleic acid and 1-octadecene to form a first mixed solution (first mixed solution preparation step). The first mixed solution is heat-treated at 150 ° C for 30 minutes to form a mixed solution containing the first lanthanide complex (complex compound forming step).

2.5 mmol of sodium hydroxide as a sodium precursor and 10 ml of a methanol solution containing 4 mmol of ammonium fluoride as a fluorine precursor were mixed into the first mixed solution to prepare a second mixed solution ). Thereafter, the second mixed solution is mixed with the mixed solution containing the first lanthanide complex to form a first reaction solution (first reaction solution preparation step).

After the first reaction solution was sufficiently mixed, methanol was removed and heat treatment was performed in an inert gas atmosphere. At this time, when the heat treatment temperature is lower than 250 ° C, a single hexagonal crystal is not completely formed, and thus the phosphor does not exhibit strong luminescence. If the temperature is higher than 370 ° C, aggregation of particles occurs due to excessive reaction, resulting in a very large particle size, a uniform distribution of the size, and a disadvantage that the luminance is lowered. Therefore, it is preferable that the heat treatment temperature is 250 to 370 ° C and the heat treatment time is 10 minutes to 4 hours (nanoparticle formation step). After the heat treatment is completed, the nanopowder is cooled to room temperature and a colloidal nanoporous phosphor having a diameter of 1 to 50 nm is obtained. The nano-phosphors thus prepared were washed with acetone or ethanol and dispersed in a non-polar solvent such as hexane, toluene or chloroform. The nanoparticles prepared in Example 4 are NaY _0.737 F _4: Yb ³⁺ _0.25 , Tm ³⁺ _0.01 , and Er ³⁺ _0.003 .

&Lt; Example 5 > ³⁺  And Tm ³⁺ And 0.5% Er ³⁺  Manufacture of Upgraded Core Nano Phosphor

0.735 mmol of yttrium chloride hydrate (YCl ₃ .6H ₂ O) as yttrium precursor, 0.25 mmol of ytterbium chloride hydrate (YbCl ₃ .6H ₂ O) as ytterbium precursor, 13.0 g of thulium chloride hydrate (TmCl ₃ .6H ₂ O) 0.01 mmol, and 0.005 mmol of erbium chloride hydrate (ErCl ₃ .6H ₂ O) as an erbium precursor are mixed with a solution containing oleic acid and 1-octadecene to form a first mixed solution (first mixed solution preparation step). The first mixed solution is heat-treated at 150 ° C for 30 minutes to form a mixed solution containing the first lanthanide complex (complex compound forming step).

2.5 mmol of sodium hydroxide as a sodium precursor and 10 ml of a methanol solution containing 4 mmol of ammonium fluoride as a fluorine precursor were mixed into the first mixed solution to prepare a second mixed solution ). Thereafter, the second mixed solution is mixed with the mixed solution containing the first lanthanide complex to form a first reaction solution (first reaction solution preparation step).

After the first reaction solution was sufficiently mixed, methanol was removed and heat treatment was performed in an inert gas atmosphere. At this time, when the heat treatment temperature is lower than 250 ° C, a single hexagonal crystal is not completely formed, and thus the phosphor does not exhibit strong luminescence. If the temperature is higher than 370 ° C, aggregation of particles occurs due to excessive reaction, resulting in a very large particle size, a uniform distribution of the size, and a disadvantage that the luminance is lowered. Therefore, it is preferable that the heat treatment temperature is 250 to 370 ° C and the heat treatment time is 10 minutes to 4 hours (nanoparticle formation step). After the heat treatment is completed, the nanopowder is cooled to room temperature and a colloidal nanoporous phosphor having a diameter of 1 to 50 nm is obtained. The nano-phosphors thus prepared were washed with acetone or ethanol and dispersed in a non-polar solvent such as hexane, toluene or chloroform. The nanoparticles prepared in Example 5 were NaY _0.735 F ₄ : Yb ³⁺ _0.25 , Tm ³⁺ _0.01 , and Er ³⁺ _0.005 .

&Lt; Example 6 > ³⁺  And Er ³⁺  Manufacture of Upgraded Core Nano Phosphor

0.73 mmol of yttrium chloride hydrate (YCl ₃ .6H ₂ O) as a yttrium precursor, 0.25 mmol of ytterbium chloride hydrate (YbCl ₃ .6H ₂ O) as an ytterbium precursor, erbium chloride hydrate (ErCl ₃ .6H ₂ O) 0.02 mmol is mixed with a solution containing oleic acid and 1-octadisene to form a first mixed solution (first mixed solution preparation step). The first mixed solution is heat-treated at 150 ° C for 30 minutes to form a mixed solution containing the first lanthanide complex (complex compound forming step).

2.5 mmol of sodium hydroxide as a sodium precursor and 10 ml of a methanol solution containing 4 mmol of ammonium fluoride as a fluorine precursor were mixed into the first mixed solution to prepare a second mixed solution ). Thereafter, the second mixed solution is mixed with the mixed solution containing the first lanthanide complex to form a first reaction solution (first reaction solution preparation step).

After the first reaction solution was sufficiently mixed, methanol was removed and heat treatment was performed in an inert gas atmosphere. At this time, when the heat treatment temperature is lower than 250 ° C, a single hexagonal crystal is not completely formed, and thus the phosphor does not exhibit strong luminescence. If the temperature is higher than 370 ° C, aggregation of particles occurs due to excessive reaction, resulting in a very large particle size, a uniform distribution of the size, and a disadvantage that the luminance is lowered. Therefore, it is preferable that the heat treatment temperature is 250 to 370 ° C and the heat treatment time is 10 minutes to 4 hours (nanoparticle formation step). After the heat treatment is completed, the nanopowder is cooled to room temperature and a colloidal nanoporous phosphor having a diameter of 1 to 50 nm is obtained. The nano-phosphors thus prepared were washed with acetone or ethanol and dispersed in a non-polar solvent such as hexane, toluene or chloroform. The nanoparticles prepared in Example 6 are NaY _0.73 F ₄ : Yb ³ _+0.25 and Er ^{3 +} _0.02 .

FIG. 1 shows a transmission electron microscope photograph of the core up-converting nano-phosphors synthesized through Examples 1 to 6 of the present invention. Referring to FIG. 1, core nano-phosphors having a uniform size within 45 nm are synthesized.

FIG. 2 shows X-ray diffraction patterns of the core upconverted nano-phosphors synthesized through Examples 1 to 6 of the present invention. The core nano-phosphors synthesized from FIG. 2 had a single hexagonal crystal phase .

&Lt; Example 7 > ³⁺  And Tm ³⁺  Resurfaced Upconversion Core / Shell Nano Phosphor Manufacture

Prepared in Example ^{_{1 NaY 0.74 F 4: Yb 3+}} 0.25, Tm 3+ 0.01 to nanoparticles in the core of the core / shell structure comprising a shell, Nd ³⁺ and Yb ³⁺ resurrection the NaYF ₄ fluoride-based compound Nano-phosphors were prepared.

0.5 mmol of yttrium chloride hydrate (YCl ₃揃 6H ₂ O) as a yttrium precursor, 0.4 mmol of neodymium chloride hydrate (NdCl ₃揃 6H ₂ O) as a neodymium precursor, 30 ml of ytterbium chloride hydrate (YbCl ₃揃 6H ₂ O) 0.05 mmol is mixed with a solution containing oleic acid and 1-octadecene to form a third mixed solution (third mixed solution preparation step). The third mixed solution is heat-treated at 150 ° C for 30 minutes to form a solution containing the second lanthanide complex (second complex formation step).

A solution containing NaY _0.74 F ₄ : Yb ³ _+0.25 and Tm ³ _+0.01 nanoparticles prepared in Example 1 was mixed with the solution containing the second Lanthanide complex to prepare a fourth mixed solution 4 mixed solution preparation step).

2.5 mmol of sodium hydroxide as a sodium precursor and 10 ml of a methanol solution containing 4 mmol of ammonium fluoride as a fluorine precursor are mixed to prepare a fifth mixed solution. The fourth mixed solution is mixed with the fifth mixed solution to prepare a second reaction solution (second reaction solution preparation step).

After the second reaction solution was sufficiently mixed, methanol was removed and heat treatment was performed in an inert gas atmosphere. If the annealing temperature is less than 200 ° C, a single hexagonal nanocrystal is not completely formed and the phosphor does not exhibit strong luminescence. If the temperature is higher than 370 ° C, aggregation of particles occurs due to excessive reaction, resulting in a very large particle size, a uniform distribution of the size, and a disadvantage that the luminance is lowered. Therefore, the heat treatment temperature is preferably 200 to 370 DEG C and the heat treatment time is preferably 10 minutes to 4 hours (core / shell formation step). After the heat treatment is completed and the mixture is cooled to room temperature, a colloidal nanoporous phosphor having a diameter of 1 to 60 nm is obtained. The nano-phosphors thus prepared were washed with acetone or ethanol and dispersed in a non-polar solvent such as hexane, toluene or chloroform.

&Lt; Example 8 > ³⁺  And Tm ³⁺ And 0.1% Er ³⁺  Resurfaced Upconversion Core / Shell Nano Phosphor Manufacture

The NaY _0.739 F ₄ : Yb ³⁺ _0.25 , Tm ³⁺ _0.01 , and Er ³⁺ _0.001 nanoparticles prepared in Example 2 as the core were used as the shell to contain Nd ³⁺ and Yb ³⁺ -activated NaYF ₄ fluoride-based compounds as a shell To prepare a nanophosphor with a core / shell structure.

0.5 mmol of yttrium chloride hydrate (YCl ₃揃 6H ₂ O) as a yttrium precursor, 0.4 mmol of neodymium chloride hydrate (NdCl ₃揃 6H ₂ O) as a neodymium precursor, 30 ml of ytterbium chloride hydrate (YbCl ₃揃 6H ₂ O) 0.05 mmol is mixed with a solution containing oleic acid and 1-octadecene to form a third mixed solution (third mixed solution preparation step). The third mixed solution is heat-treated at 150 ° C for 30 minutes to form a solution containing the second lanthanide complex (second complex formation step).

A solution containing NaY _0.739 F ₄ : Yb ³⁺ _0.25 , Tm ³⁺ _0.01 , and Er ³⁺ _0.001 nanoparticles prepared in Example 2 was mixed with a solution containing the second lanthanide complex, (Fourth mixed solution preparation step).

2.5 mmol of sodium hydroxide as a sodium precursor and 10 ml of a methanol solution containing 4 mmol of ammonium fluoride as a fluorine precursor are mixed to prepare a fifth mixed solution. The fourth mixed solution is mixed with the fifth mixed solution to prepare a second reaction solution (second reaction solution preparation step).

After the second reaction solution was sufficiently mixed, methanol was removed and heat treatment was performed in an inert gas atmosphere. If the annealing temperature is less than 200 ° C, a single hexagonal nanocrystal is not completely formed and the phosphor does not exhibit strong luminescence. If the temperature is higher than 370 ° C, aggregation of particles occurs due to excessive reaction, resulting in a very large particle size, a uniform distribution of the size, and a disadvantage that the luminance is lowered. Therefore, the heat treatment temperature is preferably 200 to 370 DEG C and the heat treatment time is preferably 10 minutes to 4 hours (core / shell formation step). After the heat treatment is completed and the mixture is cooled to room temperature, a colloidal nanoporous phosphor having a diameter of 1 to 60 nm is obtained. The nano-phosphors thus prepared were washed with acetone or ethanol and dispersed in a non-polar solvent such as hexane, toluene or chloroform.

&Lt; Example 9 > ³⁺  And Tm ³⁺ And 0.2% Er ³⁺  Resurfaced Upconversion Core / Shell Nano Phosphor Manufacture

The NaY _0.738 F ₄ : Yb ³⁺ _0.25 , Tm ³⁺ _0.01 , and Er ³⁺ _0.002 nanoparticles prepared in Example 3 as a core were used as a shell to contain Nd ³⁺ and Yb ³⁺ -activated NaYF ₄ fluoride-based compounds as a shell To prepare a nanophosphor with a core / shell structure.

0.5 mmol of yttrium chloride hydrate (YCl ₃揃 6H ₂ O) as a yttrium precursor, 0.4 mmol of neodymium chloride hydrate (NdCl ₃揃 6H ₂ O) as a neodymium precursor, 30 ml of ytterbium chloride hydrate (YbCl ₃揃 6H ₂ O) 0.05 mmol is mixed with a solution containing oleic acid and 1-octadecene to form a third mixed solution (third mixed solution preparation step). The third mixed solution is heat-treated at 150 ° C for 30 minutes to form a solution containing the second lanthanide complex (second complex formation step).

A solution containing NaY _0.738 F ₄ : Yb ³⁺ _0.25 , Tm ³⁺ _0.01 , and Er ³⁺ _0.002 nanoparticles prepared in Example 3 was mixed with a solution containing the second lanthanide complex, (Fourth mixed solution preparation step).

2.5 mmol of sodium hydroxide as a sodium precursor and 10 ml of a methanol solution containing 4 mmol of ammonium fluoride as a fluorine precursor are mixed to prepare a fifth mixed solution. The fourth mixed solution is mixed with the fifth mixed solution to prepare a second reaction solution (second reaction solution preparation step).

After the reaction solution was sufficiently mixed, methanol was removed and heat treatment was performed in an inert gas atmosphere. If the annealing temperature is less than 200 ° C, a single hexagonal nanocrystal is not completely formed and the phosphor does not exhibit strong luminescence. If the temperature is higher than 370 ° C, aggregation of particles occurs due to excessive reaction, resulting in a very large particle size, a uniform distribution of the size, and a disadvantage that the luminance is lowered. Therefore, the heat treatment temperature is preferably 200 to 370 DEG C and the heat treatment time is preferably 10 minutes to 4 hours (nanoparticle formation step). After the heat treatment is completed and the mixture is cooled to room temperature, a colloidal nanoporous phosphor having a diameter of 1 to 60 nm is obtained. The nano-phosphors thus prepared were washed with acetone or ethanol and dispersed in a non-polar solvent such as hexane, toluene or chloroform.

&Lt; Example 10 > ³⁺  And Tm ³⁺ And 0.3% Er ³⁺  Resurfaced Upconversion Core / Shell Nano Phosphor Manufacture

The NaY _0.737 F _4: Yb ³⁺ _0.25 , Tm ³⁺ _0.01 , and Er ³⁺ _0.003 nanoparticles prepared in Example 4 were used as a core to contain Nd ³⁺ and Yb ³⁺ -activated NaYF ₄ fluoride-based compounds as a shell To prepare a nanophosphor with a core / shell structure.

0.5 mmol of yttrium chloride hydrate (YCl ₃揃 6H ₂ O) as a yttrium precursor, 0.4 mmol of neodymium chloride hydrate (NdCl ₃揃 6H ₂ O) as a neodymium precursor, 30 ml of ytterbium chloride hydrate (YbCl ₃揃 6H ₂ O) 0.05 mmol is mixed with a solution containing oleic acid and 1-octadecene to form a third mixed solution (third mixed solution preparation step). The third mixed solution is heat-treated at 150 ° C for 30 minutes to form a solution containing the second lanthanide complex (second complex formation step).

A solution containing the NaY _0.737 F ₄ : Yb ³⁺ _0.25 , Tm ³⁺ _0.01 , and Er ³⁺ _0.003 nanoparticles prepared in Example 4 was mixed with the solution containing the second lanthanide complex, (Fourth mixed solution preparation step).

2.5 mmol of sodium hydroxide as a sodium precursor and 10 ml of a methanol solution containing 4 mmol of ammonium fluoride as a fluorine precursor are mixed to prepare a fifth mixed solution. The fourth mixed solution is mixed with the fifth mixed solution to prepare a second reaction solution (second reaction solution preparation step).

After the reaction solution was sufficiently mixed, methanol was removed and heat treatment was performed in an inert gas atmosphere. If the annealing temperature is less than 200 ° C, a single hexagonal nanocrystal is not completely formed and the phosphor does not exhibit strong luminescence. If the temperature is higher than 370 ° C, aggregation of particles occurs due to excessive reaction, resulting in a very large particle size, a uniform distribution of the size, and a disadvantage that the luminance is lowered. Therefore, the heat treatment temperature is preferably 200 to 370 DEG C and the heat treatment time is preferably 10 minutes to 4 hours (nanoparticle formation step). After the heat treatment is completed and the mixture is cooled to room temperature, a colloidal nanoporous phosphor having a diameter of 1 to 60 nm is obtained. The nano-phosphors thus prepared were washed with acetone or ethanol and dispersed in a non-polar solvent such as hexane, toluene or chloroform.

Example 11 Synthesis of Yb ³⁺  And Tm ³⁺ And 0.5% Er ³⁺  Resurfaced Upconversion Core / Shell Nano Phosphor Manufacture

The NaY _0.735 F ₄ : Yb ³⁺ _0.25 , Tm ³⁺ _0.01 , and Er ³⁺ _0.005 nanoparticles prepared in Example 5 were used as a core to contain Nd ³⁺ and Yb ³⁺ -activated NaYF ₄ fluoride-based compounds as a shell To prepare a nanophosphor with a core / shell structure.

0.5 mmol of yttrium chloride hydrate (YCl ₃揃 6H ₂ O) as a yttrium precursor, 0.4 mmol of neodymium chloride hydrate (NdCl ₃揃 6H ₂ O) as a neodymium precursor, 30 ml of ytterbium chloride hydrate (YbCl ₃揃 6H ₂ O) 0.05 mmol is mixed with a solution containing oleic acid and 1-octadecene to form a third mixed solution (third mixed solution preparation step). The third mixed solution is heat-treated at 150 ° C for 30 minutes to form a solution containing the second lanthanide complex (second complex formation step).

A solution containing the NaY _0.735 F ₄ : Yb ³⁺ _0.25 , Tm ³⁺ _0.01 , and Er ³⁺ _0.005 nanoparticles prepared in Example 5 was mixed with the solution containing the second lanthanide complex, (Fourth mixed solution preparation step).

2.5 mmol of sodium hydroxide as a sodium precursor and 10 ml of a methanol solution containing 4 mmol of ammonium fluoride as a fluorine precursor are mixed to prepare a fifth mixed solution. The fourth mixed solution is mixed with the fifth mixed solution to prepare a second reaction solution (second reaction solution preparation step).

After the second reaction solution was sufficiently mixed, methanol was removed and heat treatment was performed in an inert gas atmosphere. If the annealing temperature is less than 200 ° C, a single hexagonal nanocrystal is not completely formed and the phosphor does not exhibit strong luminescence. If the temperature is higher than 370 ° C, aggregation of particles occurs due to excessive reaction, resulting in a very large particle size, a uniform distribution of the size, and a disadvantage that the luminance is lowered. Therefore, the heat treatment temperature is preferably 200 to 370 DEG C and the heat treatment time is preferably 10 minutes to 4 hours (nanoparticle formation step). After the heat treatment is completed and the mixture is cooled to room temperature, a colloidal nanoporous phosphor having a diameter of 1 to 60 nm is obtained. The nano-phosphors thus prepared were washed with acetone or ethanol and dispersed in a non-polar solvent such as hexane, toluene or chloroform.

Example 12 Synthesis of Yb ³⁺  And Er ³⁺  Resurfaced Upconversion Core / Shell Nano Phosphor Manufacture

The above-described NaY prepared in example ^{_{6 0.73 F 4: Yb 3+ 0.25}} , Er 3+ 0.02 to nanoparticles in the core of the core / shell structure comprising a shell, Nd ³⁺ and Yb ³⁺ resurrection the NaYF ₄ fluoride-based compound Nano-phosphors were prepared.

0.5 mmol of yttrium chloride hydrate (YCl ₃揃 6H ₂ O) as a yttrium precursor, 0.4 mmol of neodymium chloride hydrate (NdCl ₃揃 6H ₂ O) as a neodymium precursor, 30 ml of ytterbium chloride hydrate (YbCl ₃揃 6H ₂ O) 0.05 mmol is mixed with a solution containing oleic acid and 1-octadecene to form a third mixed solution (third mixed solution preparation step). The third mixed solution is heat-treated at 150 ° C for 30 minutes to form a solution containing the second lanthanide complex (second complex formation step).

A solution containing NaY _0.73 F ₄ : Yb ³⁺ _0.25 and Er ³⁺ _0.02 nanoparticles prepared in Example 6 was mixed with a solution containing the second lanthanide complex to prepare a fourth mixed solution 4 mixed solution preparation step).

2.5 mmol of sodium hydroxide as a sodium precursor and 10 ml of a methanol solution containing 4 mmol of ammonium fluoride as a fluorine precursor are mixed to prepare a fifth mixed solution. The fourth mixed solution is mixed with the fifth mixed solution to prepare a second reaction solution (second reaction solution preparation step).

After the second reaction solution was sufficiently mixed, methanol was removed and heat treatment was performed in an inert gas atmosphere. If the annealing temperature is less than 200 ° C, a single hexagonal nanocrystal is not completely formed and the phosphor does not exhibit strong luminescence. If the temperature is higher than 370 ° C, aggregation of particles occurs due to excessive reaction, resulting in a very large particle size, a uniform distribution of the size, and a disadvantage that the luminance is lowered. Therefore, the heat treatment temperature is preferably 200 to 370 DEG C and the heat treatment time is preferably 10 minutes to 4 hours (nanoparticle formation step). After the heat treatment is completed and the mixture is cooled to room temperature, a colloidal nanoporous phosphor having a diameter of 1 to 60 nm is obtained. The nano-phosphors thus prepared were washed with acetone or ethanol and dispersed in a non-polar solvent such as hexane, toluene or chloroform.

In the above-described embodiments, various precursors have exemplarily described the specific substance, but the technical idea of the present invention is not limited to the specific substance. In view of this, the yttrium precursor may be any one selected from the group consisting of yttrium chloride hydrate (YCl ₃ .6H ₂ O), yttrium acetate (Y (CH ₃ COO) ₃ ), yttrium chloride (YCl ₃ ) Wherein the ytterbium precursor is selected from the group consisting of ytterbium chloride (YbCl ₃ .6H ₂ O), ytterbium acetate (Yb (CH ₃ COO) ₃ ), ytterbium chloride (YbCl ₃ ) which can be one, wherein the thulium precursor chloride thulium hydrate _{(TmCl 3 · 6H 2 O)} , thulium acetate _{(Tm (CH 3 COO) 3} ), chloride, thulium (TmCl ₃₎ and which is selected from the group consisting of It is one days, and the erbium precursor is chloride, erbium hydrate _{(ErCl 3 · 6H 2 O)} , erbium acetate _{(Er (CH 3 COO) 3} ), chloride, erbium (ErCl ₃₎ and at least one selected from the group consisting of days, and the precursor is neodymium chloride, neodymium hydrate _{(NdCl 3 · 6H 2 O)} , Audio may be a di acetate _{(Nd (CH 3 COO) 3} ), neodymium chloride (NdCl ₃₎ and at least one selected from the group consisting of.

FIG. 3 is a schematic view of an up-converted nano-phosphor having a core / shell structure according to an embodiment of the present invention. The core is doped with an activator capable of emitting visible light and an activator capable of absorbing 980 nm infrared. The shell is doped with a activator capable of absorbing 800 nm infrared and a curing agent capable of transferring the absorbed energy. Structure, it is possible to absorb infrared rays of 980 nm and 800 nm, and it is possible to emit various visible rays from blue to green by controlling the composition ratio of the dopant in the core.

FIG. 4 shows a transmission electron microscope photograph of the core / shell structure up-converting nano-phosphors synthesized through Examples 7 to 8 of the present invention. It can be seen that the NaYF ₄ shell is formed around the core and the size of the nanoparticles is increased. The core / shell nano-phosphors synthesized from the X-ray diffraction pattern of the upconverted nano- It can be confirmed that it has a single hexagonal crystal structure like the nanophosphor.

6, it can be seen that the luminescence intensity is greatly improved by forming a shell around the core. When the up-converted nanophosphor of the core / shell structure is excited by infrared rays as compared with the core nano- Is significantly increased.

FIG. 7 shows the emission spectra of the core / shell nanopowders synthesized through Examples 7 to 12. It can be seen from the emission spectrum under the illustrated 980 nm infrared excitation that the intensity of the emission peak in the green spectral range increases with the change of the concentration of the active agent doped into the core as compared with the emission peak intensity in the blue spectral range, From the nanophosphor luminescence photograph of the core / shell structure synthesized through Examples 7 to 12, it can be seen that the emission color changes from blue to yellow as the doping concentration of Er ³⁺ increases in the core.

The luminescence spectra of the core and the core / shell nanophosphor under the 800 nm infrared ray excitation condition shown in FIG. 9 are shown. The core nanopowder synthesized through Example 1 had no emission peak, whereas the core / shell nanopowder synthesized through Example 7 exhibited an intrinsic emission peak of Tm ³⁺ in the blue spectral region. 9, it can be seen that the core / shell nano-phosphors emit light not only by the 980 nm infrared ray but also by the infrared ray of 800 nm band through the activator doped in the shell.

FIG. 10 shows emission spectra of nanoporous phosphors of core / shell structure synthesized through Examples 7 to 12 by excitation with a 800 nm infrared laser. The intensity of the emission peak in the green spectral region tends to increase with increasing intensity of the emission peak in the blue spectral region as the concentration of doped Er ³⁺ increases in the core as in the case of exciting with 980 nm infrared, From the nanophosphor luminescence photograph of the core / shell structure synthesized through Examples 7 to 12, it can be seen that the emission color changes from blue to lime green as the doping concentration of Er ³⁺ increases in the core.

Up to now, the above-described up-converted nanophosphors capable of emitting multi-wavelength excitation light can be applied to a display device, a fluorescent contrast agent, a solar cell or an anti-falsification code.

Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. It will be understood that the present invention can be changed.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. will be.

Claims (14)

To core comprising at least a nanoparticle of any one of the doped, fluoride-based selected from, Yb ³⁺ is doped with Er ³⁺ and Tm ³⁺ represented by the general formula (1); And
A shell comprising a fluoride-based compound doped with Nd ³⁺ and Yb ³⁺ , wherein at least a portion of the core is surrounded by the shell;
Wherein the multi-wavelength excited polychromatic light-emitting up-converting nanophosphor.
[Chemical Formula 1]
NaY _1-xyzw L _w F ₄ : Yb ³⁺ _x , Tm ³⁺ _y , Er ³⁺ _z
(Wherein x is a real number of 0 < x? 0.7, y is a real number of 0? Y? 0.1, z is a real number of 0? Z? 0.2, and w is 0? W Ce, Pr, Pm, Sm, Eu, and Z are real numbers satisfying 0 < x + y + z + w & Tb, Dy, Ho, and Lu.
(2)
NaY _1-pqr N _p F ₄ : Nd ³⁺ _q , Yb ³⁺ _r
P is a real number of 0? P? 1, q is a real number of 0? Q? 1, r is a real number of 0? R <1, 0 <p + q + and N is at least one selected from the group consisting of La, Ce, Pr, Pm, Sm, Eu, Tb, Dy, Ho, Er and Lu. The method according to claim 1,
In Formula 1, Yb ³⁺ is an activator capable of absorbing near infrared rays in a wavelength band of 980 nm. In Formula 1, Tm ³⁺ and Er ³⁺ are activators capable of emitting blue and green. In Formula 2, Nd ³⁺ is an activator capable of absorbing near-infrared light in a wavelength band of 800 nm, and Yb ³⁺ in the formula 2 is an energy absorbed from 800 nm near infrared rays, at least one of Tm ³⁺ and Er ³⁺ Wherein the multi-wavelength excited nanopowder is a multi-wavelength excitation light source. The method according to claim 1,
Wherein the core has a single hexagonal crystal structure, and the nanophosphor having the core and the shell also have a single hexagonal crystal structure. A display device comprising the nanophosphor according to claim 1. A fluorescent contrast agent comprising the nanophosphor according to claim 1. A solar cell comprising the nanophosphor according to claim 1. An anti-fake cord comprising the nanophosphor according to claim 1. Yttrium precursor; Ytterbium precursor; At least one precursor selected from a thulium precursor and an erbium precursor; Oleic acid; And 1-octadisene; a first mixed solution preparation step of forming a first mixed solution including a first mixed solution,
A first complex compound forming step of heating the first mixed solution to form a solution containing the first lanthanide complex,
Preparing a first reaction solution by mixing a second mixed solution containing a sodium precursor, a fluorine precursor, and methanol with a solution containing the first lanthanide complex, and
Forming nanoparticles by removing methanol from the first reaction solution and forming a nanoparticle by heat treatment
Lt; / RTI &gt;
Wherein the nanoparticles are fluoride nanoparticles doped with Yb ³⁺ and doped with at least one selected from Tm ³⁺ and Er ³⁺ represented by the following formula 1: (Method for producing converted nano phosphor).
[Chemical Formula 1]
NaY _1-xyzw L _w F ₄ : Yb ³⁺ _x , Tm ³⁺ _y , Er ³⁺ _z
(Wherein x is a real number of 0 < x? 0.7, y is a real number of 0? Y? 0.1, z is a real number of 0? Z? 0.2, and w is 0? W Ce, Pr, Pm, Sm, Eu, and Z are real numbers satisfying 0 &lt; x + y + z + w & Tb, Dy, Ho, and Lu. 9. The method of claim 8,
The yttrium precursor is any one selected from the group consisting of yttrium chloride hydrate (YCl ₃ .6H ₂ O), yttrium acetate (Y (CH ₃ COO) ₃ ), yttrium chloride (YCl ₃ )
Wherein the ytterbium precursor is any one selected from the group consisting of ytterbium chloride (YbCl ₃ .6H ₂ O), ytterbium acetate (Yb (CH ₃ COO) ₃ ), ytterbium chloride (YbCl ₃ ) ,
The precursor thulium thulium chloride hydrate _{(TmCl 3 · 6H 2 O)} , thulium acetate _{(Tm (CH 3 COO) 3} ), thulium chloride (TmCl ₃₎ and at least one selected from the group consisting of and,
Wherein the erbium precursor is any one selected from the group consisting of erbium chloride (ErCl ₃ .6H ₂ O), erbium acetate (Er (CH ₃ COO) ₃ ), erbium chloride (ErCl ₃ )
A method for producing an up - converted nanophosphor capable of multi - wavelength excitation of multicolored light. 9. The method of claim 8,
Wherein the heat treatment in the nanoparticle formation step is performed at 250 ° C to 370 ° C for 10 minutes to 4 hours. 9. The method of claim 8,
After the nanoparticle formation step,
A third mixed solution preparation step of forming a third mixed solution including a yttrium precursor, a neodymium precursor, an ytterbium precursor, oleic acid, and 1-octadecene;
A second complex compound forming step of heating the third mixed solution to form a solution containing a second lanthanide complex;
A fourth mixed solution preparation step of mixing a solution containing the nanoparticles formed in the nanoparticle formation step with a solution containing the second lanthanide complex to form a fourth mixed solution;
Mixing the fourth mixed solution with a fifth mixed solution containing a sodium precursor, a fluorine precursor, and methanol to prepare a second reaction solution; And
Removing the methanol from the second reaction solution and heat treating the shell to form a shell surrounding at least a part of the core;
Further comprising:
Wherein the shell comprises a fluoride-based compound doped with Nd ³⁺ and Yb ³⁺ represented by the following formula (2).
(2)
NaY _1-pqr N _p F ₄ : Nd ³⁺ _q , Yb ³⁺ _r
P is a real number of 0? P? 1, q is a real number of 0? Q? 1, r is a real number of 0? R <1, 0 <p + q + and N is at least one selected from the group consisting of La, Ce, Pr, Pm, Sm, Eu, Tb, Dy, Ho, Er and Lu. 12. The method of claim 11,
The yttrium precursor is any one selected from the group consisting of yttrium chloride hydrate (YCl ₃ .6H ₂ O), yttrium acetate (Y (CH ₃ COO) ₃ ), yttrium chloride (YCl ₃ )
Wherein the ytterbium precursor is any one selected from the group consisting of ytterbium chloride (YbCl ₃ .6H ₂ O), ytterbium acetate (Yb (CH ₃ COO) ₃ ), ytterbium chloride (YbCl ₃ ) ,
Wherein the neodymium precursor is any one selected from the group consisting of neodymium chloride hydrate (NdCl ₃ .6H ₂ O), neodymium acetate (Nd (CH ₃ COO) ₃ ), neodymium chloride (NdCl ₃ ) ,
A method for producing an up - converted nanophosphor capable of multi - wavelength excitation of multicolored light. 12. The method of claim 11,
Wherein the heat treatment in the shell forming step is performed at 200 ° C to 370 ° C for 10 minutes to 4 hours. The present invention relates to an up-converting nanophosphor capable of emitting multi-wavelength excited multicolor light, which can be excited by infrared rays of 980 nm and 800 nm and exhibiting multicolor emission with a core and shell structure of a hexagonal crystal structure.

Images