KR101979082B1 - Upconversion Phosphors Comprising Non Stoichiometric Host and Method of Manufacturing Same - Google Patents

Abstract

The present invention relates to a phosphor capable of achieving a higher emission efficiency and luminescent color control than a conventional phosphor by including a non-stoichiometric oxyfluoride-based host. The present invention also provides a method for producing a non-stoichiometric oxyfluoride-based phosphor.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an up-conversion phosphor containing a non-stoichiometric host,

The present invention relates to an up-conversion phosphor containing a non-stoichiometric matrix, and more particularly to a non-stoichiometric phosphor which has high emission efficiency in a high energy region of visible light through low energy excitation of near- To an up-converting phosphor including a matrix.

The present invention also relates to a method for producing an up-conversion phosphor comprising said non-stoichiometric matrix.

Up-conversion phosphor refers to a micro-sized inorganic substance in a nano that emits light when it is included in a sensor, a display, an image, a light energy therapy, a solar cell, etc. In this case, an electron having a high energy level is transferred to a more stable energy level To the light.

Generally, luminescence occurs by downconversion, which emits light having energy smaller than the energy absorbed by the phosphor. However, in some cases, the phosphor emits light with energy greater than that absorbed by the phosphor. This phenomenon is called upconversion. Since the base-level electrons are excited to the level of the high-energy state via the intermediate energy level, the up-conversion phenomenon may occur even when the output of the excitation light source is weak.

Generally, a hydrothermal synthesis method, a sol-gel synthesis method, a complex polymerization method and the like are used for the phosphor. However, the above processes have a problem that the pressure is difficult to control and the raw material is expensive. On the other hand, the flour aid aid method has a merit that the process is relatively simple and the raw material is low cost.

Up-conversion takes place in the co-doped matrix acting as a sensitizer and activator. In the case of energy transfer upconversion (ETU), energy is transferred to the active agent by doping a sensitizer that absorbs infrared rays well. High up conversion efficiency can be obtained. In order to increase the efficiency, the nanopattern process may be used, the phosphor may be combined with the metal particles, or the mother body may be formed into a core-shell structure as in Korean Patent No. 10-164675, but the process is complicated and it is difficult to control the luminescent color .

The emission color can be controlled by controlling the intensity of the emission peak by the type of the host, the kind of the doping element, the amount of the doping element, the combination of the phosphors, and the combination of the metal particles and the phosphor. The range of luminous color that can be obtained is narrow.

In order to solve the problems of low emission efficiency and luminescent color control, development of a phosphor having a new composition has been required.

Korean Patent No. 10-1676268 Korean Patent No. 10-1646675

It is an object of the present invention to provide a phosphor containing a non-stoichiometric matrix, which is more efficient than a stoichiometric matrix and easily controls luminescent color. Another object of the present invention is to provide a method for producing a phosphor through simple materials and processes.

According to an aspect of the present invention, there is provided an oxyfluoride-based phosphor having the following general formula (1), wherein p and q in the general formula (1) are not integers.

P is a real number of 0.55? P? 0.75, q is a real number of 1.5? Q? 1.9, x is a real number of 0? X? 0.3, and A is a rare earth ion except La.

The oxyfluoride-based phosphor according to another embodiment of the present invention is represented by the following general formula (2), and p and q in the general formula (2) are not integers.

P is a real number of 0.55? P? 0.75, q is a real number of 1.5? Q? 1.9, w is a real number of 0? W? 0.1 and x is a real number of 0? X? , Y is a real number satisfying 0? Y? 0.05, and z is a real number satisfying 0? Z? 0.1.

The phosphor ^{Er 3 +, Tm 3 +,} Ho 3 +, the content of Yb ^{3 +} are each ^{(0 mol% ≤ Er 3 +} ≤ 10 mol%), (0 mol% ≤ Tm 3 + ≤ 5 mol%), ( 0 mol%? Ho ^{3 +} ? 5 mol%), (0 mol%? Yb ^{3 +} ? 10 mol%).

The emission wavelength of the phosphor may be in the range of 360 nm?? 820 nm.

The emission characteristic of the phosphor may be an up conversion.

The structure of the phosphor may be tetragonal.

A method of producing a phosphor according to one embodiment of the present invention, wherein p and q are not integers, comprises the steps of: preparing a first powder by mixing La precursor and A precursor; Adding the first powder to NH ₄ F and then drying to produce a second powder; And heat treating the second powder.

[Chemical Formula 1]

P is a real number of 0.55? P? 0.75, q is a real number of 1.5? Q? 1.9, x is a real number of 0? X? 0.3, and A is a rare earth ion except La.

Wherein the La precursor is any one selected from the group consisting of La ₂ O _{3 ,} La (NO ₃ ) ₃ and LaF ₃ , the A precursor is A ₂ O ₃ , A (NO ₃ ) ₃ , AF _3, and the like.

The step of preparing the first powder, the step of producing the second powder, and the step of heat-treating may be performed in air.

The heat treatment may be performed at a temperature of 900 ° C to 1100 ° C, preferably at 1050 ° C.

The method for producing a phosphor according to another embodiment of the present invention, wherein p and q are not integers, is characterized in that a La precursor, Er precursor, Tm precursor, Ho precursor and Yb precursor are mixed to form a third powder Producing; Adding the third powder to NH ₄ F and then drying to produce a fourth powder; And heat treating the fourth powder.

(2)

P is a real number of 0.55? P? 0.75, q is a real number of 1.5? Q? 1.9, w is a real number of 0? W? 0.1 and x is a real number of 0? X? , Y is a real number satisfying 0? Y? 0.05, and z is a real number satisfying 0? Z? 0.1.

Wherein the La precursor is any one selected from the group consisting of La ₂ O _{3 ,} La (NO ₃ ) ₃ and LaF ₃ , the Er precursor is Er ₂ O _{3 ,} Er (NO ₃ ) ₃ and ErF ₃ , the Tm precursor is any one selected from the group consisting of Tm ₂ O _{3 ,} Tm (NO ₃ ) ₃ and TmF ₃ , the Ho precursor is selected from the group consisting of Ho ₂ O _{3 ,} Ho (NO ₃ ) ₃ and HoF ₃ , and the Yb precursor may be any one selected from the group consisting of Yb ₂ O ₃ , Yb (NO ₃ ) ₃ and YbF ₃ .

The step of preparing the third powder, the step of producing the fourth powder, and the step of heat-treating are preferably carried out in air.

The heat treatment is preferably performed in a range of 900 ° C to 1100 ° C, more preferably 1050 ° C.

According to the phosphor including the non-stoichiometric matrix of the present invention, it is possible to obtain a luminescent color having a desired wavelength ranging from high efficiency to green to red light. Particularly, the phosphor including the non-stoichiometric matrix of the present invention has the effect of inducing superior up-conversion emission and maximizing up-conversion emission compared with the phosphor including the stoichiometric matrix.

According to another embodiment of the present invention, there is an effect of providing a method of manufacturing a phosphor including a non-stoichiometric matrix only by a very simple heat treatment and solidification method.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view schematically showing a matrix structure of a phosphor according to Examples 1 to 16 and Comparative Examples 1 and 2 of the present invention. FIG.
2 is a graph showing an X-ray diffraction (XRD) pattern of a phosphor according to Example 2, Comparative Example 1, and Comparative Example 2 of the present invention and a phosphor not doped with Er ^{3 +} , Yb ³⁺ to be.
3 is a chart showing excitation and up conversion emission spectra of the phosphor according to Example 2, Comparative Example 1 and Comparative Example 2 of the present invention.
4 is an image showing up-conversion emission of the phosphor according to Example 2, Comparative Example 1 and Comparative Example 2 of the present invention.
FIG. 5 is a table showing up conversion emission spectra of the phosphors according to Examples 1 to 16 of the present invention. FIG.
6 is an image and energy level chart showing up-conversion emission of phosphors according to Examples 1 to 16 of the present invention.
FIG. 7 is a chart showing up-conversion emission spectra of the phosphors according to Examples 7, 11, and 16 of the present invention. FIG.
8 is an image showing up-conversion emission of phosphors according to Examples 17 to 73 of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings according to the present invention.

According to an aspect of the present invention, there is provided an oxyfluoride-based phosphor having the following general formula (1), wherein p and q in the general formula (1) are not integers.

[Chemical Formula 1]

P is a real number of 0.55? P? 0.75, q is a real number of 1.5? Q? 1.9, x is a real number of 0? X? 0.3, and A is a rare earth ion except La.

X represents the amount of the sensitizer. Even when x is 0, the excitation light can be absorbed by the host. However, when x is more than 0.3, emission by concentration quenching may not be realized.

P and q represent the amounts of oxygen and fluorine in the mother body, respectively, and when they are not integers, they exhibit more efficient conversion characteristics in the oxyfluoride matrix and have a wider excitation range. As shown in Figure 3, Er ^{+ 3,} where the range of the non-stoichiometric La _{0 .65} F _1.7 ³ doped with Yb ⁺ Er is ^{3 +,} both chemically doped with Yb ^{3 +} stoichiometric tetragonal and the trigonal crystal system LaOF .

Further, according to the up-conversion is also shown in the emission image Er ^{3 +} 4, green emission due to the up-conversion in a non-stoichiometric LaO _{0 .65} F _1.7 phosphor doped with Yb ^{+ 3} appears, but clearly, Er ^{3 +,} Up-conversion emission is not clearly observed in the stoichiometric LaOF matrix structure doped with Yb ^{3 +} .

If p is greater than 0.75, p is less than 0.55, q is greater than or equal to 1.9, or q is less than 1.5, no up-conversion release is clearly observed.

The present invention encompasses oxyfluoride matrices that are not fluoride mates. The oxyfluoride matrix is chemically stable and has low toxicity compared to the fluoride matrix.

A is a sensitizer serving as energy transfer in a matrix and is a scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium , Sm, Eu, Gd, Tb, Dy, Ho, Er, Thr, Yb, Lu, ) Of rare earth ions including lanthanum.

The oxyfluoride-based phosphor according to another embodiment of the present invention is represented by the following general formula (2), and p and q in the general formula (2) are not integers.

(2)

P is a real number of 0.55? P? 0.75, q is a real number of 1.5? Q? 1.9, w is a real number of 0? W? 0.1 and x is a real number of 0? X? , Y is a real number satisfying 0? Y? 0.05, and z is a real number satisfying 0? Z? 0.1.

The w + x + y represents the amount of the sensitizer. Even when w + x + y is 0, the excitation light can be absorbed by the matrix itself. However, when w + x + y exceeds 0.2 Release by concentration quenching may not be realized.

Wherein z is as representing the amount of Yb ^{3 +} of the sensitizer or activators act, even if z is 0, but may be released this implementation, there is a release by the concentration quenching if z is greater than 0.1 can not be implemented .

The Er ^{3 +} , Tm ^{3 +} , and Ho ^{3 +} act as a sensitizer to absorb external excitation light and transfer it to an activator, or to transmit external excitation light absorbed by a host to an activator.

The Yb ^{3 +} can perform both a role as a sensitizer and an activator in a host, and is suitable for preparing a phosphor because the supply is stable and the price is low compared to other rare earth elements.

The phosphor ^{Er 3 +, Tm 3 +,} Ho 3 +, the content of Yb ^{3 +} are each ^{(0 mol% ≤ Er 3 +} ≤ 10 mol%), (0 mol% ≤ Tm 3 + ≤ 5 mol%), ( 0 mol%? Ho ^{3 +} ? 5 mol%), (0 mol%? Yb ^{3 +} ? 10 mol%).

P and q represent the amounts of oxygen and fluorine in the matrix, respectively, and exhibit more efficient conversion characteristics in the oxyfluoride matrix in the non-stoichiometric case than in the case of integers, . As shown in Figure 3, Er ^{+ 3,} where the range of the non-stoichiometric La _{0 .65} F _1.7 ³ doped with Yb ⁺ Er is ^{3 +,} both chemically doped with Yb ^{3 +} stoichiometric tetragonal and the trigonal crystal system LaOF .

Further, according to the up-conversion is also shown in the emission image Er ^{3 +} 4, green emission due to the up-conversion in a non-stoichiometric LaO _{0 .65} F _1.7 phosphor doped with Yb ^{+ 3} appears, but clearly, Er ^{3 +,} Up-conversion emission is not clearly observed in the stoichiometric LaOF matrix structure doped with Yb ^{3 +} .

If p is greater than 0.75, p is less than 0.55, q is greater than or equal to 1.9, or q is less than 1.5, no up-conversion release is clearly observed.

The present invention encompasses oxyfluoride matrices that are not fluoride mates. The oxyfluoride matrix is chemically stable and has low toxicity compared to the fluoride matrix.

The emission wavelength of the phosphor may be in the range of 360 nm?? 820 nm. It is an object of the present invention to adjust the emission color depending on the ratio of the activator and the sensitizer, so that the emission wavelength of the phosphor is preferably in the range of visible light.

The emission characteristic of the phosphor may be an up conversion. Unlike down conversion, which requires a high-power excitation light source, the up-conversion mechanism can emit light even when the output power of the excitation light source is weak because the base-level electrons are excited to the high energy state level via the intermediate energy level.

Figure 1 shows the structure of tetragonal stoichiometric LaOF and nonstoichiometric LaO _{0 .65} F _1.7 matrix. The structure of the phosphor may be a tetragonal system as shown in FIG. The tetragonal system is the shape of a rectangular column with a square base extending out of a grid vector in the cube. The tetragonal structure can be fabricated by a simple solid-phase method, unlike a three-dimensional structure in which a cube is elongated in a diagonal direction.

A method of producing a phosphor according to one embodiment of the present invention, wherein p and q are not integers, comprises the steps of: preparing a first powder by mixing La precursor and A precursor; Adding the first powder to NH ₄ F and then drying to produce a second powder; And heat treating the second powder.

[Chemical Formula 1]

P is a real number of 0.55? P? 0.75, q is a real number of 1.5? Q? 1.9, x is a real number of 0? X? 0.3, and A is a rare earth ion except La.

In the step of preparing the first powder, the La precursor may be La ₂ O _{3 ,} La (NO ₃ ) ₃ , LaF ₃ , and the A precursor may be A ₂ O ₃ , A (NO ₃ ) ₃ , AF ₃ .

The steps of preparing the first and second powders and the step of heat-treating may be performed in air. The hydrothermal synthesis method, the sol-gel synthesis method, the complex polymerization method, and the like, which are generally performed to produce the phosphor, are performed under high pressure conditions, but the solid phase method of the present invention is performed in air, so that the process can be simplified.

The heat treatment is preferably performed in a range of 900 ° C to 1100 ° C, more preferably 1050 ° C. When the temperature is higher than 1100 ° C or lower than 900 ° C, a problem that a single phase is not formed occurs.

The method for producing a phosphor according to another embodiment of the present invention, wherein p and q are not integers, is characterized in that a La precursor, Er precursor, Tm precursor, Ho precursor and Yb precursor are mixed to form a third powder Producing; Adding the third powder to NH ₄ F and then drying to produce a fourth powder; And heat treating the fourth powder.

(2)

P is a real number of 0.55? P? 0.75, q is a real number of 1.5? Q? 1.9, w is a real number of 0? W? 0.1 and x is a real number of 0? X? , Y is a real number satisfying 0? Y? 0.05, and z is a real number satisfying 0? Z? 0.1.

The La precursor is La ₂ O _{3 ,} La (NO ₃ ) ₃ , LaF ₃ , Er precursor is Er ₂ O _{3 ,} Er (NO ₃ ) ₃ , ErF ₃ , and the Tm precursor is _{Tm 2 O 3, Tm (NO} 3) 3, TmF 3, the Ho precursor _{Ho 2 O 3, Ho (NO} 3) 3, HoF 3, wherein Yb precursor, _{Yb 2 O 3, Yb (NO} 3) 3, YbF ₃ .

The steps of preparing the third to fourth powders and the step of heat-treating may be performed in air. The hydrothermal synthesis method, the sol-gel synthesis method, the complex polymerization method, and the like, which are generally performed to produce the phosphor, are performed under high pressure conditions, but the solid phase method of the present invention is performed in air, so that the process can be simplified.

The heat treatment is preferably performed in a range of 900 ° C to 1100 ° C, more preferably 1050 ° C. When the temperature is higher than 1100 ° C or lower than 900 ° C, a problem that a single phase is not formed occurs.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention, and the contents of the present invention are not limited to the following examples.

{Example}

One. Example  One

La ₂ O ₃ (purity 99.9%, ALFA), Er ₂ O ₃ (purity 99.9%, ALFA) and NH ₄ F (purity 99%, ALFA) The _{La (Er) O 3/2} : NH 4 F = 1: mixing molar ratio of 2, and non-chemically amount by performing a conventional method and heat-treated to 1050 ℃ for 2 hours in the air stoichiometric tetragonal La _{1 - w} Er _w O _{0 .65} F _1.7 phosphors were prepared. The content of Er ^{3 +} was 0.5 mol% and Yb ³⁺ was not added.

2. Example  2

Yb ₂ O ₃ (purity 99.9%, ALFA) adding _{La O 3/2 (Er,} Yb) in the: NH ₄ F = 1: mixture in a ratio of 2 moles except that the content of the Yb ^{3 +} is 1 mol%, and It was prepared in a non-stoichiometric tetragonal _{La 1 -w- z Er w Yb z} O 0 .65 F 1.7 phosphor in the same manner as in example 1.

3. Example  3

Yb ₂ O ₃ (purity 99.9%, ALFA) adding _{La O 3/2 (Er,} Yb) in the: NH ₄ F = 1: mixture in a ratio of 2 moles except that the content of the Yb ^{3 +} is 5 mol%, and It was prepared in a non-stoichiometric tetragonal _{La 1 -w- z Er w Yb z} O 0 .65 F 1.7 phosphor in the same manner as in example 1.

4. Example  4

Yb ₂ O ₃ (purity 99.9%, ALFA) by adding _{La (Er, Yb) O 3} /2: NH 4 F = 1: mixture ratio of two moles and the content of the Yb ^{3 +,} except in that 10 mol% It was prepared in a non-stoichiometric tetragonal _{La 1 -w- z Er w Yb z} O 0 .65 F 1.7 phosphor in the same manner as in example 1.

5. Example  5

The content of Er ^{+ 3} is a non-stoichiometric tetragonal La ₁ in the same manner as in Example 1 except that a 1 mol% _- was prepared Er _{w w} O _{0 .65} F _1.7 phosphor.

6. Example  6

Yb ₂ O ₃ (purity: 99.9%, ALFA) was further mixed and the content of Yb ^{3 +} was 1 mol%, a non-stoichiometric tetragonal La _{1 -w z w} Yb _z O _{0 .65} F _{1. 7} was produced phosphor.

7. Example  7

Yb ₂ O ₃ (purity 99.9%, ALFA) was further mixed, and the content of Yb ^{3 +} was 5 mol%, a nonstoichiometric tetragonal La _{1 -w z w} Yb _z O _{0 .65} F _{1. 7} was produced phosphor.

8. Example  8

Yb ₂ O ₃ (purity 99.9%, ALFA) was further mixed and the content of Yb ^{3 +} was 10 mol%, a nonstoichiometric tetragonal La _{1 -w z w} Yb _z O _{0 .65} F _1.7 phosphors were prepared.

9. Example  9

The content of Er ^{+ 3} is a non-stoichiometric tetragonal La ₁ in the same manner as in Example 1 except that a 1 mol% _- was prepared Er _{w w} O _{0 .65} F _1.7 phosphor.

10. Example  10

Yb ₂ O ₃ (purity 99.9%, ALFA) was further mixed and the content of Yb ^{3 +} was 1 mol%, a nonstoichiometric tetragonal La _{1 -w z w} Yb _z O _{0 .65} F _{1. 7} was produced phosphor.

11. Example  11

Yb ₂ O ₃ (purity 99.9%, ALFA) was further mixed and the content of Yb ^{3 +} was 5 mol%, a non-stoichiometric tetragonal La _{1 -w z w} Yb _z O _{0 .65} F _{1. 7} was produced phosphor.

12. Example  12

Yb ₂ O ₃ (purity 99.9%, ALFA) was further mixed, and the content of Yb ^{3 +} was 10 mol%, a nonstoichiometric tetragonal La _{1 -w z w} Yb _z O _{0 .65} F _1.7 phosphors were prepared.

13. Example  13

The content of Er ^{+ 3} is the example 1 and the non-stoichiometric tetragonal La ₁ in the same manner except that a 1 mol% _- to prepare a _{w Er w O 0 .65 F 1.} 7 phosphors.

14. Example  14

Yb ₂ O ₃ (purity: 99.9%, ALFA) was further mixed and the content of Yb ^{3 +} was 1 mol%, a non-stoichiometric tetragonal La _{1 -w z w} Yb _z O _{0 .65} F _1.7 phosphors were prepared.

15. Example  15

Yb ₂ O ₃ (purity 99.9%, ALFA) was further mixed and the content of Yb ^{3 +} was 5 mol%, a non-stoichiometric tetragonal La _{1 -w z w} Yb _z O _{0 .65} F _1.7 phosphors were prepared.

16. Example  16

Yb ₂ O ₃ (purity 99.9%, ALFA) was further mixed and the content of Yb ^{3 +} was 10 mol%, a nonstoichiometric tetragonal La _{1 -w z w} Yb _z O _{0 .65} F _1.7 phosphors were prepared.

17. Example  17

La ₂ O ₃ (purity _{99.9%, ALFA), Tm 2} O 3 ( purity _{99.9%, ALFA), Yb 2} O 3 ( purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Tm _{, Yb) O 3/2:} NH 4 F = 1: 2 mixture of molar ratio, and that the heat treatment is performed at 1050 ℃ for 2 hours in air to perform a conventional method to non-stoichiometric tetragonal La _{1 -x- z} Tm _x Yb _z O _{0 .65} F _1.7 phosphors were prepared. The content of Tm ^{3 +} was 0.25 mol%, the content of Yb ^{3 +} was 5 mol%, and Er ^{3 +} and Ho ^{3 +} were not added.

18. Example  18

La ₂ O ₃ (purity _{99.9%, ALFA), Tm 2} O 3 ( purity _{99.9%, ALFA), Ho 2} O 3 ( purity _{99.9%, ALFA), Yb 2} O 3 ( purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Tm, Ho, Yb) O 3/2: NH 4 F = 1: a mixture of a molar ratio of 2, and performs high-conventional method of heat treating to 1050 ℃ for two hours in air Non-stoichiometric tetragonal La _{1 -xy- z} Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared. The content of Tm ^{3 +} was 0.25 mol%, the content of Ho ^{3 +} was 0.05 mol%, the content of Yb ^{3 +} was 5 mol%, and the content of Er ^{3 +} was not added.

19. Example  19

The nonstoichiometric tetragonal La _{1 -xy- z} Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 18 except that the content of Ho ^{3 +} was 0.075 mol%.

20. Example  20

The nonstoichiometric tetragonal La _{1 -xy- z} Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 18 except that the content of Ho ^{3 +} was 0.1 mol%.

21. Example  21

A non-stoichiometric tetragonal La _{1 -xy- z} Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphor was prepared in the same manner as in Example 18 except that the content of Ho ^{3 +} was 0.5 mol%.

22. Example  22

La ₂ O ₃ (purity _{99.9%, ALFA), Er 2} O 3 ( purity _{99.9%, ALFA), Tm 2} O 3 ( purity _{99.9%, ALFA), Yb 2} O 3 ( purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Er, Tm, Yb) O 3/2: NH 4 F = 1: a mixture of a molar ratio of 2, and performs high-conventional method of heat treating to 1050 ℃ for two hours in air Non-stoichiometric tetragonal La _{1 -wx- z} Er _w Tm _x Yb _z O _{0 .65} F _1.7 phosphors were prepared. The content of Tm ^{3 +} was 0.25 mol%, the content of Er ^{3 +} was 0.05 mol%, the content of Yb ^{3 +} was 5 mol% and the content of Ho ^{3 +} was not added.

23. Example  23

La ₂ O ₃ (purity _{99.9%, ALFA), Er 2} O 3 ( purity _{99.9%, ALFA), Tm 2} O 3 ( purity _{99.9%, ALFA), Ho 2} O 3 ( purity 99.9%, ALFA), Yb ₂ O ₃ (purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Er, Tm, Ho, Yb) O 3/2: NH 4 F = 1: a molar ratio of the second mixture, and the air And a non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphor was prepared by performing a solid-phase method in which the _substrate was heat-treated at 1050 ° C. for 2 hours. The content of Er ^{3 +} was 0.05 mol%, the content of Tm ^{3 +} was 0.25 mol%, the content of Ho ^{3 +} was 0.05 mol%, and the content of Yb ^{3 +} was 5 mol%.

24. Example  24

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 23 except that the content of Ho ^{3 +} was 0.075 mol% Respectively.

25. Example  25

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were produced in the same manner as in Example 23 except that the content of Ho ^{3 +} was 0.1 mol% Respectively.

26. Example  26

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 23 except that the content of Ho ^{3 +} was 0.5 mol% Respectively.

27. Example  27

The non-stoichiometric tetragonal La _{1 -wx- z} Er _w Tm _x Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 22 except that the content of Er ^{3 +} was 0.075 mol%.

28. Example  28

La ₂ O ₃ (purity _{99.9%, ALFA), Er 2} O 3 ( purity _{99.9%, ALFA), Tm 2} O 3 ( purity _{99.9%, ALFA), Ho 2} O 3 ( purity 99.9%, ALFA), Yb ₂ O ₃ (purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Er, Tm, Ho, Yb) O 3/2: NH 4 F = 1: a molar ratio of the second mixture, and the air And a non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphor was prepared by performing a solid-phase method in which the _substrate was heat-treated at 1050 ° C. for 2 hours. The content of Er ^{3 +} is 0.075 mol%, the content of Tm ^{3 +} is 0.25 mol%, the content of Ho ^{3 +} is 0.05 mol%, and the content of Yb ^{3 +} is 5 mol%.

29. Example  29

_{Zirconium tetrafluoroborate} was prepared in the same manner as in Example 28 except that the content of Ho ^{3 +} was 0.075 mol%. The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 Respectively.

30. Example  30

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 28 except that the content of Ho ^{3 +} was 0.1 mol% Respectively.

31. Example  31

The nonstoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 28 except that the content of Ho ^{3 +} was 0.5 mol% Respectively.

32. Example  32

The non-stoichiometric tetragonal La _{1 -wx- z} Er _w Tm _x Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 22 except that the content of Er ^{3 +} was 0.1 mol%.

33. Example  33

La ₂ O ₃ (purity _{99.9%, ALFA), Er 2} O 3 ( purity _{99.9%, ALFA), Tm 2} O 3 ( purity _{99.9%, ALFA), Ho 2} O 3 ( purity 99.9%, ALFA), Yb ₂ O ₃ (purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Er, Tm, Ho, Yb) O 3/2: NH 4 F = 1: a molar ratio of the second mixture, and the air , And a non-stoichiometric tetragonal La _{1 -wxyz} Er _w Tm _x Ho _y Yb _z O _0.65 F _1.7 phosphor was prepared by performing the solid-phase method of heat treatment at 1050 ° C. for 2 hours. The content of Er ^{3 +} was 0.1 mol%, the content of Tm ^{3 +} was 0.25 mol%, the content of Ho ^{3 +} was 0.05 mol%, and the content of Yb ^{3 +} was 5 mol%.

34. Example  34

_{Zirconium tetrafluoroborate} was prepared in the same manner as in Example 33 except that the content of Ho ^{3 +} was 0.075 mol%. The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 Respectively.

35. Example  35

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 33 except that the content of Ho ^{3 +} was 0.1 mol% Respectively.

36. Example  36

The content of Ho ^{3 +} is 0.5 mol% in the example of manufacturing the non-stoichiometric tetragonal _{La 1 -wxy- z Er w Tm x} Ho y Yb z O 0 .65 F 1.7 Phosphor 33 in the same manner except that Respectively.

37. Example  37

The non-stoichiometric tetragonal La _{1 -wx- z} Er _w Tm _x Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 22 except that the content of Er ^{3 +} was 0.25 mol%.

38. Example  38

La ₂ O ₃ (purity _{99.9%, ALFA), Er 2} O 3 ( purity _{99.9%, ALFA), Tm 2} O 3 ( purity _{99.9%, ALFA), Ho 2} O 3 ( purity 99.9%, ALFA), Yb ₂ O ₃ (purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Er, Tm, Ho, Yb) O 3/2: NH 4 F = 1: a molar ratio of the second mixture, and the air And a non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphor was prepared by performing a solid-phase method in which the _substrate was heat-treated at 1050 ° C. for 2 hours. The content of Er ^{3 +} was 0.25 mol%, the content of Tm ^{3 +} was 0.25 mol%, the content of Ho ^{3 +} was 0.05 mol%, and the content of Yb ^{3 +} was 5 mol%.

39. Example  39

_{Zirconium tetrafluoroborate} was prepared in the same manner as in Example 38 except that the content of Ho ^{3 +} was 0.075 mol%. The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 Respectively.

40. Example  40

The nonstoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were produced in the same manner as in Example 38 except that the content of Ho ^{3 +} was 0.1 mol% Respectively.

41. Example  41

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 38 except that the content of Ho ^{3 +} was 0.5 mol% Respectively.

42. Example  42

The non-stoichiometric tetragonal La _{1 -wx- z} Er _w Tm _x Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 22 except that the content of Er ^{3 +} was 0.35 mol%.

43. Example  43

La ₂ O ₃ (purity _{99.9%, ALFA), Er 2} O 3 ( purity _{99.9%, ALFA), Tm 2} O 3 ( purity _{99.9%, ALFA), Ho 2} O 3 ( purity 99.9%, ALFA), Yb ₂ O ₃ (purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Er, Tm, Ho, Yb) O 3/2: NH 4 F = 1: a molar ratio of the second mixture, and the air And a non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphor was prepared by performing a solid-phase method in which the _substrate was heat-treated at 1050 ° C. for 2 hours. The content of Er ^{3 +} was 0.35 mol%, the content of Tm ^{3 +} was 0.25 mol%, the content of Ho ^{3 +} was 0.05 mol%, and the content of Yb ^{3 +} was 5 mol%.

44. Example  44

The nonstoichiometric tetragonal La _1-wxyz Er _w Tm _x Ho _y Yb _z O _0.65 F _1.7 phosphors were prepared in the same manner as in Example 43 except that the content of Ho ^{3 +} was 0.075 mol%.

45. Example  45

_{Zirconium tetrafluoroborate} was prepared in the same manner as in Example 43 except that the content of Ho ^{3 +} was 0.1 mol%. The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 Respectively.

46. Example  46

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were produced in the same manner as in Example 43 except that the content of Ho ^{3 +} was 0.5 mol% Respectively.

47. Example  47

The non-stoichiometric tetragonal La _{1 -wx- z} Er _w Tm _x Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 22 except that the content of Er ^{3 +} was 0.5 mol%.

48. Example  48

La ₂ O ₃ (purity _{99.9%, ALFA), Er 2} O 3 ( purity _{99.9%, ALFA), Tm 2} O 3 ( purity _{99.9%, ALFA), Ho 2} O 3 ( purity 99.9%, ALFA), Yb ₂ O ₃ (purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Er, Tm, Ho, Yb) O 3/2: NH 4 F = 1: a molar ratio of the second mixture, and the air And a non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphor was prepared by performing a solid-phase method in which the _substrate was heat-treated at 1050 ° C. for 2 hours. The content of Er ^{3 +} was 0.5 mol%, the content of Tm ^{3 +} was 0.25 mol%, the content of Ho ^{3 +} was 0.05 mol%, and the content of Yb ^{3 +} was 5 mol%.

49. Example  49

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 48 except that the content of Ho ^{3 +} was 0.075 mol% Respectively.

50. Example  50

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 48 except that the content of Ho ^{3 +} was 0.1 mol% Respectively.

51. Example  51

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 48 except that the content of Ho ^{3 +} was 0.5 mol% Respectively.

52. Example  52

The non-stoichiometric tetragonal La _{1 -wx- z} Er _w Tm _x Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 22 except that the content of Er ^{3 +} was 1 mol%.

53. Example  53

La ₂ O ₃ (purity _{99.9%, ALFA), Er 2} O 3 ( purity _{99.9%, ALFA), Tm 2} O 3 ( purity _{99.9%, ALFA), Ho 2} O 3 ( purity 99.9%, ALFA), Yb ₂ O ₃ (purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Er, Tm, Ho, Yb) O 3/2: NH 4 F = 1: a molar ratio of the second mixture, and the air And a non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphor was prepared by performing a solid-phase method in which the _substrate was heat-treated at 1050 ° C. for 2 hours. The content of Er ^{3 +} is 1 mol%, the content of Tm ^{3 +} is 0.25 mol%, the content of Ho ^{3 +} is 0.05 mol%, and the content of Yb ^{3 +} is 5 mol%.

54. Example  54

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 53 except that the content of Ho ^{3 +} was 0.075 mol% Respectively.

55. Example  55

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were produced in the same manner as in Example 53 except that the content of Ho ^{3 +} was 0.1 mol% Respectively.

56. Example  56

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 53 except that the content of Ho ^{3 +} was 0.5 mol% Respectively.

57. Example  57

The non-stoichiometric tetragonal La _{1 -wx- z} Er _w Tm _x Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 22 except that the content of Er ^{3 +} was 2 mol%.

58. Example  58

La ₂ O ₃ (purity _{99.9%, ALFA), Er 2} O 3 ( purity _{99.9%, ALFA), Tm 2} O 3 ( purity _{99.9%, ALFA), Ho 2} O 3 ( purity 99.9%, ALFA), Yb ₂ O ₃ (purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Er, Tm, Ho, Yb) O 3/2: NH 4 F = 1: a molar ratio of the second mixture, and the air And a non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphor was prepared by performing a solid-phase method in which the _substrate was heat-treated at 1050 ° C. for 2 hours. The content of Er ^{3 +} is 2 mol%, the content of Tm ^{3 +} is 0.25 mol%, the content of Ho ^{3 +} is 0.05 mol%, and the content of Yb ^{3 +} is 5 mol%.

59. Example  59

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 58 except that the content of Ho ^{3 +} was 0.075 mol% Respectively.

60. Example  60

In the same manner as in Example 58 except that the content of Ho ^{3 +} was 0.1 mol%, non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 Respectively.

61. Example  61

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 58 except that the content of Ho ^{3 +} was 0.5 mol% Respectively.

62. Example  62

The non-stoichiometric tetragonal La _{1 -wx- z} Er _w Tm _x Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 22 except that the content of Er ^{3 +} was 2.5 mol%.

63. Example  63

La ₂ O ₃ (purity _{99.9%, ALFA), Er 2} O 3 ( purity _{99.9%, ALFA), Tm 2} O 3 ( purity _{99.9%, ALFA), Ho 2} O 3 ( purity 99.9%, ALFA), Yb ₂ O ₃ (purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Er, Tm, Ho, Yb) O 3/2: NH 4 F = 1: a molar ratio of the second mixture, and the air And a non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphor was prepared by performing a solid-phase method in which the _substrate was heat-treated at 1050 ° C. for 2 hours. The content of Er ^{3 +} is 2.5 mol%, the content of Tm ^{3 +} is 0.25 mol%, the content of Ho ^{3 +} is 0.05 mol%, and the content of Yb ^{3 +} is 5 mol%.

64. Example  64

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 63 except that the content of Ho ^{3 +} was 0.075 mol% Respectively.

65. Example  65

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were produced in the same manner as in Example 63 except that the content of Ho ^{3 +} was 0.1 mol% Respectively.

66. Example  66

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 63 except that the content of Ho ^{3 +} was 0.5 mol% Respectively.

67. Example  67

The non-stoichiometric tetragonal La _{1 -wx- z} Er _w Tm _x Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 22 except that the content of Er ^{3 +} was 5 mol%.

68. Example  68

La ₂ O ₃ (purity _{99.9%, ALFA), Er 2} O 3 ( purity _{99.9%, ALFA), Tm 2} O 3 ( purity _{99.9%, ALFA), Ho 2} O 3 ( purity 99.9%, ALFA), Yb ₂ O ₃ (purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Er, Tm, Ho, Yb) O 3/2: NH 4 F = 1: a molar ratio of the second mixture, and the air And a non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphor was prepared by performing a solid-phase method in which the _substrate was heat-treated at 1050 ° C. for 2 hours. The content of Er ^{3 +} is 5 mol%, the content of Tm ^{3 +} is 0.25 mol%, the content of Ho ^{3 +} is 0.05 mol%, and the content of Yb ^{3 +} is 5 mol%.

69. Example  69

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 68 except that the content of Ho ^{3 +} was 0.075 mol% Respectively.

70. Example  70

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 68 except that the content of Ho ^{3 +} was 0.1 mol% Respectively.

71. Example  71

The non-stoichiometric tetragonal La _{1 -wxy- z} Er _w Tm _x Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared in the same manner as in Example 68 except that the content of Ho ^{3 +} was 0.5 mol% Respectively.

72. Example  72

La ₂ O ₃ (purity _{99.9%, ALFA), Ho 2} O 3 ( purity _{99.9%, ALFA), Yb 2} O 3 ( purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Ho _{, Yb) O 3/2:} NH 4 F = 1: 2 mixture of molar ratio, and that the heat treatment is performed at 1050 ℃ for 2 hours in air to perform a conventional method to non-stoichiometric tetragonal La _{1 -wy- z} Ho _y Yb _z O _{0 .65} F _1.7 phosphors were prepared. The content of Ho ³⁺ was 0.05 mol%, the content of Yb ^{3 +} was 5 mol%, and Er ^{3 ++} and Tm ³ were not added.

73. Example  73

La ₂ O ₃ (purity _{99.9%, ALFA), Er 2} O 3 ( purity _{99.9%, ALFA), Yb 2} O 3 ( purity 99.9%, ALFA), and NH ₄ F (purity 99%, ALFA) of La (Er _{, Yb) O 3/2:} NH 4 F = 1: 2 mixture of molar ratio, and the air from the second high heat treating to 1050 ℃ for a time by performing a conventional method non-stoichiometric tetragonal La _{1 -wy-} Er _{z w} Yb _z O _{0 .65} F _1.7 phosphors were prepared. The content of Er ⁺ was 5 mol%, the content of Yb ^{3 +} was 5 mol%, and Tm ^{3 +} and Ho ^{3 +} were not added.

74. Comparative Example  One

The content of Er ^{3 +} is 0.5 mol%, Yb ^{3 +} is in the content by adding a 1 mol% a (Er, Yb ) O 3/2: NH 4 F = 1: molar ratio of the stoichiometric tetragonal La 1 _{0 . 99} Er _{0. 005} Yb _{0 . 01} OF phosphor was prepared by performing a solid - phase method of heat treatment at 950 ℃ for 2 hours in air to obtain a stoichiometric tetragonal La _{0 . 99} Er _{0. 005} Yb _{0 . 01} OF phosphor.

75. Comparative Example  2

And the stoichiometric trigonal crystal system in the same manner as in Comparative Example 1 except that the heat treatment temperature of 1050 ℃ La _{0. 99} Er _{0. 005} Yb _{0 . 01} OF phosphor.

The conditions and crystal structures of Examples 1 to 16 and Comparative Examples 1 and 2 are shown in Table 1 below.

Er (mol%) x Yb (mol%) y Heat treatment temperature rescue Example 1 0.5 0.005 0 0 1050 ° C Tetragonal system Example 2 0.5 0.005 One 0.01 1050 ° C Tetragonal system Example 3 0.5 0.005 5 0.05 1050 ° C Tetragonal system Example 4 0.5 0.005 10 0.1 1050 ° C Tetragonal system Example 5 One 0.01 0 0 1050 ° C Tetragonal system Example 6 One 0.01 One 0.01 1050 ° C Tetragonal system Example 7 One 0.01 5 0.05 1050 ° C Tetragonal system Example 8 One 0.01 10 0.1 1050 ° C Tetragonal system Example 9 5 0.05 0 0 1050 ° C Tetragonal system Example 10 5 0.05 One 0.01 1050 ° C Tetragonal system Example 11 5 0.05 5 0.05 1050 ° C Tetragonal system Example 12 5 0.05 10 0.1 1050 ° C Tetragonal system Example 13 10 0.1 0 0 1050 ° C Tetragonal system Example 14 10 0.1 One 0.01 1050 ° C Tetragonal system Example 15 10 0.1 5 0.05 1050 ° C Tetragonal system Example 16 10 0.1 10 0.1 1050 ° C Tetragonal system Comparative Example 1 0.5 0.005 One 0.001 950 ℃ Tetragonal system Comparative Example 2 0.5 0.005 One 0.001 1050 ° C Three-way system

{evaluation}

X-ray diffraction (XRD) characteristics of the phosphors prepared in Examples 1 to 16 and Comparative Examples 1 and 2 were identified using an X-ray diffractometer (Shimadzu, XRD-600) using Cu-Ka radiation . Unit cell parameters were measured using Rietica, a Rietveld structural purification program. UV spectroscopy for measuring the excitation and emission spectrum of the phosphor material was performed using a spectrophotometer (Sinco, Fluoromate FS-2) at room temperature. The up-conversion emission spectra were observed with a 980 nm diode laser (Ocean Optics) at room temperature.

1. X-ray diffraction ( XRD ) Characterization

The X-ray diffraction patterns of the LaOF and LaO _{0 .65} F _1.7 phosphors of the phosphors according to Examples 1 to 16 and Comparative Examples 1 and 2 of the present invention were observed to confirm the crystallographic phase. 2 (a) to 2 (c) show the XRD patterns of the triplet-state LaOF, tetragonal LaOF and tetragonal LaO _{0 .65} F _1.7 structures, respectively. 2 (d) to 2 (f) show the XRD patterns of the triploid LaOF, tetragonal LaOF and tetragonal LaO _0.65 F _1.7 structures doped with Er ^{3 +} , Yb ^{3 +} .

As can be seen in the XRD pattern of Figure 2 (f), the effective spectral conversion emission was observed only in non-stoichiometric La _{0 .65} F _1.7 doped with Er ^{3 +} , Yb ^{3 +} .

Tetragonal unit cells (Fig. 2 (F)) with cell parameters a = 4.0996 (2) and c = 5.8446 (3) of the nonstoichiometric La _{0 .65} F _1.7 matrix doped with Er ^{3 +} , Yb ^{3 +} ICSD 40371). Compared with the stoichiometric phosphor phase, the a-axis and c-axis of the nonstoichiometric phosphor were slightly expanded by about 0.6 and 0.3%, respectively. This expansion is caused by the high coordination of excess F ^- ions and La ^{3 +} (Er ^{3 +} , Yb ^{3 +} ) cations in nonstoichiometric LaO _{0 .65} F _1.7 unit cells. In addition, the XRD pattern difference between tetragonal LaOF and tetragonal LaO _{0 .65} F _1.7 appears at 26 ° to 28 ° peak position (2θ) due to abundant F ^- ions.

2. Up-conversion emission measurement 1

Fig. 4 is a graph showing the relationship between the triplet and tetragonal La ₀ .05 when excited with a 980 nm diode laser with an output of 193 mW _{. 99} Er _{0. 005} Yb _{0 . 01} OF and tetragonal La _{0 . 985R 0 . 005} Yb _{0 . 0.0} > ₀ < / RTI > _0.65 F _1.7 . Er ^3+, Yb ³⁺ doped with a non-stoichiometric LaO _{0 .65} F green emission due to the up-conversion in the phosphors is _1.7 appears clearly Er ^{3 +,} in a stoichiometric LaOF matrix structure doped with Yb ^{3 +} No up-conversion emission was clearly observed.

3. Emission spectrum measurement

The excitation range of non-stoichiometric La _{0 .65} F _1.7 doped with Er ^{3 +} , Yb ^{3 +} is shown in FIG. 3 as the stoichiometric tetragonal and the anisotropic LaOF phase doped with Er ^{3 +} , Yb ^{3 +} . LaO _0.65 F _{1.7 When} the La ^{3 +} of the matrix structure is replaced by Er ^{3 +} and Yb ^{3 +} ions, it becomes a highly efficient upconverting phosphor that has proven to be very intense up-conversion emission as shown in FIG.

Figure 5 (a) and (b) is shown in Examples 1 to as the Yb ³⁺ content is increased in the phosphor 8, the Er ³⁺ ions in the H _{^{11/2, 4 S 3/2 → 4}} I 1/2 and ⁴ F _9/2 → ⁴ I _{15 /} that derived from a mixture of _two transition, green, yellow and orange-red color to the emission band is observed at 550 and 670 nm, in particular, Yb ³⁺ content from 0 to 1 mol% increasing, Er ^{3 +} is a green emission spectrum derived from _{^{2 H 11/2, 4 S}} 3/2 → 4 I 15/2 transition of ions is observed.

As shown in Figs. 5 (c) and 5 (d), strong orange and red emission of 670 nm were observed in the phosphors of Examples 9 to 16. Especially Er ^{3 +} or Yb ^{3 +} ion, if the content is 5 mol%, the yellow and orange emission spectrum derived from the _{^{4 F 9/2 → 4 I 15/}} 2 transition of Er ³⁺ ions were observed.

5 (a) to 5 (d), when the content of Er ^{3 +} or Yb ³⁺ in the phosphors of Examples 1 to 16 reaches 10 mol%, ⁴ F _9/2 → ⁴ I ₁₅ of Er ^{3 +} _{/ 2} transition and the orange and red emission spectra were strong.

Figure 6 (a) shows the green, yellow, orange and red up-conversion emission images of the excited state phosphors by a 980 nm diode laser at 193 mW output.

It can also be seen that as shown in Figure 6 (b), the energy transfer (ET) mechanism is undergoing the upconversion in non-stoichiometric La _0.65 F _1.7 phosphor doped with Er ^{3 +} , Yb ^{3 +} . As it demonstrated by the presence of _{^{red-emitting, Er 3 + (4 I 11}} /2) + Er 3 + (4 I 13/2) → Er 3+ (4 I 15/2) + Er 3 + (4 F _9/2 ) The upconversion involving energy transfer is caused by the interaction between two adjacent Er ^{3 +} ions in the nonstoichiometric La _{0 .65} F _1.7 matrix. This also adjacent two ^{_{Er 3 + 4 F 7/2 + 4}} I 11/2 between ion → ⁴ F _9/2 + ⁴ F _9/2 and a cross-releasing process proceeds red emission in the matrix is improved.

To confirm the photon process of the upconversion mechanism, the IR pump output (P _IR ⁿ ) dependence of the _up conversion emission intensity (I _up ) is investigated. Also, the up-conversion emission intensity is proportional to the nth IR pump output (ie, I _up ∞ P _IR ⁿ , where n is the number of pump photons for one up-converted photon) (I _up ) vs. ln (P _IR ⁿ ) slope.

7 (a) to (c) show the up-conversion emission spectra of the phosphors according to Examples 7, 11 and 16 of the present invention. At 193 ~ 310mW range as a function of pump output transformed infrared _(IR P ^n), the two peaks are ^{_{550nm (4 S 3/2 →}} 4 I 15/2 transition) and ^{_{670nm (4 F 9/2 → 4 I}} 15/2 Transition), corresponding to green and red emissions, respectively.

The number of pump photons of the phosphor according to Example 7 for both emissions at 550 and 670 nm is 1.2. The number of pump photons at 550 and 670 nm of the phosphor according to Example 11 is about 1.1 and 1.4, respectively. The number of pump photons of the phosphor according to Example 16 showing red emission at 670 nm is 1.1. It can be seen that the multi-photon process operates from the slope calculated in the linear plot.

4. Up-conversion emission measurement 2

Fig. 8 shows the tetragonal La _{1 -x- z} Tm _x Yb _z O _{0 .65} F _1.7 , La _{1 -xy- z} Tm _{x of the} examples 17 to 73 when excited by a 980 nm diode laser with an output of _{193 mW} Yb _{0 .65} F _y O _z Ho _1.7, La _{1 -wxz} Er _w Yb _z Tm _x F _1.7 O _0.65, La _{1 -wxy- z} Tm _x Er _w Yb _y Ho _z O _{0 .65} F _1.7, La _{1 - wy- z} Ho _y Yb _z O _{0 .65} F _1.7 , La _{1 -wyzer w} Yb _z O _0.65 F _1.7 . It can be seen that the emission wavelength can be controlled by controlling the content of Er ^{3 +} , Tm ^{3 +} , and Ho ^{3 +} . By controlling the contents of Er ^{3 +} , Tm ^{3 +} , and Ho ^{3 +} , desired wavelengths can be obtained from red emission to green emission.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

Claims (12)

1. A phosphor represented by the following general formula (1), wherein p and q in the general formula (1) are not integers:
[Chemical Formula 1]

P is a real number of 0.55? P? 0.75,
Q is a real number satisfying 1.5? Q? 1.9,
X is a real number satisfying 0 < x < = 0.3,
A is a rare earth ion except La. A phosphor represented by the following general formula (2), wherein p and q in the general formula (1) are not integers:
(2)

P is a real number of 0.55? P? 0.75,
Q is a real number satisfying 1.5? Q? 1.9,
W is a real number satisfying 0 < w? 0.1,
X is a real number satisfying 0 < x? 0.05,
Y is a real number satisfying 0 < y? 0.05,
Z is a real number satisfying 0 < z? 0.1. 3. The method according to claim 1 or 2,
Wherein the emission wavelength is in a range of 360 nm < / = 820 nm. 3. The method according to claim 1 or 2,
Wherein the emission characteristics of the phosphor are up-conversion. 3. The method according to claim 1 or 2,
Wherein the structure of the phosphor is a tetragonal system. Mixing the La precursor and the A precursor to produce a first powder;
Adding the first powder to NH ₄ F and then drying to produce a second powder; And
And heat treating the second powder. ≪ RTI ID = 0.0 >
A process for producing an oxyfluoride-based phosphor represented by the following formula (1) wherein p and q are not integers:
[Chemical Formula 1]

P is a real number of 0.55? P? 0.75,
Q is a real number satisfying 1.5? Q? 1.9,
X is a real number satisfying 0 < x < = 0.3,
A is a rare earth ion except La. The method according to claim 6,
The La precursor may be any one selected from the group consisting of La ₂ O _{3 ,} La (NO ₃ ) ₃ and LaF ₃ ,
Wherein the A precursor is any one selected from the group consisting of A ₂ O _{3 ,} A (NO ₃ ) ₃ and AF ₃ . A La precursor, an Er precursor, a Tm precursor, a Ho precursor, and a Yb precursor to prepare a third powder;
Adding the third powder to NH ₄ F and then drying to produce a fourth powder; And
And heat treating the fourth powder. ≪ RTI ID = 0.0 > 11. < / RTI &
A process for producing an oxyfluoride-based phosphor represented by the following general formula (2) wherein p and q are not integers:
(2)

P is a real number of 0.55? P? 0.75,
Q is a real number satisfying 1.5? Q? 1.9,
W is a real number satisfying 0 < w? 0.1,
X is a real number satisfying 0 < x? 0.05,
Y is a real number satisfying 0 < y? 0.05,
Z is a real number satisfying 0 < z? 0.1. 9. The method of claim 8,
The La precursor may be any one selected from the group consisting of La ₂ O _{3 ,} La (NO ₃ ) ₃ and LaF ₃ ,
The Er precursor may be any one selected from the group consisting of Er ₂ O _{3 ,} Er (NO ₃ ) ₃ and ErF ₃ ,
The Tm precursor may be any one selected from the group consisting of Tm ₂ O _{3 ,} Tm (NO ₃ ) ₃ , and TmF ₃ ,
The Ho precursor may be any one selected from the group consisting of Ho ₂ O _{3 ,} Ho (NO ₃ ) ₃ and HoF ₃ ,
Wherein the Yb precursor is any one selected from the group consisting of Yb ₂ O ₃ , Yb (NO ₃ ) ₃ and YbF ₃ . The method according to claim 6,
Wherein the step of preparing the first powder, the step of producing the second powder, and the step of heat-treating are performed in air. 9. The method of claim 8,
Wherein the step of preparing the third powder, the step of producing the fourth powder, and the step of heat-treating are performed in air. 9. The method according to claim 6 or 8,
Wherein the heat treatment is performed in a range of 900 ° C to 1100 ° C.

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