JP6259609B2 - Upconversion type phosphor and method for producing the same - Google Patents

Description

  The present invention relates to an up-conversion phosphor that is expected to be used in various fields.

  A phosphor is a substance that converts external energy taken into visible light, such as a fluorescent lamp, a white LED (light-emitting diode), a CRT (cathode-ray tube) display, a plasma display, a backlight for a liquid crystal display, etc. Widely used in lighting and displays.

  Among the phosphors described above, the fluorescence phenomenon due to photoexcitation is a phenomenon in which light is emitted when electrons excited by absorbing light energy return to the ground state in atoms serving as activators.

Luminescence that occurs in such a phosphor is roughly classified into the following two.
One is known as down-conversion, which refers to a phenomenon in which a phosphor emits light of lower energy than absorbed light as fluorescence.

  More specifically, electromagnetic waves such as normal X-rays, ultraviolet rays, visible rays, or infrared rays are absorbed by the down-conversion type phosphor, and electromagnetic waves having energy lower than the absorbed electromagnetic wave are emitted from the down-conversion type phosphor. Is. As shown in the left diagram of FIG. 1, after the light energy is absorbed and excited in one stage at the emission center (arrow numbered 1 (red solid line)), the thermal energy is released by thermal relaxation (numbering). 2 (black dotted line)), because it emits light (numbered 3 (green solid line) arrow), part of the absorbed light energy is lost due to thermal relaxation, so the light emission energy is lower than the absorbed light energy. . That is, fluorescence (arrow number 3 (green solid line) arrow) = absorbed light energy (arrow number 1 (red solid line) arrow) −thermal relaxation (arrow number 2 (black dotted line) arrow).

For example, YVO ₄ : Eu, which is a red phosphor, BaMgAl ₁₀ O ₁₇ : Eu, which is a blue phosphor, and Zn ₂ SiO ₄ : Mn, which is a green phosphor, are known as substances that perform the above-described conversion. Yes.

However, among the down-version phosphors, those that convert ultraviolet light into visible light are not suitable for use in living bodies that are damaged by ultraviolet light.
The other is known as up-conversion, which is a method of converting energy by emitting an electromagnetic wave having higher energy than the absorbed electromagnetic wave as fluorescence, contrary to the down-conversion.

  More specifically, red energy having energy higher than that of absorbed infrared light is absorbed by the up-conversion phosphor, which is an energy line having a longer wavelength than visible light, such as infrared light. This is a method of converting energy by emitting external light or visible light. Several different processes are possible for such conversion, but one example is described as follows. As shown in the center diagram of FIG. No. 5 (arrow indicated by the red solid line on the right orbit map)), the photosensitizer also absorbs light and is excited one step (number 4 (arrow indicated by the red solid line on the left orbit map)). The energy of the photosensitizer is immediately transferred to the emission center (arrow number 6 (black dotted line between the two orbital maps)), and the emission center excites the second stage (number 7 (right). (Solid red line above the orbit map). Next, the heat energy is released by thermal relaxation (arrow number 8 (black dotted line in the right orbit map)) and light is emitted (arrow number 9 (green solid line)). Although some of the light energy absorbed by thermal relaxation is lost, the energy received from the photosensitizer exceeds that, so the light energy absorbed by the luminescent center (number 5 (red below the right orbit map) The light emission energy (numbered 9 (green solid line arrow)) is larger than the solid line arrow). That is, fluorescence (numbered 9 (green solid line) arrow) = {light energy absorbed by the emission center (numbered 5 (red solid line under the right trajectory) arrow) + emission center from the photosensitizer Received light energy (arrow with number 7 (red solid line above right orbit))-thermal relaxation (arrow with number 8 (black dotted line on right orbit)).

For example, NaYF ₄ : Er, Yb, Y ₂ O ₃ : Er, Yb, Gd ₂ O ₃ : Er, Yb are known as up-conversion phosphors.
Among these phosphors, up-conversion phosphors, unlike down-conversion phosphors, use ultraviolet light, which tends to damage the irradiated object as excitation light, in order to obtain visible light emission. There is no need to use it. Therefore, the up-conversion phosphor hardly damages the irradiated object even if the irradiated object is, for example, a living tissue, and transmits the living tissue as compared with ultraviolet rays or visible light. Infrared light having a long distance, particularly near infrared light can be used as excitation light, and its application to the biomedical field is particularly expected.

  Conventionally, in the biomedical field, for example, fluorescent proteins, nano-down conversion phosphors, and quantum dots have been used for bioimaging. However, since there is a concern about the chemical stability and safety of these substances, up-conversion phosphors are attracting attention instead.

An example of a substance of such up-conversion phosphor, Nd _x and Y _1-X Ba ₂ Cl ₇ to the YBa ₂ Cl ₇ as the base material doped with Nd atom, a NaYF ₄ as the base material Er, Halide ceramics such as NaYF ₄ : Er, Yb doped with Yb atoms are known.

  However, although fluoride-based ceramics are high in brightness and stable, they contain a large amount of fluorine atoms that are considered dangerous for living bodies such as the human body. In addition, fluoride ceramics cannot be synthesized by firing, and complete removal of oxygen, water, etc. is essential from the reaction system. Metal halides are often lost from the reaction system due to their high volatility. The synthesis is difficult because the composition of the product is difficult to control.

Halide ceramics other than fluoride are easily hydrolyzed and generate hydrogen halide by hydrolysis, and therefore cannot be used for living bodies such as the human body or precision instruments.
On the other hand, oxide-based ceramics are basically oxides that can be manufactured and synthesized by mixing and heat-treating the base material, activator and photosensitizer in the air, and are oxides. So it has excellent stability. Therefore, it would be useful if a novel oxide ceramic up-conversion phosphor could be provided. On the other hand, conventional oxide ceramic up-conversion phosphors have lower luminance than fluoride ceramics represented by NaYF ₄ : Er, Yb. It would be more useful if an oxide ceramic up-conversion phosphor with higher brightness than the phosphor could be provided.

Incidentally, YTa ₇ O YTa ₇ doped with thulium (Tm) in ₁₉ O _19: although down-conversion phosphor consisting Tm ³⁺ is known (Non-Patent Document 4), a YTA ₇ O ₁₉ and the base member There is no known up-conversion type phosphor. In addition, as described above, the down-conversion type phosphor and the up-conversion type phosphor have different emission principles, so even if the base material is the same, know the properties of the up-conversion type phosphor from the properties of the down-conversion type phosphor. I don't get it.

  For example, as shown in the right diagram of FIG. 1, in the down-conversion type phosphor, light energy excited at the emission center is immediately used for thermal relaxation and light emission, and even if a photosensitizer is added, Effective energy transfer from the sensitizer to the emission center does not occur, and the two-stage excitation as in the up-conversion type phosphor does not necessarily occur. Therefore, even if a photosensitizer is added to the down-conversion type phosphor, it does not become an up-conversion type phosphor.

JP 2004-292599 A

Advanced Materials, 16, p2102-2105 Nano Letters, 4, p2191-2196 Journal of the American Chemical Society, 128, p7444-7445 The Chemical Society of Japan, No. 5, 630-634p, May 1993 Materials Letters Vol. 62, Issue 16, PP. 2500-2502 216th ECS Meeting, Abstract # 3213

  An object of the present invention is to provide a novel up-conversion type phosphor which is made of ceramics which shows high chemical stability and is easy to manufacture, and preferably has high luminance.

As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have found a novel up-conversion type phosphor composed of compounds represented by the following general formulas (1) to (3).
Furthermore, the present inventors have a crystal structure that is greatly related to the brightness of the up-conversion phosphor. If an oxide-based up-conversion phosphor having a specific crystal structure is produced, the oxide system It has been found that the brightness of the up-conversion type phosphor can be improved as compared with the prior art.

For example, in the conventional oxide-based up-conversion type phosphor whose base material is CeO ₂ , the crystal structure of the base material (CeO ₂ ) adopts a crystal structure in which rare earth atoms are close to each other, and the rare earth atoms (Ce) are three-dimensional. Therefore, it is presumed that the brightness decreases due to concentration quenching and does not become high brightness. That is, as shown in the upper diagram of FIG. 2, in the base material (CeO ₂ ) of the conventional up-conversion type phosphor, the rare earth atoms (Ce) are three-dimensionally distributed and close to each other, so that the brightness is not increased. It is guessed.

On the other hand, in the up-conversion type phosphor of the present invention, for example, when the base material is (LnTa ₇ O ₁₉ ), Ln is a specific + trivalent metal ion containing a specific lanthanide metal described later 2), as shown in the lower diagram of FIG. 2, specific + trivalent metal ions (Ln ³⁺ ) and tantalum ions (Ta ⁵⁺ ) containing a specific lanthanide metal are arranged in a layer of 1: 1 by ion number ( 2), the specific + trivalent metal (Ln ³⁺ ) is separated through the tantalum oxide layer, so that the luminance is hardly lowered due to concentration quenching and high luminance. It is assumed that

  That is, the up-conversion type phosphor according to the present invention is characterized by comprising ceramics represented by the following general formula (1), general formula (2), or general formula (3).

（上記一般式（１）中、ａは０〜０．９９８の範囲であり、ｂ＋ｃは０．００２〜1の範囲であり、ｂ：ｃは１００：１〜１：１００の範囲であり、ａ＋ｂ＋ｃ＝１である。

(In the general formula (1), a is in the range of 0 to 0.998, b + c is in the range of 0.002 to 1, b: c is in the range of 100: 1 to 1: 100, and a + b + c. = 1.

  In the general formula (2), a is in the range of 0.50 to 0.998, b + c is in the range of 0.002 to 0.50, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.

  In the general formula (3), a is in the range of 0.3 to 0.998, b + c is in the range of 0.002 to 0.7, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.

In the above general formula (1), general formula (2) and general formula (3), M ¹ is at least one trivalent metal atom having an ionic radius of 0.75 to 1.2Å (provided that Erbium (Er), holmium (Ho), ytterbium (Yb) and thulium (Tm) below are excluded),
M ² is at least one trivalent metal atom selected from the group consisting of erbium (Er), holmium (Ho) and thulium (Tm);
M ³ is at least one pentavalent metal atom selected from the group consisting of tantalum (Ta) and niobium (Nb).

_{However, YTaO 4: Er, Yb,} LaTaO 4: Er, Yb, GdTaO 4: Er, Yb, YTaO 4: Tm, Yb, YNbO 4: Er, Yb, and, YNbO _4: Tm, Yb is excluded. )
In the upconversion phosphor according to the present invention, in the general formula (1), the general formula (2), and the general formula (3), M ¹ is scandium (Sc), yttrium (Y), lanthanum (La), Cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), indium (In), bismuth (Bi), It is preferable from the viewpoint of providing an up-conversion phosphor having higher luminance that is at least one trivalent metal element selected from the group consisting of thallium (Tl) and antimony (Sb).

The upconversion phosphor according to the present invention is the above general formula (1), general formula (2), and general formula (3), wherein M ¹ is scandium, yttrium (Y), lanthanum (La), gadolinium (Gd ), Indium (In), bismuth (Bi), and antimony (Sb), at least one trivalent metal element selected from the group consisting of, can provide an up-conversion phosphor having higher brightness From the viewpoint of

In the upconversion phosphor according to the present invention, M ¹ in the general formula (1), the general formula (2), and the general formula (3) is yttrium (Y), lanthanum (La), and gadolinium (Gd). Is preferable from the viewpoint of providing an up-conversion phosphor having higher luminance.

  The up-conversion type phosphor according to the present invention preferably satisfies any one of the following requirements (I) to (IX) from the viewpoint of providing an up-conversion type phosphor having higher luminance.

(I) It consists of ceramics represented by the general formula (1), M ² is erbium (Er), a is in the range of 0 to 0.8, and b + c is in the range of 0.2 to 1. B: c is in the range of 1:10 to 10: 1 and a + b + c = 1;
(II) The ceramic is represented by the general formula (1), M ² is holmium (Ho), a is in the range of 0 to 0.8, and b + c is in the range of 0.2 to 1. B: c is in the range of 1:20 to 1: 2 and a + b + c = 1;
(III) It consists of ceramics represented by the general formula (1), M ² is thulium (Tm), a is in the range of 0 to 0.8, and b + c is in the range of 0.2 to 1. B: c is in the range of 1:20 to 1: 2 and a + b + c = 1;
(IV) Made of the ceramic represented by the general formula (2), M ² is erbium (Er), a is in the range of 0.5 to 0.95, and b + c is 0.05 to 0.5. B: c is in the range of 10: 1 to 1:10 and a + b + c = 1;
(V) It consists of ceramics represented by the general formula (2), M ² is holmium (Ho), a is in the range of 0.5 to 0.95, and b + c is 0.05 to 0.5. B: c is in the range of 1:20 to 1: 2, and a + b + c = 1;
(VI) It consists of ceramics represented by the above general formula (2), M ² is thulium (Tm), a is in the range of 0.5 to 0.95, and b + c is 0.05 to 0.5. B: c is in the range of 1:20 to 1: 2, and a + b + c = 1;
(VII) The ceramic is represented by the general formula (3), M ² is erbium (Er), a is in the range of 0.3 to 0.99, and b + c is 0.01 to 0.7. B: c is in the range of 1:10 to 10: 1 and a + b + c = 1;
(VIII) The ceramic is represented by the general formula (3), M ² is holmium (Ho), a is in the range of 0.3 to 0.99, and b + c is 0.01 to 0.7. B: c is in the range of 1:20 to 1: 2, and a + b + c = 1;
(IX) The ceramic is represented by the general formula (3), M ² is thulium (Tm), a is in the range of 0.3 to 0.99, and b + c is 0.01 to 0.7. B: c is in the range of 1:20 to 1: 2, and a + b + c = 1.

  The up-conversion type phosphor according to the present invention preferably satisfies any of the following requirements (I ′) to (IX ′) from the viewpoint of providing an up-conversion type phosphor with higher luminance.

(I ') It consists of ceramics represented by the above general formula (1), M ² is erbium (Er), a is in the range of 0 to 0.75, and b + c is in the range of 0.25 to 1. Yes, b: c is in the range of 1: 5-5: 2, a + b + c = 1;
(II ′) made of the ceramic represented by the general formula (1), M ² is holmium (Ho), a is in the range of 0 to 0.75, and b + c is in the range of 0.25 to 1. Yes, b: c is in the range of 1:20 to 1: 4, a + b + c = 1;
(III ') It consists of ceramics represented by the general formula (1), M ² is thulium (Tm), a is in the range of 0 to 0.75, and b + c is in the range of 0.25 to 1. Yes, b: c is in the range of 1:20 to 1: 5, a + b + c = 1;
(IV ′) Made of the ceramic represented by the general formula (2), M ² is erbium (Er), a is in the range of 0.6 to 0.95, and b + c is 0.05 to 0.00. 4; b: c is in the range 1: 5-5: 2; a + b + c = 1;
(V ′) Made of the ceramic represented by the general formula (2), M ² is holmium (Ho), a is in the range of 0.6 to 0.95, and b + c is 0.05 to 0.00. 4; b: c is in the range 1:20 to 1: 4; a + b + c = 1;
(VI ′) Made of the ceramic represented by the general formula (2), M ² is thulium (Tm), a is in the range of 0.6 to 0.95, and b + c is 0.05 to 0.00. 4; b: c is in the range 1: 20-1: 5; a + b + c = 1;
(VII ′) Made of the ceramic represented by the general formula (3), M ² is erbium (Er), a is in the range of 0.5 to 0.99, and b + c is 0.01 to 0.00. A range of 5; b: c is in the range of 1: 5 to 5: 2, and a + b + c = 1;
(VIII ′) Made of the ceramic represented by the above general formula (3), M ² is holmium (Ho), a is in the range of 0.5 to 0.99, and b + c is 0.01 to 0.00. A range of 5; b: c is in the range of 1:20 to 1: 4; a + b + c = 1;
(IX ′) It is made of ceramics represented by the above general formula (3), M ² is thulium (Tm), a is in the range of 0.5 to 0.9, and b + c is 0.1 to 0.00. 5, b: c is in the range of 1:20 to 1: 5, and a + b + c = 1.

  The first method for producing an up-conversion phosphor made of ceramics represented by the following general formula (1), general formula (2) or general formula (3) according to the present invention has an ionic radius of 0.75 to 0.75. First of at least one base material (A) that is a compound of a trivalent metal (except erbium (Er), holmium (Ho), ytterbium (Yb) and thulium (Tm)) that is 1.2% And a second raw material (a ′) of a base material (A) comprising a compound of at least one pentavalent metal selected from the group consisting of a tantalum (Ta) compound and a niobium (Nb) compound ), An activator raw material compound (B) that is a compound of at least one trivalent metal selected from an erbium (Er) compound, a holmium (Ho) compound, and a thulium (Tm) compound, and ytterbi The photosensitizer raw material compound (C) composed of the compound (Yb) is mixed so as to satisfy any of the following conditions (XI) to (XIII), and the obtained powder mixture is mixed at 800 to 1500 ° C. It is characterized by firing.

（上記一般式（１）中、ａは０〜０．９９８の範囲であり、ｂ＋ｃは０．００２〜１の範囲であり、ｂ：ｃは１００：１〜１：１００の範囲であり、ａ＋ｂ＋ｃ＝１である。

(In the general formula (1), a is in the range of 0 to 0.998, b + c is in the range of 0.002 to 1, b: c is in the range of 100: 1 to 1: 100, and a + b + c. = 1.

  In the general formula (2), a is in the range of 0.50 to 0.998, b + c is in the range of 0.002 to 0.50, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.

  In the general formula (3), a is in the range of 0.30 to 0.998, b + c is in the range of 0.002 to 0.70, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.

In the above general formula (1), general formula (2) and general formula (3), M ¹ is at least one trivalent metal atom having an ionic radius of 0.75 to 1.2Å (provided that Erbium (Er), holmium (Ho), ytterbium (Yb) and thulium (Tm) below are excluded),
M ² is at least one trivalent metal atom selected from the group consisting of erbium (Er), holmium (Ho) and thulium (Tm);
M ³ is at least one pentavalent metal atom selected from the group consisting of tantalum (Ta) and niobium (Nb).

_{However, YTaO 4: Er, Yb,} LaTaO 4: Er, Yb, GdTaO 4: Er, Yb, YTaO 4: Tm, Yb, YNbO 4: Er, Yb, and, YNbO _4: Tm, Yb is excluded. )
(XI) When producing an up-conversion phosphor made of ceramics represented by the general formula (1),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 0 to 99.8 atomic%, the metal atom of the activator raw material compound (B) and the metal atom of the photosensitizer raw material compound (C). The total is 0.2-100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). Mixing so that it may become a ratio of 490-910 with respect to the total number of atoms 100 of an atom and the metal atom of a photosensitizer raw material compound (C);
(XII) When producing an up-conversion type phosphor composed of the ceramic represented by the general formula (2), the metal atom of the first raw material (a) of the base material (A), the activator raw material compound ( When the sum of the metal atoms of B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%,
The metal atom of the first raw material (a) of the base material (A) is 99.8 to 50.0 atomic%, the metal atom of the activator raw material compound (B) and the metal of the photosensitizer raw material compound (C). The total number of atoms is 0.2-50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). Mixing so that it may become a ratio of 70-130 with respect to the total number of atoms 100 of an atom and the metal atom of a photosensitizer raw material compound (C);
(XIII) When manufacturing an up-conversion phosphor made of ceramics represented by the general formula (3),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 99.8 to 30.0 atomic%, the metal atom of the activator raw material compound (B), and the metal of the photosensitizer raw material compound (C). The total number of atoms is 0.2-70 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). It mixes so that it may become a ratio of 23-43 with respect to the total number of atoms 100 of an atom and the metal atom of a photosensitizer raw material compound (C).

  The second production method of the up-conversion type phosphor according to the present invention is a trivalent metal having an ionic radius of 0.75 to 1.2% (however, erbium (Er), holmium (Ho), ytterbium (Yb)). And a first raw material (a) of at least one base material (A) composed of a compound of erbium (Er), a compound of holmium (Ho) and thulium (Tm). Activator raw material compound (B) which is a compound of at least one trivalent metal selected from compounds, photosensitizer raw material compound (C) containing ytterbium (Yb) as a metal compound, and base material (A And at least one pentavalent metal compound selected from the group consisting of a compound of tantalum (Ta) and a compound of niobium (Nb) which is the second raw material (a ′) of the base material (A) At least one coordinating organic compound complex selected from the group consisting of a coordinating organic compound complex of tantalum and niobium coordinating organic compound complex as the second raw material (a ′); A compound and a solvent are mixed so as to satisfy any of the following conditions (XI) to (XIII) to prepare a mixed solution, and then the obtained mixed solution is heated at 120 to 150 ° C. The liquid component is evaporated, the resulting product is heated at 400-500 ° C. to form a ceramic precursor, and then the obtained ceramic precursor is calcined at 800-1500 ° C.

（上記一般式（１）中、ａは０〜０．９９８の範囲であり、ｂ＋ｃは０．００２〜１の範囲であり、ｂ：ｃは１００：１〜１：１００の範囲であり、ａ＋ｂ＋ｃ＝１である。

(In the general formula (1), a is in the range of 0 to 0.998, b + c is in the range of 0.002 to 1, b: c is in the range of 100: 1 to 1: 100, and a + b + c. = 1.

  In the general formula (2), a is in the range of 0.50 to 0.998, b + c is in the range of 0.002 to 0.50, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.

  In the general formula (3), a is in the range of 0.30 to 0.998, b + c is in the range of 0.002 to 0.70, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.

In the above general formula (1), general formula (2) and general formula (3), M ¹ is at least one trivalent metal atom having an ionic radius of 0.75 to 1.2Å (provided that Erbium (Er), holmium (Ho), ytterbium (Yb) and thulium (Tm) below are excluded),
M ² is at least one trivalent metal atom selected from the group consisting of erbium (Er), holmium (Ho) and thulium (Tm);
M ³ is at least one pentavalent metal atom selected from the group consisting of tantalum (Ta) and niobium (Nb).

_{However, YTaO 4: Er, Yb,} LaTaO 4: Er, Yb, GdTaO 4: Er, Yb, YTaO 4: Tm, Yb, YNbO 4: Er, Yb, and, YNbO _4: Tm, Yb is excluded. )
(XI) When producing an up-conversion phosphor made of ceramics represented by the general formula (1),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 0 to 99.8 atomic%, the metal atom of the activator raw material compound (B) and the metal atom of the photosensitizer raw material compound (C). The total is 0.2-100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(XII) When producing an up-conversion type phosphor composed of the ceramic represented by the general formula (2), the metal atom of the first raw material (a) of the base material (A), the activator raw material compound ( When the sum of the metal atoms of B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%,
The metal atom of the first raw material (a) of the base material (A) is 99.8 to 50.0 atomic%, the metal atom of the activator raw material compound (B) and the metal of the photosensitizer raw material compound (C). The total number of atoms is 0.2-50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(XIII) When manufacturing an up-conversion phosphor made of ceramics represented by the general formula (3),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 99.8 to 30.0 atomic%, the metal atom of the activator raw material compound (B), and the metal of the photosensitizer raw material compound (C). The total number of atoms is 0.2-70 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100,
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
It mixes so that the quantity of the said coordinating organic compound may be 1-10 times mole with respect to all the metals.

  Hereinafter, unless otherwise specified, the first manufacturing method of the up-conversion phosphor and the second manufacturing method of the up-conversion phosphor are collectively referred to as “up-conversion phosphor manufacturing method”.

  In the method for producing an upconversion phosphor according to the present invention, the metal of the first raw material (a) of the base material (A) is scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce). ), Praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), indium (In), bismuth (Bi), thallium (Tl) And at least one trivalent metal selected from the group consisting of antimony (Sb) is preferred from the standpoint that an up-conversion phosphor having higher luminance can be produced.

  In the method for producing an upconversion phosphor according to the present invention, the metal of the first raw material (a) of the base material (A) is scandium, yttrium (Y), lanthanum (La), gadolinium (Gd), indium. From the viewpoint that at least one trivalent metal element selected from the group consisting of (In), bismuth (Bi) and antimony (Sb) can produce an up-conversion phosphor having higher luminance. preferable.

  In the second method for producing an up-conversion phosphor according to the present invention, it is preferable that the oxycarboxylic acid is citric acid from the viewpoint of producing an up-conversion phosphor having higher luminance.

  In the method for producing an up-conversion phosphor according to the present invention, the metal of the first raw material (a) of the base material (A) is yttrium (Y), lanthanum (La), and gadolinium (Gd). However, it is preferable from the viewpoint that an up-conversion type phosphor having higher luminance can be manufactured.

In the method for producing an up-conversion type phosphor according to the present invention, it is possible to perform the above mixing so as to satisfy any one of the following conditions (I ″) to (IX ″). Is preferable from the standpoint that a phosphor can be manufactured.
(I ″) When manufacturing an up-conversion type phosphor made of a ceramic represented by the above general formula (1) and M ² being erbium (Er),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 0 to 80 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 20-100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:10 to 10: 1, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(II ″) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (1) and M ² being holmium (Ho),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 0 to 80 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 20-100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(III ″) When manufacturing an up-conversion type phosphor composed of ceramics represented by the above general formula (1) and M ² being thulium (Tm),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 0 to 80 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 20-100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(IV ″) When manufacturing an up-conversion type phosphor composed of ceramics represented by the above general formula (2) and M ² being erbium (Er),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total amount of metal atoms of the first raw material (a) of the base material (A) is 50 to 95 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 5 to 50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 10: 1 to 10: 1, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(V ″) When manufacturing an up-conversion type phosphor composed of ceramics represented by the above general formula (2) and M ² being holmium (Ho),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total amount of metal atoms of the first raw material (a) of the base material (A) is 50 to 95 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 5 to 50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(VI ″) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (2) and M ² being thulium (Tm),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total amount of metal atoms of the first raw material (a) of the base material (A) is 50 to 95 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 5 to 50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(VII ″) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (3) and M ² being erbium (Er),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 30 to 99 atomic%, the metal atoms of the activator raw material compound (B) and the metal sensitizer raw material compound (C). 1-70 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:10 to 10: 1, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(VIII ″) In the case of producing an upconversion phosphor comprising the ceramic represented by the general formula (3) and M ² being holmium (Ho),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 30 to 99 atomic%, the metal atoms of the activator raw material compound (B) and the metal sensitizer raw material compound (C). 1-70 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(IX ″) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (3) and M ² being thulium (Tm),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 30 to 99 atomic%, the metal atoms of the activator raw material compound (B) and the metal sensitizer raw material compound (C). 1-70 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
It mixes so that the quantity of the said coordinating organic compound may be 1-10 times mole with respect to all the metals.

In the method for producing an up-conversion phosphor according to the present invention, it is further brighter to perform the mixing so as to satisfy any of the following conditions (I ′ ′ ′) to (IX ′ ′ ′). It is more preferable from the standpoint that an up-conversion type phosphor can be manufactured.
(I ′ ′ ′) In the case of producing an upconversion phosphor comprising the ceramic represented by the general formula (1) and M ² being erbium (Er),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 0 to 75 atomic%, the total of the metal atom of the activator raw material compound (B) and the metal atom of the photosensitizer raw material compound (C) is 25 to 100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1: 5 to 5: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(II ′ ′ ′) In the case of producing an up-conversion type phosphor made of ceramics represented by the above general formula (1) and M ² being holmium (Ho),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 0 to 75 atomic%, the total of the metal atom of the activator raw material compound (B) and the metal atom of the photosensitizer raw material compound (C) is 25 to 100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 4, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(III ′ ′ ′) In the case of producing an upconversion phosphor comprising the ceramic represented by the general formula (1) and M ² being thulium (Tm),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 0 to 75 atomic%, the total of the metal atom of the activator raw material compound (B) and the metal atom of the photosensitizer raw material compound (C) is 25 to 100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 5, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(IV ′ ′ ′) In the case of producing an up-conversion type phosphor made of ceramics represented by the above general formula (2) and M ² being erbium (Er),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 60 to 95 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 5-40 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1: 5 to 5: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(V ′ ′ ′) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (2) and M ² being holmium (Ho),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 60 to 95 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 5-40 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 4, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(VI ′ ′ ′) In the case of producing an up-conversion type phosphor composed of ceramics represented by the above general formula (2) and M ² being thulium (Tm),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 60 to 95 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 5-40 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 5, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(VII ′ ′ ′) In the case of producing an upconversion phosphor comprising the ceramic represented by the general formula (3) and M ² being erbium (Er),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 50 to 99 atomic%, the metal atoms of the activator raw material compound (B) and the metal sensitizer raw material compound (C). 1 to 50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1: 5 to 5: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(VIII ′ ′ ′) In the case of producing an upconversion phosphor comprising the ceramic represented by the general formula (3) and M ² being holmium (Ho),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 50 to 99 atomic%, the metal atoms of the activator raw material compound (B) and the metal sensitizer raw material compound (C). 1 to 50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 4, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(IX ′ ′ ′) When manufacturing an up-conversion phosphor made of ceramics represented by the above general formula (3) and M ² being thulium (Tm),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total amount of metal atoms of the first raw material (a) of the base material (A) is 50 to 90 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 10-50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 5, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
It mixes so that the quantity of the said coordinating organic compound may be 1-10 times mole with respect to all the metals.

  In the method for producing an up-conversion phosphor according to the present invention, at least one flux agent selected from the group consisting of a boron compound, an alkali metal halide and an alkaline earth metal halide is added to the ceramic precursor. From the standpoint that it is possible to produce an up-conversion phosphor with higher luminance, by adding the amount of 0.1 to 50% by weight with respect to 100% by weight of the up-conversion phosphor and performing the above baking. preferable.

  According to the present invention, there are provided an up-conversion phosphor made of ceramics that exhibits high chemical stability and is easy to manufacture, and preferably has high brightness, and a method for manufacturing the same.

FIG. 1 shows the emission principle of a down-conversion phosphor (left), the emission principle of an up-conversion phosphor (center), and the difference between a down-conversion and up-conversion phosphor (right). FIG. FIG. 2 is a diagram showing the crystal structure of the base material of the up-conversion type phosphor. FIG. 3 is a diagram illustrating an example of a complex gel method scheme. FIG. 4 is a diagram showing X-ray diffraction (XRD) of a single crystal of YTa ₇ O ₁₉ and XRD of Er ³⁺ , Yb ³⁺ co-added YTa ₇ O ₁₉ powder. FIG. 5 is a graph showing the emission intensity of the phosphor of the present invention and the conventional oxide phosphor (CeO ₂ : Er, Yb). FIG. 6 shows the blending amounts of Er and Yb (b and c) in (M ¹ _a M ² _b Yb _c ) M ³ ₇ O ₁₉ (M ¹ = Y, M ² = Er, M ³ = Ta) of the present invention. (The left figure is a live-action image, the right figure is a color diagram, and the contents to be represented are the same). FIG. 7 shows that in the (M ¹ _a M ² _b Yb _c ) M ³ ₇ O ₁₉ (M ¹ = Ln, M ² = Er, M ³ = Ta) of the present invention, Ln is replaced with Y, La, Gd, Furthermore, it is a figure which shows the result of having compared the light emission luminance of the fluorescent substance from which a base material composition differs when the ratio of a-c was changed. FIG. 8 shows the first of the base material (A) when the base material is formed by mixing the first raw material (a) and the second raw material (a ′) of the base material (A) during phosphor synthesis. It is a graph depicting the relationship between the presence of single-phase formation in the ratio of M ³ atoms of a second material of the base material (a) (a '), phosphor obtained for M ¹ atom of the raw material of (a) . FIG. 9 shows (Y _0.5 Er _0.1 Yb _0.4 ) Ta ₇ O ₁₉ (number 12), (Y _0.5 Ho _0.1 Yb _0.4 ) Ta ₇ O ₁₉ (number 13) and (Y _0.5 Tm _0.1 Yb _0.4 ) Ta ₇ O ₁₉ (numbering 14) is a graph showing an emission intensity of. Figure 10 is represented by ^{_{(M 1 a M 2 b Yb}} c) M 3 of M ³ ₇ O ₁₉ is mixed _{system, (Y 0.5 Er 0.1 Yb 0.4} ) (Ta 1-x Nb x) 7 O 19 It is a figure which shows the up-conversion light emission intensity | strength of a Ta-Nb mixed system. Figure 11 is a diagram showing a relative brightness of the up-conversion phosphor is ^{_{(M 1 a M 2 b Yb}} c) M 3 7 M 1 of O ₁₉ is mixed system. FIG. 12 is a diagram showing the light emission intensity of an up-conversion phosphor composed of (M ¹ _a M ² _b Yb _c ) M ³ ₇ O ₁₉ and an up-conversion phosphor composed of CeO ₂ : Er, Yb.

[Definition]
In this specification, the following terms are defined as follows.
“Visible light” refers to an electromagnetic wave having a wavelength of 380 to 750 nm, and is also referred to as visible light.
“Ultraviolet light” refers to an electromagnetic wave having a wavelength of 1 nm or more and less than 380 nm, and is also referred to as ultraviolet light.
“Infrared light” refers to electromagnetic waves having a wavelength exceeding 750 nm and 1 mm or less, and is also referred to as infrared rays.
“Near-infrared light” refers to an electromagnetic wave having a wavelength exceeding 750 nm and not more than 2500 nm among infrared light, and is also referred to as near-infrared light.

When the ceramic composition is expressed by an element in parentheses and an element outside the parentheses such as “(Y _0.5 Er _0.1 Yb _0.4 ) Ta ₇ O ₁₉ ”, the elements inside the parentheses and the elements outside the parentheses are Forms the basic skeleton structure of ceramics. The element corresponding to M ² in the parentheses (Er in the above example) represents the type of atom derived from the activator raw material compound doped in the base material, and the rightmost element in the parentheses (Yb in the above). Represents the type of atom derived from the photosensitizer doped in the base material, and the subscript number represents the number of atoms of each element, but the subscript number in parentheses is set to be 1 The

On the other hand, for example, in the case where a subscript number in the parenthesis is not described, such as “(YErYb) Ta ₇ O ₁₉ ”, in this example, the activator is added to the base material YTa ₇ O _19. It represents that Er which is an atom derived from the raw material compound and Yb which is an atom derived from the photosensitizer raw material compound are doped. This notation does not indicate the actual composition of ceramics (composition ratio of each atom).

For example, in the case of “(YErYb) Ta ₇ O ₁₉ ”, the notation indicating the composition of ceramics with parentheses as described above is the position of Y, Er, Yb at the X position of XTa ₇ O ₁₉ . Indicates that each atom is present in any proportion.

In addition, when the composition of ceramics is expressed by a composition formula, a colon (:), an element symbol and a number (all displayed for each element), for example, “Ce _0.84 O _1.98 : Er _0.035 Yb _0.0044 Si _0.12 ” The composition formula on the left side of the colon indicates the composition formula of the basic skeleton structure of ceramics, the element symbol on the right side of the colon indicates the type of atoms doped in the base material, and the subscript numbers are silicon atoms (Si) and cerium atoms (Ce) and the number of each atom when the total number of all rare earth atoms is 1, respectively. This notation indicates the actual composition of ceramics determined by, for example, elemental analysis measurement. Note that the colon may be omitted.

On the other hand, for example, when no number is written on the right side of the colon as in “CeO ₂ : Er, Yb”, the left side of the colon represents the base material, and the right side of the colon represents the type of dopant. This notation does not indicate the actual composition of ceramics (composition ratio of each atom). Note that the colon may be omitted.

For example, in the case of “YTa ₇ O ₁₉ : Er, Yb”, the notation with a colon as described above indicates that Y or Ta is substituted with Er or Yb. However, in the up-conversion type phosphor according to the present invention, the activator and the photosensitizer are trivalent atoms, and therefore the actual substitution with Er (activator) or Yb (photosensitizer) Y which is a trivalent atom and Ta which is a pentavalent atom are not substituted.

That is, the upconversion phosphor according to the present invention is the same solid solution, for example, “(YErYb) Ta ₇ O ₁₉ ” or “YTa ₇ O ₁₉ : Er, Yb”. Indicates.

In the ceramic represented by (M ¹ _a M ² _b Yb _c ) M ³ ₇ O ₁₉ , the “base material” is a material doped with a dopant such as a metal atom represented by M ² or Yb. It means what constitutes a doped body (a body to be doped). The composition of the “base material” does not indicate the actual composition in the ceramic. When the actual composition in ceramics is indicated, it is separately indicated as “basic structure skeleton”. For example, in a ceramic having a composition of “(Y _0.5 Er _0.1 Yb _0.4 ) Ta ₇ O ₁₉ ”, the basic structure skeleton is “YTa ₇ O ₁₉ ”, and the basic structure is almost maintained, and a part of Y Is substituted with Er and Yb. However, in the X-ray diffraction measurement, even if the composition is different from YTa ₇ O ₁₉ which is the base material, the peak value almost coincides with “YTa ₇ O ₁₉ ”. When the amount of M ² or Yb is large, or when M ¹ is 0 and the ionic radius of M ² or Yb is close to the ionic radius of M ¹ , the basic structural skeleton similar to YTa ₇ O ₁₇ is used. Form.

  “Doping” or “doping” refers to adding a small amount of impurities (dopant) to a base material. The dopant may be present in some form in the base material, may be substituted for atoms in the base material crystal lattice, or may exist in a space surrounded by the base material crystal lattice. Also good.

The “doping amount” refers to an amount doped in the base material (amount of dopant contained in the base material).
“Atom%” refers to the ratio (percentage) of the number of target atoms when the total number of specific atomic groups is 100 atomic%.

“Au” is an abbreviation for “arbitrary unit” and indicates an arbitrary unit.
Ln is generally a generic name for lanthanide metals, but in this specification, unless otherwise specified, M ^{1 in the} general formula (1), (2) or (3) is the ionic radius of M ¹ and A metal ion that satisfies the valence (trivalent) requirement is called Ln.
The present invention will be described below.

1. Up-conversion type phosphor The up-conversion type phosphor according to the present invention is an up-conversion type phosphor composed of a compound represented by the following general formula (1), general formula (2) or general formula (3).

（上記一般式（１）中、ａは０〜０．９９８の範囲であり、ｂ＋ｃは０．００２〜１の範囲であり、ｂ：ｃは１００：１〜１：１００の範囲であり、ａ＋ｂ＋ｃ＝１である。

(In the general formula (1), a is in the range of 0 to 0.998, b + c is in the range of 0.002 to 1, b: c is in the range of 100: 1 to 1: 100, and a + b + c. = 1.

  In the general formula (2), a is in the range of 0.50 to 0.998, b + c is in the range of 0.002 to 0.50, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.

  In the general formula (3), a is in the range of 0.30 to 0.998, b + c is in the range of 0.002 to 0.70, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.

In the above general formula (1), general formula (2) and general formula (3), M ¹ is at least one trivalent metal atom having an ionic radius of 0.75 to 1.2Å (provided that The following erbium (Er), holmium (Ho), ytterbium (Yb) and thulium (Tm) are excluded).

M ² is at least one pentavalent metal atom selected from the group consisting of erbium (Er), holmium (Ho), and thulium (Tm).
M ³ is at least one pentavalent metal atom selected from the group consisting of tantalum (Ta) and niobium (Nb).

However, from the up-conversion type phosphor according to the present invention, YTaO ₄ : Er _, Yb, LaTaO ₄ : Er _, Yb, GdTaO ₄ : Er _, Yb, YTaO ₄ : Tm _, Yb, YNbO ₄ : Er, Yb, and YNbO ₄ : Tm and Yb are excluded.

(M ¹ _a M ² _b Yb _c ) M ³ ₇ O ₁₉ (M ¹ _a M ² _b Yb _c ), M ³ , O atom ratio (1: 7: 19), (M ¹ _a M ² _b Yb _c ) M ³ O ₄ (M ¹ _a M ² _b Yb _c ), M ³ , O atom ratio (1: 1: 4), (M ¹ _a M ² _b Yb _c ) ₃ M ³ The ratio of the number of atoms of O ₇ (M ¹ _a M ² _b Yb _c ), M ³ , and O (3: 1: 7) is determined according to the raw materials (trivalent metal compounds, This is achieved by using a pentavalent metal compound, an activator raw material compound, a photosensitizer raw material compound).

1-1. M ^{1 in} general formula (1), general formula (2) and general formula (3)
In the above general formula (1), general formula (2) and general formula (3), M ¹ is at least one trivalent metal atom having an ionic radius of 0.75 to 1.2 Å (provided that The following erbium (Er), holmium (Ho), ytterbium (Yb) and thulium (Tm) are excluded).

The ion radius is a value obtained by rounding off the third decimal place after the decimal point.
The ionic radius of M ¹ is preferably 0.75 to 1.20 観 点 from the viewpoint of providing an up-conversion phosphor having higher luminance.

From the viewpoint of providing a higher-brightness up-conversion phosphor, the atomic species of M ¹ is scandium (Sc, ionic radius 0.75%), yttrium (Y, ionic radius 0.90%), lanthanum (La, Ion radius 1.03Å), cerium (Ce, ion radius 1.01Å), praseodymium (Pr, ion radius 0.99Å), neodymium (Nd, ion radius 0.98Å), samarium (Sm, ion radius 0.96Å) , Europium (Eu, ion radius 0.95Å), gadolinium (Gd, ion radius 0.94Å), terbium (Tb, ion radius 0.92Å), dysprosium (Dy, ion radius 0.91Å), indium (In, ion Radius 0.94 mm), bismuth (Bi, ion radius 1.17 mm), thallium (Tl, ion radius 1.0) Preferably at least one trivalent metal element selected from the group consisting of モ ン) and antimony (Sb, ionic radius 0.90Å), scandium (Sc, ionic radius 0.75Å), yttrium (Y, ion Radius 0.90Å), lanthanum (La, ion radius 1.03Å) and gadolinium (Gd, ion radius 0.94Å), indium (In, ion radius 0.94Å), bismuth (Bi, ion radius 1.17Å), More preferably, it is at least one trivalent metal element selected from the group consisting of antimony (Sb, ionic radius 0.90Å), yttrium (Y, ionic radius 0.90Å), lanthanum (La, ionic radius 1). 0.03) and gadolinium (Gd, ionic radius 0.94 cm) are particularly preferred.

In the up-conversion phosphor, the ionic radius of M ¹ is very important in forming the up-conversion phosphor. For example, as described above, a specific ion radius of 0.75 to 1.20１．２ The trivalent metal ion species stably forms an LnTa ₇ O ₁₉ type crystal structure as shown in FIG. 2 in the up-conversion phosphor represented by the general formula (1). Therefore, other atomic species (other than M ¹ ) forming the up-conversion phosphor, that is, activator atom (M ² ), photosensitizer atom (Yb), tantalum, niobium (both M ³ ), and oxygen At the same time, an up-conversion phosphor having excellent luminous efficiency can be formed.

1-2. M ^{2 in} general formula (1), general formula (2) and general formula (3)
In the general formula (1), general formula (2), and general formula (3), M ² is at least one trivalent selected from the group consisting of erbium (Er), holmium (Ho), and thulium (Tm). Metal atom.

These trivalent metal atoms can be appropriately selected in consideration of the wavelength and luminance (fluorescence) of the emission color.
Specific absorption wavelength and emission wavelength will be described later.

From the viewpoint of providing an up-conversion phosphor having higher luminance, erbium (Er) and holmium (Ho) are preferable, and erbium (Er) is more preferable. Since different M ² emits light in different wavelength ranges, M ² can be selected according to a desired emission color. By using one or more kinds of M ² at an arbitrary ratio, the emission color can be adjusted.

1-3. M ^{3 in} general formula (1), general formula (2) and general formula (3)
In the above general formula (1), general formula (2) and general formula (3), M ³ is at least one metal atom selected from the group consisting of tantalum (Ta) and niobium (Nb).
Tantalum (Ta): Niobium (Nb) is atomic%, and in the upconversion material of the general formula (1), 1: 0 to 0.5: 0.5, of the general formula (2) and the general formula (3) In the upconversion material, 1: 0 to 0: 1 is preferable from the viewpoint of luminance.
From the viewpoint of providing a higher-brightness upconversion phosphor, M ³ preferably contains tantalum (Ta), more preferably tantalum (Ta).

1-4. The ceramics in which the combinations M ¹ , M ² , and M ³ of M ¹ , M ² , and M ^{3 in} the general formula (1), general formula (2), and general formula (3) are as described above are all up-converted. Although it is a fluorescent substance that emits light in a mold, an up-conversion fluorescent substance with higher luminance can be provided by combining the preferable atoms with respect to M ¹ , M ² , and M ³ .

For example, (YErYb) Ta ₇ O ₁₉ , (LaErYb) Ta ₇ O ₁₉ , and (GdErYb) Ta ₇ O ₁₉ have higher brightness than other up-conversion phosphors, but (YErYb) Ta ₇ O ₁₉ is particularly bright (see FIG. 7).

1-5. A, b, c in general formula (1), general formula (2), and general formula (3)
A, b, and c in the general formula (1), the general formula (2), and the general formula (3) are as described above.
From the viewpoint of providing an up-conversion type phosphor having higher luminance, it will be described below in more detail for each kind of M ² atoms.

<When M ² is Erbium (Er)>
When M ² is erbium (Er), the following is more preferable from the viewpoint of the luminance of the up-conversion phosphor.

In the general formula (1), a is in the range of 0 to 0.8, b + c is in the range of 0.2 to 1, b: c is in the range of 1:10 to 10: 1, and a + b + c = 1.
In the general formula (2), a is in the range of 0.5 to 0.95, b + c is in the range of 0.05 to 0.5, and b: c is in the range of 1:10 to 10: 1. Yes, a + b + c = 1.

In the general formula (3), a is in the range of 0.3 to 0.99, b + c is in the range of 0.01 to 0.7, and b: c is in the range of 1:10 to 10: 1. Yes, a + b + c = 1.
From the same viewpoint, the following is more preferable.

In the general formula (1), a is in the range of 0 to 0.75, b + c is in the range of 0.25 to 1, b: c is in the range of 1: 5 to 5: 2, and a + b + c = 1.
In the general formula (2), a is in the range of 0.6 to 0.95, b + c is in the range of 0.05 to 0.4, and b: c is in the range of 1: 5 to 5: 2. Yes, a + b + c = 1.
In the general formula (3), a is in the range of 0.5 to 0.99, b + c is in the range of 0.01 to 0.5, and b: c is in the range of 1: 5 to 5: 2. Yes, a + b + c = 1.

<When M ² is Holmium (Ho)>
When M ² is holmium (Ho), the following is more preferable from the viewpoint of the luminance of the up-conversion phosphor.

In the general formula (1), a is in the range of 0 to 0.8, b + c is in the range of 0.2 to 1, b: c is in the range of 1:20 to 1: 2, and a + b + c = 1.
In the general formula (2), a is in the range of 0.5 to 0.95, b + c is in the range of 0.05 to 0.5, and b: c is in the range of 1:20 to 1: 2. Yes, a + b + c = 1.

In the general formula (3), a is in the range of 0.3 to 0.99, b + c is in the range of 0.01 to 0.7, and b: c is in the range of 1:20 to 1: 2. Yes, a + b + c = 1.
From the same viewpoint, the following is more preferable.

In the general formula (1), a is in the range of 0 to 0.75, b + c is in the range of 0.25 to 1, b: c is in the range of 1:20 to 1: 4, and a + b + c = 1.
In the general formula (2), a is in the range of 0.6 to 0.95, b + c is in the range of 0.05 to 0.4, and b: c is in the range of 1:20 to 1: 4. Yes, a + b + c = 1.

In the general formula (3), a is in the range of 0.5 to 0.99, b + c is in the range of 0.01 to 0.5, and b: c is in the range of 1:20 to 1: 4. Yes, a + b + c = 1.
From the same viewpoint, the following is more preferable.

<When M ² is Thulium (Tm)>
When M ² is thulium (Tm), the following is more preferable from the viewpoint of the luminance of the up-conversion phosphor.

In the general formula (1), a is in the range of 0 to 0.8, b + c is in the range of 0.2 to 1, b: c is in the range of 1:20 to 1: 2, and a + b + c = 1.
In the general formula (2), a is in the range of 0.5 to 0.95, b + c is in the range of 0.05 to 0.5, and b: c is in the range of 1:20 to 1: 2. Yes, a + b + c = 1.

In the general formula (3), a is in the range of 0.3 to 0.99, b + c is in the range of 0.01 to 0.7, and b: c is in the range of 1:20 to 1: 2. Yes, a + b + c = 1.
From the same viewpoint, the following is more preferable.

In the general formula (1), a is in the range of 0 to 0.75, b + c is in the range of 0.25 to 1, b: c is in the range of 1:20 to 1: 5, and a + b + c = 1.
In the general formula (2), a is in the range of 0.6 to 0.95, b + c is in the range of 0.05 to 0.4, and b: c is in the range of 1:20 to 1: 5. Yes, a + b + c = 1.

In the general formula (3), a is in the range of 0.5 to 0.9, b + c is in the range of 0.1 to 0.5, and b: c is in the range of 1:20 to 1: 5. Yes, a + b + c = 1.
The up-conversion type phosphor having the above composition can be produced by adjusting the blending amount of each raw material as described in the item of the production method described later.

  The composition can be confirmed by elemental analysis. For example, by performing elemental analysis of an upconversion phosphor using an energy dispersive X-ray analyzer (EDX), the composition of the upconversion phosphor can be determined. I can confirm.

1-6. Other components The up-conversion type phosphor of the present invention includes (M ¹ _a M ² _b Yb _c ) M ³ ₇ O ₁₉ , (M ¹ _a M ² _b Yb _c ) M ³ O or (M ¹ _a M ² _{In addition to b} Yb _c ) ₃ M ³ O ₇ , other components such as aluminum (Al) may be included as necessary within the range not impairing the object of the present invention.

  In general, metal ions having an ion charge other than +3 and +5, and ions whose ion radius deviates significantly from the ions constituting the upconversion phosphor according to the present invention are excluded from the crystal phase of the upconversion phosphor according to the present invention. However, since another phase is formed, it does not greatly contribute to the decrease in the luminous efficiency of the up-conversion phosphor.

  The halogen-based elements include those that are easily hydrolyzed and those that are dangerous for the living body, such as the human body. Therefore, it is preferable that the halogen-based elements are not substantially included in the up-conversion phosphor of the present invention.

1-7. Properties of up-conversion phosphor
1-7-1. Crystal structure
The crystal structure of the upconversion phosphor according to the present invention can be confirmed by (crystal or powder) X-ray diffraction. For example, when an X-ray diffraction is performed on an upconversion phosphor using a powder X-ray diffraction analyzer and CuKα as an X-ray source, an X-ray diffraction pattern of the upconversion phosphor is obtained, By analyzing the X-ray diffraction pattern, the crystal structure of the upconversion phosphor can be confirmed.

In the upconversion phosphor according to the present invention, for example, the basic structure skeleton is “YTa ₇ O ₁₉ ”.
In this case, the Y atom of the crystal site occupied by Y of this basic structure skeleton is replaced by M ¹ , M ² , Yb other than Y.

M ¹ and M ² defined in the present invention are those in which the oxidation state (+ trivalent) of their atoms and the ionic radius in the oxidation state are suitable for maintaining this basic structure skeleton. Therefore, the phosphor having the basic structure skeleton of “YTa ₇ O ₁₉ ” is substituted with substitution ions Y (M ¹ ), Ta (M ² ), and Yb as compared with “YTa ₇ O ₁₉ ” as a base material. Although there are some differences in the crystal structure in terms of the ratio and the size of the ions with respect to Y ions, the peak value in X-ray diffraction measurement almost coincides with “YTa ₇ O ₁₉ ”.

Of the photosensitizer ions (Yb) and activator ions (Er, Ho, Tm) that substitute Y, it is difficult to estimate the proportion that functions effectively as a photosensitizer or activator. However, qualitatively, regarding the crystal structure of the up-conversion type phosphor, it is considered effective to improve the up-conversion efficiency to increase the proportion of the sequences satisfying the following conditions with respect to all the sequences.
The activator ion and the photosensitizer ion are arranged in the vicinity of each other, so that an efficient energy transfer from the photosensitizer ion to the activator ion occurs.
On the other hand, both the activator ion and the photosensitizer ion are less likely to cause a phenomenon in which the excited state is short-lived by so-called ions or atomic groups (so-called quenching).

1-7-2. The external energy, which is the excitation light that irradiates the up-conversion phosphor to emit up-conversion light of the excitation light and the emitted light , is exposed to the excitation light when the up-conversion phosphor is irradiated with the excitation light. Light (electromagnetic wave) having a wavelength in the range of 500 to 2000 nm is preferable from the viewpoint of not irradiating an irradiated object such as a living tissue, and light in a range of 800 to 1500 nm from the viewpoint of a long transmission distance in the living body. Is more preferable, and light in the range of 960 to 1100 nm is most preferable from the viewpoint that a laser light source suitable for an excitation light source can be obtained easily and inexpensively.

When irradiation is performed using light having such a wavelength as excitation light, visible light is generated from the up-conversion phosphor.
For example, the up-conversion phosphor is YTA ₇ O ₁₉ as the base material, the type of doped metal atom YTA ₇ O ₁₉ is a base material of ceramics, blue wavelength is in the region of less than 500nm or 400nm , At least one kind of light emission selected from the group consisting of green in the region of 500 nm to 600 nm and red in the region of 600 nm to 800 nm occurs.

  Specifically, in an embodiment in which both Tm and Yb are doped (Tm and Yb co-doping), blue light emission in a region of 400 nm or more and less than 500 nm and red light emission in a region of a wavelength of 600 nm or more and less than 800 nm. In a mode in which both Er and Yb are doped (Er, Yb co-doping) and a mode in which both Ho and Yb are doped (Ho, Yb co-doping), the wavelength is 500 nm or more and less than 600 nm. Strong green light emission in the region and weak red light emission in the region where the wavelength is 600 nm or more and less than 800 nm are generated (see also FIGS. 5 and 9). In addition, among the above, when the colored light of a phosphor that emits light of a plurality of colors is viewed (without spectroscopy), it is observed as a mixed color of the plurality of colored light, so the type and amount of dopant By appropriately adjusting the ratio, it is possible to emit light of a desired color in addition to the above color. That is, multi-coloring is also possible.

More specifically, for example, when the ceramic base material is YTa ₇ O ₁₉ , and when the activation atom (M ^{2 in the} general formula (1)) is a single atom, the color of the light obtained is the blue color described above. When the activation atom (M ^{2 in the} general formula (1)) is a mixed system of two or more, it is possible to obtain emitted light having the following color. For example, in Tm, Ho, Yb co-doping, it becomes a light blue which is a mixed color of blue in a wavelength range of 400 nm or more and less than 500 nm and green in a wavelength range of 500 nm or more and less than 600 nm (so-called color-added method using emission color). ).

Thus, in the up-conversion type phosphor according to the present invention, by appropriately selecting and combining atoms derived from the activator raw material compound (B) (M ^{2 in the} general formulas (1) to (3)), a wide range can be obtained. Multi-coloring is possible.

  Among these aspects, the up-conversion type phosphor that emits visible light of 450 to 750 nm when absorbing near infrared light of 960 to 1100 nm does not damage the irradiated object such as the above-mentioned biological tissue. And is preferable from the viewpoint of easy detection of emitted light.

1-7-3. Fluorescence intensity measurement (luminance evaluation)
The brightness of the upconversion phosphor according to the present invention can be evaluated by the fluorescence intensity.

  The fluorescence intensity is measured, for example, by using a 980 nm semiconductor laser (500 mA, THORLABS, TCLD-M9) as a light source, and detecting the generated fluorescence with a multichannel spectrophotometer. Etc. can be confirmed.

In this specification, if the emission intensity is higher than the luminance of CeO ₂ : Er, Yb, it is determined that the luminance is high. Preferably it is 2 times or more. The upper limit is usually about 250 times ((M ¹ _a M ² _b Yb _c ) when the luminance of the phosphor of M ³ ₇ O ₁₉ is 25 times the quantum yield (two-photon excitation yield). 100%)), but is not limited to this.

2. Production method of up-conversion type phosphor The up-conversion type phosphor according to the present invention comprises a first raw material (a) of a base material (A), a second raw material (a ') of the base material (A), and an activator. A precursor of ceramics (up-conversion phosphor) (hereinafter referred to as “ceramic precursor”) by adding the raw material compound (B) and the photosensitizer raw material compound (C) (and other components as necessary) and mixing them sufficiently uniformly. The ceramic precursor thus obtained is subjected to high-temperature firing for an appropriate period of time, and the fired product obtained is further pulverized as necessary to form fine particle groups.

A base material is formed from the first raw material (a) of the base material (A) and the second raw material (a ′) of the base material (A).
More specific description will be given below.
Unless otherwise noted, the pressure condition in the production method is substantially normal pressure.

2-1. The manufacturing method of the up-conversion type phosphor of the present invention such as manufacturing conditions includes at least a ceramic precursor preparation step and a ceramic precursor firing step. Moreover, the manufacturing method of the up-conversion type | mold phosphor of this invention may also include other processes, such as a grinding | pulverization process of a baked material, as needed.

  As a manufacturing method of the up-conversion type phosphor made of the ceramic represented by the general formula (1), the general formula (2) or the general formula (3) according to the present invention, for example, in a ceramic precursor preparation step, Using the solid phase method, the first raw material (a) of the base material (A), the second raw material (a ′) of the base material (A), the activator raw material compound (B), and photosensitization Examples include a method in which the agent raw material compound (C) is mixed and the obtained powder mixture is fired (a solid phase method described later).

Moreover, as a manufacturing method of the up-conversion type phosphor according to the present invention, for example, the first raw material (a) of the base material (A) and the activator using the liquid phase method in the ceramic precursor preparation step The raw material compound (B), the photosensitizer raw material compound (C), the second raw material (a ′) of the base material (A), and the second raw material (a ′) of the base material (A). A coordinating organic compound complex, a coordinating organic compound, and a solvent are mixed to prepare a mixed solution, and then the resultant mixed solution is heated to heat the resulting product to heat the ceramic precursor. And forming the body, and then firing the obtained ceramic precursor (liquid phase method described later).
Each process will be described below in order, including these methods.

2-1-1. Ceramic Precursor Preparation Step In the ceramic precursor preparation step, an unfired ceramic precursor, which is a precursor of the upconversion phosphor (ceramics) of the present invention, is prepared.

Examples of the method for producing the unfired ceramic precursor include a solid phase method, a liquid phase method, and a gas phase method.
The solid-phase method is basically a simple method in which raw material powders are mixed and sintered, the work process is simple, mass production is possible at low cost, and productivity is high.

Therefore, for example, it is generally often used when manufacturing on a factory scale.
On the other hand, the diffusion rate of ions in the solid is very slow, and it tends to be difficult to obtain desirable fine particles.

The liquid phase method has an advantage that a fired product having a uniform composition can be easily obtained, and high-purity fine particles can be easily obtained.
The gas phase method is not suitable for mass production, but has the advantage that the reaction proceeds according to the stoichiometric ratio with high purity, and ultrafine particles can be synthesized.

Since any method can be used to produce an unfired ceramic precursor, a method to be appropriately employed may be selected in consideration of productivity and desired physical properties, but the liquid phase method has high brightness and From the viewpoint of the advantage that an unfired ceramic precursor composed of fine particles having a uniform particle diameter is easily obtained, it is more convenient. The solid phase method is generally an industrially superior method because the synthesis process is simple and the apparatus is simple.
Hereinafter, the solid phase method and the liquid phase method will be described in more detail.

<Solid phase method>
In the method for producing an up-conversion phosphor according to the present invention, in the solid phase method, the first raw material (a) of the base material (A), the second raw material (a ′) of the base material (A), The activator raw material compound (B) and the photosensitizer raw material compound (C) are mixed, and the obtained powder mixture is fired at 800 to 1500 ° C.

Each raw material is mixed so as to satisfy any of the following conditions (XI) to (XIII).
(XI) When producing an up-conversion phosphor made of ceramics represented by the general formula (1),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 0 to 99.8 atomic%, the metal atom of the activator raw material compound (B) and the metal atom of the photosensitizer raw material compound (C). The total is 0.2-100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). Mixing so that it may become a ratio of 490-910 with respect to the total number of atoms 100 of an atom and the metal atom of a photosensitizer raw material compound (C);
(XII) When producing an up-conversion type phosphor composed of the ceramic represented by the general formula (2), the metal atom of the first raw material (a) of the base material (A), the activator raw material compound ( When the sum of the metal atoms of B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%,
50 to 99.8 atomic% of metal atoms of the first raw material (a) of the base material (A), metal atoms of the activator raw material compound (B) and metal atoms of the photosensitizer raw material compound (C). The total is 0.2-50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). Mixing so that it may become a ratio of 70-130 with respect to the total number of atoms 100 of an atom and the metal atom of a photosensitizer raw material compound (C);
(XIII) When manufacturing an up-conversion phosphor made of ceramics represented by the general formula (3),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
30 to 99.8 atomic% of metal atoms of the first raw material (a) of the base material (A), metal atoms of the activator raw material compound (B), and metal atoms of the photosensitizer raw material compound (C). The total is 0.2-70 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). It mixes so that it may become a ratio of 23-43 with respect to the total number of atoms 100 of an atom and the metal atom of a photosensitizer raw material compound (C).

Here, the amount of metal atoms in each raw material corresponds to the amount of each metal element in the above-described upconversion phosphor. A preferable amount or the like may be applied thereto.
Specifically, for example, in (M ¹ _a M ² _b Yb _c ) M ³ ₇ O ₁₉ represented by the general formula (1), the amount of each element is the number of atoms of M ¹ , M ² , and Yb. The total is represented by a value of ¹ , but this may be converted to a value when the total number of atoms of M ¹ , M ² , and Yb is 100 atomic%. The same applies to the amount ratio of (M ¹ _a M ² _b Yb _c ), M ³ and O.

Further, (M ¹ _a M ² _b Yb _c ) M ³ O ₄ represented by the general formula (2) and (M ¹ _a M ² _b Yb _c ) ₃ M ³ O ₇ represented by the general formula (3). The same applies to.
When the number of M ³ atoms in the second raw material (a ′) of the base material (A) deviates from the above range, it is represented by general formula (1), general formula (2), or general formula (3). It tends to be difficult to obtain an up-conversion type phosphor made of ceramics with a single phase and high purity. On the other hand, in that case, a mixture containing at least one kind of ceramics represented by the general formula (1), the general formula (2), or the general formula (3) is generated. Since the emission color due to up-conversion greatly depends on the type of activated ions, up-conversion emission with almost a single color can be obtained even with a mixture.

<Liquid phase method>
Hereinafter, the liquid phase method will be described in more detail.
The liquid phase method is a method of preparing an unfired ceramic precursor by preparing a solution containing at least the above raw materials and then sufficiently mixing the raw materials in the solution. The unsintered ceramic precursor is subjected to a firing process.

  Therefore, the liquid phase method tends to require a longer manufacturing process as compared with the solid phase method or the gas phase method. However, on the other hand, it is easy to proceed with a predetermined reaction by constructing a reaction system in which raw materials are uniformly distributed at the molecular level, and the unfired ceramic precursor obtained by the liquid phase method is crystallized by firing. Ceramics with high crystallinity can be easily manufactured.

  As a result, the unfired ceramic precursor obtained by the liquid phase method has high purity and high uniformity. By firing this, the fluorescence extraction efficiency, which is the conversion rate of excitation light energy to fluorescence energy, is high, and the average particle size is high. It is easy to produce ceramics composed of fine particles having a uniform diameter and particle form.

Therefore, when importance is attached to the properties of the ceramics to be manufactured as a phosphor, the liquid phase method is a more preferable manufacturing method than the solid phase method or the gas phase method.
Specific means of the liquid phase method include precipitation method, coprecipitation method, complex polymerization method, complex gel method (also known as amorphous metal complex method). It is preferable from the viewpoint that an unfired ceramic precursor (excellent in mixing properties) can be manufactured, and the complex gel method is preferable from the viewpoint of ease of manufacturing a ceramic phosphor.

(Complex polymerization method, complex gel method)
Hereinafter, the complex polymerization method and the complex gel method will be described in detail.
An unfired ceramic precursor for use in the firing step can be produced by a complex polymerization method or a complex gel method.

  In the method for producing an upconversion phosphor according to the present invention, in the complex polymerization method and complex gel method which are one of the liquid phase methods, for example, the first raw material (a) of the base material (A) and the activator Raw material compound (B), photosensitizer raw material compound (C), coordination organic compound complex as second raw material (a ′) of base material (A), coordination organic compound, solvent To prepare a mixed solution, and then the obtained mixed solution is heated at 120 to 150 ° C. to evaporate the liquid component (preferably to dryness), and the resulting product is heated to 400 to Heat at 500 ° C. to form a ceramic precursor.

Here, each raw material is mixed so as to satisfy any of the following conditions (XI) to (XIII).
(XI) When producing an up-conversion phosphor made of ceramics represented by the general formula (1),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 0 to 99.8 atomic%, the metal atom of the activator raw material compound (B) and the metal atom of the photosensitizer raw material compound (C). The total is 0.2-100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(XII) When producing an up-conversion type phosphor composed of the ceramic represented by the general formula (2), the metal atom of the first raw material (a) of the base material (A), the activator raw material compound ( When the sum of the metal atoms of B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%,
50 to 99.8 atomic% of metal atoms of the first raw material (a) of the base material (A), metal atoms of the activator raw material compound (B) and metal atoms of the photosensitizer raw material compound (C). The total is 0.2-50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(XIII) When manufacturing an up-conversion phosphor made of ceramics represented by the general formula (3),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
30 to 99.8 atomic% of metal atoms of the first raw material (a) of the base material (A), metal atoms of the activator raw material compound (B), and metal atoms of the photosensitizer raw material compound (C). The total is 0.2-70 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100,
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
It mixes so that the quantity of the said coordinating organic compound may be 1-10 times mole with respect to all the metals.

(M ¹ _a M ² _b Yb _c ) M ³ ₇ O ₁₉ represented by the general formula (1), (M ¹ _a M ² _b Yb _c ) M ³ O ₄ represented by the general formula (2), The same applies to the method of converting the number of atoms of each atom in (M ¹ _a M ² _b Yb _c ) ₃ M ³ O ₇ represented by the formula (3) into atomic%.

Similar to the solid phase method, in the liquid phase method, when the number of M ³ atoms in the second raw material (a ′) of the base material (A) deviates from the above range, the general formula (1), the general formula (2) ) Or the general formula (3), it tends to be difficult to obtain an up-conversion type phosphor made of ceramics in a single phase with high purity. The general formula (1), the general formula (2) or the general formula Although a mixture containing at least one kind of ceramics represented by (3) is generated, up-conversion light emission with almost a single color can be obtained even with the mixture. Such examples are shown in Examples 78-80.

Further details are as follows.
In the liquid phase method, for example, first, the first raw material (a) of the base material (A), the activator raw material compound (B), the photosensitizer raw material compound (C), and the base material (A). The coordinating organic compound complex of the second raw material (a ′), the coordinating organic compound, and a solvent are mixed.

  Coordination of the first raw material (a) of the base material (A), the activator raw material compound (B), the photosensitizer raw material compound (C), and the second raw material (a ′) of the base material (A). As described above, the organic compound complex and the coordinating organic compound may be dissolved separately in advance in a solvent and mixed as a solution, or mixed as they are, and the mixture is dissolved in the solvent in a later operation to prepare a solution. May be prepared. In short, when the obtained mixture is heated at 120 to 150 ° C., it is sufficient that the mixture is prepared in a state of a solution containing each of the above raw materials.

The solution containing the second raw material (a ′) of the base material (A) may be a solution of a metal (= M ³ tantalum (Ta) and / or niobium (Nb))-coordinating organic compound complex. Then, as a metal compound represented by M ³ , a coordinating organic compound is added separately from the solution containing the second raw material (a ′) of the base material (A), and an M ³ -coordinating organic compound complex is added. May be formed. The temperature condition at this time is usually 20 to 90 ° C.

  The solvent includes the first raw material (a) of the base material (A), the activator raw material compound (B), the photosensitizer raw material compound (C), and the second raw material (a ′) of the base material (A). The coordinating organic compound complex and the coordinating organic compound are not particularly limited as long as they can be dissolved, and may be an organic solvent or an inorganic solvent.

Specific examples of the solvent include water, methanol, ethanol, acetone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide and the like.
A solvent may be used individually by 1 type and may be used as a 2 or more types of mixed solvent.

  Here, the resulting mixed solution is subjected to gelation by adding a polyol such as ethylene glycol or propylene glycol, and then the method of producing the ceramic precursor is a complex polymerization method, and the gelation is performed without adding the polyol. The method of carrying out and then producing the ceramic precursor is a complex gel method.

  In the complex polymerization method, for example, when an oxycarboxylic acid or a carboxylic acid is contained in the coordinating organic compound, a polyol such as ethylene glycol or propylene glycol is added to the obtained mixture as necessary. When heated at ˜150 ° C. for 300 to 600 minutes, the esterification reaction proceeds to produce polyester. Moreover, when carboxylic acid (or polyol) has three or more reactive functional groups, a gel-like product is obtained. At this time, all of the water may be evaporated (evaporated to dryness), or a liquid substance such as a solvent may remain so as not to hinder the next operation.

Subsequently, the product is heated at a temperature within a specific range by a normal method using a heating furnace to produce a ceramic precursor. The heating temperature depends on the type of polymer obtained above, but when heated to about 400 to 500 ° C., the decomposition reaction of the polymer in the product proceeds.
In this way, a ceramic (phosphor) precursor having a uniform crystal structure is obtained.
An example of a schematic diagram of an example of the complex gel method is shown in FIG.

2-1-2. Firing step The firing step is performed after at least the preparation step of the ceramic precursor.
The firing of the ceramic precursor may be performed for 60 to 600 minutes under a temperature condition of usually 800 to 1500 ° C., preferably 1000 to 1200 ° C. according to a conventional method using a heating furnace.

  The ceramics thus obtained (up-conversion type phosphor) can obtain a group of crystalline fine particles having a small average particle size of primary particles and a uniform shape and average particle size. Showing gender.

2-1-3. Other Steps The method for producing the upconversion phosphor may include steps other than the ceramic precursor preparation step and the firing step.

For example, the residual raw material may be removed from the mixture containing the ceramic precursor obtained in the ceramic precursor preparation step before the firing step.
In addition, the shape (powder and the like) and size of the obtained phosphor vary depending on the purpose of use (use), but are not particularly limited as long as the purpose of the present invention is not impaired. Examples thereof include up-conversion phosphors having an average particle diameter of 1 to 200 nm obtained by pulverizing the obtained ceramics into a powder using a pulverizer such as a ball mill or a bead mill after the firing step.

  In the process of preparing the ceramic precursor, materials other than the raw materials may be added and mixed. Examples of such a material include boron compounds, alkali metal halides and alkalis for increasing crystallinity. Examples thereof include fluxing agents such as earth metal halides.

2-2. The raw materials will be described below. M ¹ , M ² and M ^{3 in the following} are the same as those described in the item of the up-conversion phosphor.

2-2-1. First raw material (a) of base material (A)
The first raw material (a) of the base material (A) includes M ¹ M ³ ₇ O ₁₉ and M ¹ M ³ O, which are the base materials, together with a second raw material (a ′) of the base material (A) described later. ₄ or M ¹ ₃ M ³ O ₇ is formed.

The first raw material (a) of the base material (A) is a metal atom represented by M ¹ of M ¹ M ³ ₇ O ₁₉ , M ¹ M ³ O ₄ or M ¹ ₃ M ³ O ₇ as the base material. The source is a metal compound represented by M ¹ .
The metal compound represented by M ¹ is chemically converted before the above-described firing process is completed, and M ¹ M ³ ₇ O ₁₉ , M ¹ M ³ O _4, or M ¹ ₃ M ³ O as a base material. What constitutes ₇ may be used. The compound of such a metal atom represented by M ^1, nitrates of the metal atom represented by M ^1, chloride, acetate, carbonate, and the like complex compounds with organic chelating agents. Among them, for example, a compound composed of M ¹ and an atomic group derived from an anion of nitrate, chloride, acetate, or carbonate such as Y (NO ₃ ) ₃ is preferable from the viewpoint of ease of handling ( same as below.). These may be hydrates containing crystal water.

Among these, nitrates are preferable from the viewpoints of stability, ease of handling, solubility in water, and the like.
The purity of the metal atom compound represented by M ¹ is preferably 98.0% or more from the viewpoint of obtaining a stable composition.

2-2-2. Second raw material (a ′) of base material (A)
The second raw material (a ′) of the base material (A) is a metal represented by M ³ of the base material M ¹ M ³ ₇ O ₁₉ , M ¹ M ³ O ₄ or M ¹ ₃ M ³ O _7. It is an atomic source and is a metal compound represented by M ³ .

The metal compound represented by M ³ is chemically converted before the above-described firing process is completed, and M ¹ M ³ ₇ O ₁₉ , M ¹ M ³ O ₄ or M ¹ ₃ M ³ O as a base material. What constitutes ₇ may be used. The compound of a metal represented by such M ^3, a metal nitrate represented by M ^3, chloride, acetate, and the like carbonates. Alternatively, it may be a complex of an M ³ -organic coordination compound. These may be hydrates containing crystal water.

Among these, M ³ -oxycarboxylic acid complexes are preferable from the viewpoints of stability, ease of handling, solubility in water, and uniformity of the composition of the resulting ceramic.
The purity of the metal atom compound represented by M ³ is preferably 98.0% or more from the viewpoint of obtaining a stable composition.

2-2-3. Activator raw material compound (B)
The activator raw material compound (B) is (M ¹ _a M ² _b Yb _c ) M ³ ₇ O ₁₉ , (M ¹ _a M ² _b Yb _c ) M ³ O ₄ or (M ¹ _a M ² _b Yb _c ) ₃ M ³ O ₇ is a metal atom source represented by M ² of a compound of a metal represented by M ^2.

The activator raw material compound (B) may be any material capable of doping M ² into the base material M ¹ M ³ ₇ O ₁₉ , M ¹ M ³ O ₄ or M ¹ ₃ M ³ O ₇ . The compound of a metal represented by such M ^2, a metal nitrate represented by M ^2, chlorides, acetates, carbonates, and complex compounds with organic ligands or organic chelating agents include . These may be hydrates containing crystal water.

Among these, nitrates are preferable from the viewpoints of stability, ease of handling, solubility in water, and the like.
The purity of the metal compound represented by M ² is preferably 98.0% or more from the viewpoint of obtaining a stable composition.

2-2-4. Photosensitizer raw material compound (C)
The photosensitizer raw material compound (C) is (M ¹ _a M ² _b Yb _c ) M ³ ₇ O ₁₉ , (M ¹ _a M ² _b Yb _c ) M ³ O ₄ or (M ¹ _a M ² _b Yb _c ) Yb (ytterbium) atom source of ₃ M ³ O ₇ and a compound of ytterbium.

The photosensitizer raw material compound (C) may be any material that can be doped with Yb (ytterbium) in the base material M ¹ M ³ ₇ O ₁₉ , M ¹ M ³ O ₄ or M ¹ ₃ M ³ O _7. . Examples of such Yb (ytterbium) compounds include Yb (ytterbium) nitrates, chlorides, acetates, carbonates, organic ligands, and complex compounds with organic chelating agents. These may be hydrates containing crystal water.

Among these, nitrates are preferable from the viewpoints of stability, ease of handling, solubility in water, and the like.
The purity of the compound of Yb (ytterbium) is preferably 98.0% or more from the viewpoint of obtaining a stable composition.

2-2-5. Coordinating Organic Compound The coordinating organic compound is a compound that is added when preparing the solution of the raw material in the complex polymerization method or complex gel method, and is also a raw material for forming the coordinating organic compound complex. The coordination organic compound complex is a metal in which a coordination organic compound is coordinated.
Examples of the coordinating organic compound include oxycarboxylic acid, carboxylic acid, β-diketone, ethylenediaminetetraacetic acid (EDTA), monoalcohol, and polyol.

[Oxycarboxylic acid]
Examples of the oxycarboxylic acid include aliphatic hydroxycarboxylic acids having 2 to 6 carbon atoms such as lactic acid, glyceric acid, tartaric acid, and citric acid.

[carboxylic acid]
Although it does not specifically limit as carboxylic acid, For example, an acetic acid, propionic acid, oxalic acid, a citric acid, lactic acid, glycolic acid, tartaric acid etc. are mentioned. Among them, a carboxylic acid having three or more carboxyl groups is preferable from the viewpoint of obtaining a phosphor having a complex forming ability and a uniform crystal structure. Citric acid ((CH ₂ COOH) ₂ C (OH) (COOH) )) Is particularly advantageous from this point of view.

Here, the above is common to the raw material of the metal (= M ³ tantalum (Ta) and / or niobium (Nb))-carboxylic acid complex and the carboxylic acid compound added separately.

Carboxylic acid has a total equivalent amount of carboxylic acid compound of metal (= M ³ tantalum (Ta) and / or niobium (Nb))-carboxylic acid complex and the amount of carboxylic acid added separately from the complex. First metal (a) of base material (A), second raw material (a ′) of base material (A), activator raw material compound (B), and all metal of photosensitizer raw material compound (C) It is preferably used in such an amount that the molar ratio is 1 to 10 times equivalent, more preferably 2 to 8 times equivalent, and particularly preferably 2.5 to 5 times equivalent in terms of molar ratio.

  When the carboxylic acid is used in such an amount, an up-conversion phosphor having the above composition can be produced. When a complex polymerization method is employed, a polymer in which the above raw materials are uniformly distributed is produced. can do.

[Β-diketone]
Examples of β-diketone include acetylacetone, benzoylacetone, benzoyltrifluoroacetone, dibenzoylmethane, furoylacetone and the like.

[Monoalcohol]
Examples of the monoalcohol include aliphatic alcohols having 1 to 6 carbon atoms such as methanol, ethanol, n-propanol, 2-propyl alcohol, sec-butyl alcohol, n-butanol, n-pentanol, and n-hexanol.

[Polyol]
The polyol is an optional component used when employing the complex polymerization method, and is not particularly limited, and examples thereof include alkylene glycols such as ethylene glycol and propylene glycol, and triols such as glycerin. Among these, ethylene glycol, propylene glycol, and glycerin are advantageous from the viewpoint of low toxicity.

  The polyol is composed of the first raw material (a) of the base material (A), the second raw material (a ′) of the base material (A), the activator raw material compound (B), and the photosensitizer raw material compound (C). The amount is preferably 5 to 50 times equivalent, more preferably 8 to 30 times equivalent, and particularly preferably 10 to 20 times equivalent to the total of all metal atoms.

  When adopting the complex polymerization method, if such an amount of polyol is used, the reactivity of the coordinating organic compound other than the polyol reacts with the hydroxyl group of the polyol to form a gel, and the above raw materials are uniformly formed. A distributed polymer (gel) can be produced.

2-2-6. Addition of flux component In both the liquid phase method and the solid phase method described above, by adding a small amount of flux component to a mixture of raw materials or a firing precursor in a step before the firing step, an improvement obtained by firing is achieved. The light emission luminance of the conversion phosphor can be improved.

  Considering that it is desirable that the fluxing agent is uniformly mixed, the timing of adding the fluxing agent is before the firing step, and specifically, it is better to add and mix the ceramic precursor (for example, (See the flow diagram in FIG. 3).

Examples of the flux component include boron compounds, alkali metal halides, and alkaline earth metal halides.
The boron compound is not particularly limited as long as it can be converted into an oxide of boron by a reaction such as hydrolysis and oxidation that can occur in the raw material mixing to firing step and does not contain other nonvolatile impurities.

Since the boron-based flux agent becomes an oxide in the firing process and is lost from the solid phase by sublimation, it is not substantially included in the composition of the up-conversion phosphor.
For example, boron compounds such as boron oxide, boric acid, boric acid ester and the like can be mentioned. More specifically, organic boron compounds such as trimethyl boron and trimethoxy boron, boron trichloride, and boron triiodide are representative. Examples thereof include inorganic boron compounds and metal boron.

Since the boron oxide generated from such a boron compound is finally lost from the solid phase by sublimation, that is, in the firing step, the boron compound is not added too much. Considering the volumetric efficiency of the reaction and the point that an unnecessarily large amount of boron compound is not used, 0.1 to 50 with respect to 100% by weight of the upconversion phosphor obtained in terms of boron oxide (B ₂ O ₃ ). It may be added in an amount of about%, and in order to act more efficiently and effectively, it may be added in an amount of 0.2 to 10%, more preferably 0.5 to 5%.

Specific examples of the alkali metal halide and the alkaline earth metal halide include lithium chloride, sodium chloride, and calcium chloride.
The fluxing agent may be a mixture of an alkali metal halide and an alkaline earth metal halide.

  In the production process of the up-conversion type phosphor according to the present invention, for example, when removing these halides from the obtained ceramics (up-conversion type phosphor), those that volatilize at a high temperature may be removed by volatilization. Moreover, the halide which is not volatilized and removed after firing may be extracted and removed from the target composite oxide with a polar solvent such as water.

2-2-7. Other components In addition to the above, other metal compounds may be used as necessary within the range not impairing the object of the present invention.

  As described above, in general, metal ions other than ions having an ion charge of +3 or +5, or ions whose ion radius greatly deviates from the ion radius of the ions constituting the up-conversion phosphor according to the present invention, are used for the up-conversion according to the present invention. Since a phase different from the crystal phase of the phosphor is formed, the luminous efficiency of the up-conversion phosphor is not greatly reduced.

2-2-8. The following specific example of a manufacturing method of up-conversion phosphor is as follows when a specific example of a manufacturing method of up-conversion phosphor according to the present invention (when M ¹ is a rare earth atom).

A 0.1 mol / L aqueous solution of each rare earth nitrate (rare earth = M ¹ , M ² and Yb) is prepared, and an aqueous solution containing a total of 0.25 mmol of rare earth elements is taken in a test tube.
A 0.1 mol / L tantalum citrate complex aqueous solution or a 0.1 mol / L niobium citrate complex aqueous solution or a mixture thereof was added at a stoichiometric ratio of total rare earth elements: (total of Nb and Ta), Mix.

The tantalum citrate complex aqueous solution and the niobium citrate complex aqueous solution were added with TaCl ₅ or NbCl ₅ to the hydrogen peroxide solution, added with ammonia water, and further 5 times the mole number of Ta and Nb. Prepare by adding citric acid.

To the mixed solution of rare earth and Ta (or a mixture of Nb or Ta-Nb), citric acid is further added in 5 times the number of moles of the total amount of metal, dissolved, and then evaporated to dryness at 120 ° C.
This is heated at 400 ° C. to thermally decompose citric acid to obtain a ceramic precursor.

If necessary, 1 to 3% by weight of a flux agent such as H ₃ BO ₃ is added to the ceramic precursor, pulverized and mixed in a mortar, and fired in the atmosphere at 1200 ° C. for 5 hours to synthesize the target product. To do.

3. Use of the up-conversion phosphor The up-conversion phosphor of the present invention is, for example,
Energy conversion materials such as solar cells;
Prints with anti-counterfeiting technology (see, for example, Japanese Patent Application Laid-Open No. 2006-1094);
Analytical instruments such as laser scanning microscopes;
A display device such as a three-dimensional stereoscopic visible light display;
Upconversion laser oscillators such as laser light sources for display devices such as laser projectors and color displays, and laser light sources for printing devices such as digital printing systems and color printers for business use;
Light-emitting devices such as LCD panel backlights;
Storage devices such as optical memory:
Measuring devices such as optical measuring devices;
Optical information processing equipment such as CD and DVD;
Medical applications such as tumor markers using antibodies and cancer treatments that attack cancer with visible light;
Biological cell imaging device using IR laser and optical microscope in biomedical field;
It can use suitably for.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
In the following examples and comparative examples, unless otherwise specified, the pressure conditions in production and measurement are normal pressures.

[Example 1]
<Raw material>
The raw materials used in Example 1 are as follows.
Yttrium nitrate: Y (NO ₃ ) ₃ , manufactured by Nippon Yttrium Co., Ltd., purity 99.9%
Lanthanum nitrate: La (NO ₃ ) ₃ , manufactured by Japan Yttrium Co., Ltd., purity 99.9%,
Gadolinium nitrate: Gd (NO ₃ ) ₃ , manufactured by Nippon Yttrium Co., Ltd., purity 99.9%
Erbium nitrate: Er (NO ₃ ) ₃ , manufactured by Nippon Yttrium Co., Ltd., purity 99.9%
Ytterbium nitrate: Yb (NO ₃ ) ₃ , manufactured by Nippon Yttrium Co., Ltd., purity 99.9%
Thulium nitrate: Tm (NO ₃ ) ₃ , manufactured by Japan Yttrium Co., Ltd., purity 99.9%
Citric _{acid: (CH 2 COOH) 2 C} (OH) (COOH), manufactured by Wako Pure Chemical Industries, Ltd., purity of 98%,
Propylene glycol: Wako Pure Chemical Industries, Ltd., purity 99%.

<Manufacture of up-conversion phosphor>
5 ml of 0.1 mol / L aqueous solution of yttrium nitrate (Y (NO ₃ ) ₃ ), 1 ml of 0.1 mol / L aqueous solution of erbium nitrate (Er (NO ₃ ) ₃ ), ytterbium nitrate (Yb (NO ₃ ) ₃ ) 4 ml of a 0.1 mol / L aqueous solution was taken in a test tube. To this, 70 ml of a tantalum citrate complex aqueous solution having a tantalum concentration of 0.1 mol / L was added and mixed. Note that an aqueous solution of a tantalum citrate complex (ammonium citrate ammonium ((NH ₄ ) ₄ [Ta ₂ (C ₃ H ₄ O ₃ ) ₄ (O ₂ ) ₂ O) .3H ₂ O)) contains TaCl ₅ . It was prepared by adding aqueous ammonia to this, adding aqueous ammonia, and then adding citric acid 5 times as many as tantalum (in accordance with the method described in Inorganic Chemistry 2006, 45 (23): 9251-9256). ).

To the mixed solution of the rare earth (Y, Er, Yb) nitrate and tantalum citrate complex obtained as described above, citric acid was further added 5 times in terms of the number of moles of all metals, and after dissolution, evaporated to dryness at 120 ° C. Solidified. This was heated at 400 ° C. to thermally decompose citric acid to obtain a phosphor precursor (ceramic precursor). To this ceramic precursor, H ₃ BO ₃ (flux agent) in an amount of 1% by weight with respect to 100% by weight of the target product (Y _0.5 Er _0.1 Yb _0.4 Ta ₇ O ₁₉ ) is added and pulverized and mixed in a mortar. The product was fired in the air at 1200 ° C. for 5 hours to synthesize the up-conversion phosphor as the target product.

  Then, the obtained fired product was subjected to elemental analysis, X-ray diffraction analysis, measurement of luminance of fluorescence generated when a semiconductor laser having a wavelength of 980 nm was irradiated as excitation light, and photographing of an electron micrograph as follows. .

[Elemental analysis]
When elemental analysis of the obtained fired product (up-conversion type phosphor) was performed using an energy dispersive X-ray analyzer (EDX) (manufactured by Horiba, Ltd., EMAX-2770), the fired product was , (Y _0.5 Er _0.1 Yb _0.4 ) Ta ₇ O ₁₉ .

[X-ray diffraction analysis]
X-ray diffraction analysis was performed using an X-ray source (CuKα) using a powder X-ray diffraction analyzer (manufactured by Rigaku Corporation, GeigerFlex RAD-2X).

The X-ray diffraction pattern of the obtained fired product approximated the X-ray diffraction pattern of YTa ₇ O ₁₉ which is a standard substance.
The results are shown in FIG. The upper part is the standard substance (YTa ₇ O ₁₉ single crystal), and the lower part is the obtained up-conversion phosphor. Since both XRDs are almost the same, Er ³⁺ , Yb ³⁺ co-added YTa ₇ O ₁₉ is considered to be almost single phase like the single crystal of YTa ₇ O ₁₉ .

[Measurement of fluorescence intensity (evaluation of luminance)]
The fluorescence intensity is measured by a 980 nm semiconductor laser (500 mA, THORLABS, TCLD-M9).
Was used as a light source, and the generated fluorescence was detected by a multichannel spectrophotometer.

The obtained fired product emitted green fluorescence around 550 nm in the above measurement.
The result of scanning the fluorescence intensity at 450 nm to 750 nm is shown in FIG. 5 (the line with higher luminance), and the measurement result of the fluorescence intensity at 560 nm is shown in FIG.
The results are shown in Table 1 (hereinafter, the group of Table 1 (all of Tables 1-1-1 to 1-14 shown later) are collectively referred to as “Table 1”).

[Reference Example 1] Preparation of cerium oxide-based upconversion material 0.96 mmol of cerium nitrate, 0.03 mmol of erbium nitrate and 0.006 mmol of ytterbium nitrate were dissolved in 10 mL of distilled water.

To the obtained mixed solution, citric acid was added in an amount (2.5 mmol) corresponding to about 2.5 times the total amount of the total amount of all metals of the compound used previously.
Further, an amount (10 mmol) of propylene glycol corresponding to about 10 times mole of the total amount of all the metals was added to the obtained liquid, and the mixture was allowed to stand at 70 ° C. for 12 hours.

Next, the obtained mixed solution was heated under a temperature condition of 120 to 150 ° C. to evaporate the water and proceed the esterification reaction to obtain a polymer gel.
Next, the obtained polymer gel was heated on a sand bath set at 450 ° C. to thermally decompose the polyester in the polymer gel. Furthermore, the residue obtained after the thermal decomposition of the polyester was baked by heating for 300 minutes in an electric furnace set at 1200 ° C.
In this way, a fired product (ceramics) of CeO ₂ : Er, Yb (Er 3 mol%, Yb 0.6 mol%) was obtained (composition was Ce _0.96 Er _0.03 Yb _0.006 O ₂ ).

The obtained fired article (ceramics) was measured for fluorescence intensity (evaluation of luminance) in the same manner as in Example 1.
The results are shown in FIG.

[Examples 2-73]
In Example 1, except that the amount and type of each raw material were changed as shown in Table 1, an up-conversion type phosphor was produced in the same manner as in Example 1, and an up-conversion type having a single-layer crystal structure In the example in which the phosphor was obtained, various measurements other than X-ray diffraction analysis were performed in the same manner as in Example 1.
The results are shown in Table 1 and Figs.

[Example 74]
In Example 1, 0.15 mmol of yttrium nitrate, 0.05 mmol of holmium nitrate, 0.80 mmol of ytterbium nitrate, and 7.00 mmol of tantalum citrate complex (Ta conversion) were used. An upconversion phosphor was manufactured, and various measurements other than X-ray diffraction analysis were performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 75]
In the following procedure, an up-conversion type phosphor having M ¹ of 0 in the general formula (1) was produced.

  In Example 1, upconversion was carried out in the same manner as in Example 1 except that holmium nitrate 0.10 mmol, ytterbium nitrate 0.90 mmol, tantalum citrate complex 7.00 mmol (Ta conversion) was used, and yttrium nitrate was not used. Type phosphor was manufactured, and various measurements other than X-ray diffraction analysis were performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 76]
In the following procedure, an up-conversion type phosphor having M ¹ of 0 in the general formula (1) was produced.

  In Example 1, upconversion was performed in the same manner as in Example 1 except that 0.50 mmol of holmium nitrate, 0.50 mmol of ytterbium nitrate, 7.00 mmol of tantalum citrate complex (Ta conversion) was used, and yttrium nitrate was not used. Type phosphor was manufactured, and various measurements other than X-ray diffraction analysis were performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 77]
In Example 1, except that no boron-based fluxing agent (H ₃ BO ₃ ) is used, an up-conversion phosphor is produced in the same manner as in Example 1, and various measurements other than X-ray diffraction analysis are the same as in Example 1. Went to. The results are shown in Table 1.

[Example 78]
5 ml of 0.1 mol / L aqueous solution of yttrium nitrate (Y (NO ₃ ) ₃ ), 1 ml of 0.1 mol / L aqueous solution of erbium nitrate (Er (NO ₃ ) ₃ ), ytterbium nitrate ytterbium nitrate (Yb (NO ₃ )) ₃ ) 4 ml of a 0.1 mol / L aqueous solution was placed in a test tube. To this, 30 ml of a tantalum citrate complex aqueous solution having a tantalum concentration of 0.1 mol / L was added and mixed. To the mixed solution of the rare earth (Y, Er, Yb) nitrate and tantalum citrate complex obtained above, citric acid was further added 5 times in terms of the number of moles of all metals, and after dissolution, evaporated to dryness at 120 ° C. . This was heated at 400 ° C. to thermally decompose citric acid to obtain a phosphor precursor (ceramic precursor). To this ceramic precursor, H ₃ BO ₃ (flux agent) in an amount of 1% by weight with respect to 100% by weight of the target product (Y _0.5 Er _0.1 Yb _0.4 Ta ₃ O ₉ ) is added and pulverized and mixed in a mortar. The product was fired in the air at 1200 ° C. for 5 hours to synthesize the up-conversion phosphor as the target product.

From the X-ray diffraction analysis results, the ceramics represented by the general formulas (1) and (2), that is, Y _0.5 Er _0.1 Yb _0.4 Ta ₇ O ₁₉ and Y _0.5 Er _0.1 Yb _0.4 TaO _4, were 1: 2. It was found that a mixture mixed at a molar ratio was formed.

[Examples 79 and 80]
A reaction using lanthanum nitrate and gadolinium nitrate in place of yttrium nitrate in Example 78 was performed in the same manner as in Example 78 to obtain an upconversion phosphor. From the X-ray diffraction analysis results, a mixture of La _0.5 Er _0.1 Yb _0.4 Ta ₇ O ₁₉ and La _0.5 Er _0.1 Yb _0.4 TaO ₄ , Gd _0.5 Er _0.1 Yb _0.4 Ta ₇ O ₁₉ and Gd _0.5 Er _0.1 Yb _0.4 TaO ₄ , respectively. It was confirmed that.

[Comparative Example 1]
10 ml of a 0.1 mol / L aqueous solution of yttrium nitrate (Y (NO ₃ ) ₃ ) was placed in a test tube, and 70 ml of a tantalum citrate complex aqueous solution having a tantalum concentration of 0.1 mol / L was added thereto and mixed. To the mixed solution of yttrium nitrate and tantalum citrate complex obtained above, citric acid was further added 5 times in terms of the number of moles of all metals, dissolved, and then evaporated to dryness at 120 ° C. This was heated at 400 ° C. to thermally decompose citric acid to obtain a phosphor precursor (ceramic precursor). To this ceramic precursor, H ₃ BO ₃ (flux agent) in an amount of 1% by weight with respect to 100% by weight of the target product (YTa ₇ O ₁₉ ) was added, pulverized and mixed in a mortar, and 1200 ° C. for 5 hours. The target yttrium-tantalum oxide was synthesized by firing in air. Elemental analysis using an energy dispersive X-ray analyzer (EDX) confirmed that the fired product had a composition of YTa ₇ O ₁₉ . X-ray diffraction analysis confirmed that it was YTa ₇ O ₁₉ . Light emission by 980 nm infrared light was not observed.

以下に考察を述べるが、上記実施例の結果より得られる考察は下記に述べるものに限られるものではない。

Although consideration is described below, the consideration obtained from the result of the above-mentioned embodiment is not limited to the following.

(1) Molar ratio of M ² and Yb As shown in Tables 1-1 to 1-7, the molar ratio of M ² and Yb affects the emission intensity (luminance) of the up-conversion phosphor. It can be seen that the emission intensity (luminance) of the up-conversion phosphor can be adjusted by the molar ratio of M ² and Yb and that a high-brightness up-conversion phosphor can be provided.

  In FIG. 6, information on the luminance in Tables 1-1 to 1-7 is shown as a real photograph in the left figure, and a color diagram is shown in the right figure (the contents are the same). FIG. 6 shows that Er = 10 mol% and Yb = 40 mol% have the highest luminance. Relative luminance is 40% or more, it can be said that the luminance is high (see the horizontal bar below the graph for the relationship between the color in the graph and Relative luminance%).

(2) Regarding the crystal structure of the base material, as shown in Tables 1-8 to 1-10, up-conversion having the target crystal structure even if the atomic species of M ¹ and M ³ are changed with respect to Example 1. It can be seen that a type phosphor can be manufactured.

FIG. 8 summarizes the results of Tables 1-8 to 1-10 in tabular form.
When (M ¹ M ² Yb) is described as Ln, among LnTa ₇ O ₁₉ , LnTaO ₄ , and Ln ₃ TaO ₇ , LnTaO ₄ has a higher luminance, LnTa ₇ O ₁₉ has a much higher luminance, and LnTa _a Ta _b O in _{c a: b: c = 1} : 1: 4 is preferred, a: b: c = 1 : 7: 19 it can be seen particularly preferably.

(3) About M ¹ species As shown in Tables 1-8 and 1-9, even if the crystal structure of the base material and the up-conversion phosphors with the same M ² type and M ³ type are used, the M ¹ type is effective in luminance. It can be seen that there is an effect (see also FIGS. 7 and 12). The emission intensity is affected not only by the type of M ¹ but also by many factors such as the amount of M ¹ , the type and amount of M ² , the amount of Yb, the ratio of M ² and Yb, and the crystallinity of the product. Although Y cannot be said, generally Y, Gd, and La are preferable, and Y is more preferable among them.

(4) as shown in Table 1-11 M ² species, changing the ^two M, can provide up-conversion phosphor of high brightness, it can be seen that the luminescent color of which can be regulated by ^two M.
More specifically, as shown in FIGS. 5 and 9, it is understood that the emission wavelength can be changed by changing the element type of the emission center (Er, Ho, Tm).

(5) About the mixed system of M ^{3 As} shown in Table 1-12, it can be seen that a high-intensity up-conversion phosphor can be provided even in the mixed system of M ³ types.

From FIG. 10, it can be seen that even if M ³ is a mixed system, an up-conversion phosphor having high luminance can be obtained, and an up-conversion phosphor capable of obtaining a ratio of tantalum (Ta) to niobium (Nb). It can be seen that this affects the brightness.

(6) About the mixed system of M ^{1 As} shown in Table 1-13, it can be seen that even in the mixed system of M ¹ , a high-intensity up-conversion phosphor can be provided.

FIG. 11 shows that even if M ¹ is a mixed system, a high-brightness up-conversion phosphor can be obtained, and the luminance of the up-conversion phosphor obtained with the configuration of M ¹ is affected. I understand.

(7) Comparison with Conventional Oxide-Based Upconversion Phosphor FIG. 5 shows the phosphor of the present invention (numbered 10 (red line arrow)) and the conventional oxide-based phosphor shown as a reference example ( CeO ₂ : Er, Yb shows the emission intensity of number 11 (blue arrow). By comparing the two, it can be seen that the phosphor of the present invention (oxide type) is about 10 times as bright as the conventional oxide type phosphor.

FIG. 12 shows the emission intensity of the up-conversion phosphor composed of (M ¹ _a M ² _b Yb _c ) M ³ ₇ O ₁₉ and the up-conversion phosphor composed of CeO ₂ : Er, Yb (Table 1). -8, see also Reference Example 1). (M ¹ _a M ² _b Yb _c ) Up-conversion phosphors composed of M ³ ₇ O ₁₉ have higher brightness than up-conversion phosphors composed of CeO ₂ : Er, Yb, regardless of M ¹ species. I understand.

(8) Presence / absence of M ^{1 From} the results of Examples 75 and 76, it can be seen that the high-intensity up-conversion phosphor having M ¹ of 0 has high luminance.

(9) Presence / absence of flux agent From the results of Example 77, it can be seen that a high-brightness up-conversion phosphor can be produced without using a flux agent during the production of the up-conversion phosphor.

  The up-conversion phosphor obtained in the present invention includes an energy conversion material, a printed matter with anti-counterfeiting technology, an analytical instrument, a display device, an up-conversion laser oscillation device, a light emitting device, a storage device, a measuring device, and an optical information processing. Applications to devices, medical drugs, devices, and biological cell imaging devices can be expected.

_{10: (Y 0.5 Er 0.1 Yb} 0.4) Ta 7 O 19 ( in FIG. _{5, YTa 7 O 19: Er10mol%} , Yb40mol% hereinafter) of the fluorescence intensity 11: CeO _2: Er3mol%, fluorescence Yb0.6Mol% Intensity 12: (Y _0.50 Er _0.1 Yb _0.4 ) Ta ₇ O ₁₉ (indicated as Er10, Yb40 in FIG. 9) Fluorescence intensity 13: (Y _0.50 Tm _0.1 Yb _0.4 ) Ta ₇ O ₁₉ (in FIG. 9 Fluorescence intensity 14 of Tm10, Yb40): (Ho _0.5 Yb _0.5 ) Ta ₇ O ₁₉ (shown as Ho50, Yb50 in FIG. 9) 15: (Y _0.85 Er _0.05 Yb _0.1 ) Ta ₇ O ₁₉ (in FIG. _{12, YTa 7 O 19: Er5mol%} , and Yb10mol% notation) fluorescence intensity of _{16: (Gd 0.85 Er 0.05 Yb} 0.1) Ta 7 O 19 ( in FIG. 12 _{GdYTa 7 O 19: Er5mol%,} Y Fluorescence intensity of 17: (La _0.85 Er _0.05 Yb _0.1 ) Ta ₇ O ₁₉ (indicated as LaTa ₇ O ₁₉ : Er 5 mol%, Yb 10 mol% in FIG. 12) 18: CeO ₂ : Er3 mol %, Yb 0.6 mol% fluorescence intensity

Claims (11)

Upconversion type phosphors made of ceramics represented by the following general formula (1), general formula (2) or general formula (3);

(In the general formula (1), a is in the range of 0 to 0.998, b + c is in the range of 0.002 to 1, b: c is in the range of 100: 1 to 1: 100, and a + b + c. = 1.
In the general formula (2), a is in the range of 0.50 to 0.998, b + c is in the range of 0.002 to 0.50, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.
In the general formula (3), a is in the range of 0.30 to 0.998, b + c is in the range of 0.002 to 0.70, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.
In the above general formula (1), general formula (2) and general formula (3), M ¹ is scandium (Sc), yttrium (Y), lanthanum (La), gadolinium (Gd), indium (In), bismuth. (Bi) and at least one trivalent metal element selected from the group consisting of antimony (Sb),
M ² is at least one trivalent metal atom selected from the group consisting of erbium (Er), holmium (Ho) and thulium (Tm);
M ³ is at least one pentavalent metal atom selected from the group consisting of tantalum (Ta) and niobium (Nb).
_{However, YTaO 4: Er, Yb,} LaTaO 4: Er, Yb, GdTaO 4: Er, Yb, YTaO 4: Tm, Yb, YNbO 4: Er, Yb, and, YNbO _4: Tm, Yb is excluded. ) The upconversion phosphor according to claim 1, wherein M ¹ in the general formula (1), the general formula (2), and the general formula (3) is yttrium (Y), lanthanum (La), or gadolinium (Gd). . The upconversion phosphor according to claim 1 or 2 , which satisfies any of the following requirements (I) to (IX):
(I) It consists of ceramics represented by the general formula (1), M ² is erbium (Er), a is in the range of 0 to 0.8, and b + c is in the range of 0.2 to 1. B: c is in the range of 1:10 to 10: 1 and a + b + c = 1;
(II) The ceramic is represented by the general formula (1), M ² is holmium (Ho), a is in the range of 0 to 0.8, and b + c is in the range of 0.2 to 1. B: c is in the range of 1:20 to 1: 2 and a + b + c = 1;
(III) It consists of ceramics represented by the general formula (1), M ² is thulium (Tm), a is in the range of 0 to 0.8, and b + c is in the range of 0.2 to 1. B: c is in the range of 1:20 to 1: 2 and a + b + c = 1;
(IV) Made of the ceramic represented by the general formula (2), M ² is erbium (Er), a is in the range of 0.5 to 0.95, and b + c is 0.05 to 0.5. B: c is in the range of 10: 1 to 1:10 and a + b + c = 1;
(V) It consists of ceramics represented by the general formula (2), M ² is holmium (Ho), a is in the range of 0.5 to 0.95, and b + c is 0.05 to 0.5. B: c is in the range of 1:20 to 1: 2, and a + b + c = 1;
(VI) It consists of ceramics represented by the above general formula (2), M ² is thulium (Tm), a is in the range of 0.5 to 0.95, and b + c is 0.05 to 0.5. B: c is in the range of 1:20 to 1: 2, and a + b + c = 1;
(VII) The ceramic is represented by the general formula (3), M ² is erbium (Er), a is in the range of 0.3 to 0.99, and b + c is 0.01 to 0.7. B: c is in the range of 1:10 to 10: 1 and a + b + c = 1;
(VIII) The ceramic is represented by the general formula (3), M ² is holmium (Ho), a is in the range of 0.3 to 0.99, and b + c is 0.01 to 0.7. B: c is in the range of 1:20 to 1: 2, and a + b + c = 1;
(IX) The ceramic is represented by the general formula (3), M ² is thulium (Tm), a is in the range of 0.3 to 0.99, and b + c is 0.01 to 0.7. B: c is in the range of 1:20 to 1: 2, and a + b + c = 1. The up-conversion phosphor according to any one of claims 1 to 3 , which satisfies any one of the following requirements (I ') to (IX'):
(I ') It consists of ceramics represented by the above general formula (1), M ² is erbium (Er), a is in the range of 0 to 0.75, and b + c is in the range of 0.25 to 1. Yes, b: c is in the range of 1: 5-5: 2, a + b + c = 1;
(II ′) made of the ceramic represented by the general formula (1), M ² is holmium (Ho), a is in the range of 0 to 0.75, and b + c is in the range of 0.25 to 1. Yes, b: c is in the range of 1:20 to 1: 4, a + b + c = 1;
(III ') It consists of ceramics represented by the general formula (1), M ² is thulium (Tm), a is in the range of 0 to 0.75, and b + c is in the range of 0.25 to 1. Yes, b: c is in the range of 1:20 to 1: 5, a + b + c = 1;
(IV ′) Made of the ceramic represented by the general formula (2), M ² is erbium (Er), a is in the range of 0.6 to 0.95, and b + c is 0.05 to 0.00. 4; b: c is in the range 1: 5-5: 2; a + b + c = 1;
(V ′) Made of the ceramic represented by the general formula (2), M ² is holmium (Ho), a is in the range of 0.6 to 0.95, and b + c is 0.05 to 0.00. 4; b: c is in the range 1:20 to 1: 4; a + b + c = 1;
(VI ′) Made of the ceramic represented by the general formula (2), M ² is thulium (Tm), a is in the range of 0.6 to 0.95, and b + c is 0.05 to 0.00. 4; b: c is in the range 1: 20-1: 5; a + b + c = 1;
(VII ′) Made of the ceramic represented by the general formula (3), M ² is erbium (Er), a is in the range of 0.5 to 0.99, and b + c is 0.01 to 0.00. A range of 5; b: c is in the range of 1: 5 to 5: 2, and a + b + c = 1;
(VIII ′) Made of the ceramic represented by the above general formula (3), M ² is holmium (Ho), a is in the range of 0.5 to 0.99, and b + c is 0.01 to 0.00. A range of 5; b: c is in the range of 1:20 to 1: 4; a + b + c = 1;
(IX ′) It is made of ceramics represented by the above general formula (3), M ² is thulium (Tm), a is in the range of 0.5 to 0.9, and b + c is 0.1 to 0.00. 5, b: c is in the range of 1:20 to 1: 5, and a + b + c = 1. Compound of at least one trivalent metal selected from the group consisting of scandium (Sc), yttrium (Y), lanthanum (La), gadolinium (Gd), indium (In), bismuth (Bi) and antimony (Sb) A first raw material (a) of at least one kind of base material (A) and at least one pentavalent metal compound selected from the group consisting of a tantalum (Ta) compound and a niobium (Nb) compound. A second raw material (a ′) of the base material (A) and at least one trivalent metal compound selected from an erbium (Er) compound, a holmium (Ho) compound, and a thulium (Tm) compound. The activator raw material compound (B) and the photosensitizer raw material compound (C) comprising the ytterbium (Yb) compound are subjected to any of the following conditions (XI) to (XIII): Upconversion comprising ceramics represented by the following general formula (1), general formula (2), or general formula (3), which is mixed so as to satisfy the conditions, and the obtained powder mixture is fired at 800 to 1500 ° C. Type phosphor manufacturing method:

(In the general formula (1), a is in the range of 0 to 0.998, b + c is in the range of 0.002 to 1, b: c is in the range of 100: 1 to 1: 100, and a + b + c. = 1.
In the general formula (2), a is in the range of 0.50 to 0.998, b + c is in the range of 0.002 to 0.50, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.
In the general formula (3), a is in the range of 0.30 to 0.998, b + c is in the range of 0.002 to 0.70, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.
In the above general formula (1), general formula (2) and general formula (3), M ¹ is scandium (Sc), yttrium (Y), lanthanum (La), gadolinium (Gd), indium (In), bismuth. (Bi) and at least one trivalent metal element selected from the group consisting of antimony (Sb),
M ² is at least one trivalent metal atom selected from the group consisting of erbium (Er), holmium (Ho) and thulium (Tm);
M ³ is at least one pentavalent metal atom selected from the group consisting of tantalum (Ta) and niobium (Nb).
_{However, YTaO 4: Er, Yb,} LaTaO 4: Er, Yb, GdTaO 4: Er, Yb, YTaO 4: Tm, Yb, YNbO 4: Er, Yb, and, YNbO _4: Tm, Yb is excluded. )
(XI) When producing an up-conversion phosphor made of ceramics represented by the general formula (1),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 0 to 99.8 atomic%, the metal atom of the activator raw material compound (B) and the metal atom of the photosensitizer raw material compound (C). The total is 0.2-100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). Mixing so that it may become a ratio of 490-910 with respect to the total number of atoms 100 of an atom and the metal atom of a photosensitizer raw material compound (C);
(XII) When producing an up-conversion type phosphor composed of the ceramic represented by the general formula (2), the metal atom of the first raw material (a) of the base material (A), the activator raw material compound ( When the sum of the metal atoms of B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%,
The metal atom of the first raw material (a) of the base material (A) is 99.8 to 50.0 atomic%, the metal atom of the activator raw material compound (B) and the metal of the photosensitizer raw material compound (C). The total number of atoms is 0.2-50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). Mixing so that it may become a ratio of 70-130 with respect to the total number of atoms 100 of an atom and the metal atom of a photosensitizer raw material compound (C);
(XIII) When manufacturing an up-conversion phosphor made of ceramics represented by the general formula (3),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 0.2 to 70.0 atomic%, the metal atom of the activator raw material compound (B), and the metal of the photosensitizer raw material compound (C). The total number of atoms is 30-99.8 atomic percent,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). It mixes so that it may become a ratio of 23-43 with respect to the total number of atoms 100 of an atom and the metal atom of a photosensitizer raw material compound (C). Compound of at least one trivalent metal selected from the group consisting of scandium (Sc), yttrium (Y), lanthanum (La), gadolinium (Gd), indium (In), bismuth (Bi) and antimony (Sb) At least one selected from the group consisting of a first raw material (a) of at least one base material (A) comprising erbium (Er), holmium (Ho) and thulium (Tm) Activator raw material compound (B) which is a compound of a valent metal, photosensitizer raw material compound (C) containing ytterbium (Yb) as a metal compound, and second raw material (a ′) of the base material (A) At least one pentavalent metal compound selected from the group consisting of tantalum (Ta) compounds and niobium (Nb) compounds, and a second raw material (a) of the base material (A) ') At least one coordination organic compound complex selected from the group consisting of a tantalum coordination organic compound complex and a niobium coordination organic compound complex, a coordination organic compound, and a solvent. In order to satisfy any one of the following conditions (XI) to (XIII), a mixed solution is prepared, and then the obtained mixed solution is heated at 120 to 150 ° C. to evaporate the liquid component. The obtained product is heated at 400 to 500 ° C. to form a ceramic precursor, and then the obtained ceramic precursor is fired at 800 to 1500 ° C. The following general formula (1) and general formula (2) Or the manufacturing method of the up-conversion type | mold phosphor which consists of ceramics represented by General formula (3):

(In the general formula (1), a is in the range of 0 to 0.998, b + c is in the range of 0.002 to 1, b: c is in the range of 100: 1 to 1: 100, and a + b + c. = 1.
In the general formula (2), a is in the range of 0.50 to 0.998, b + c is in the range of 0.002 to 0.50, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.
In the general formula (3), a is in the range of 0.30 to 0.998, b + c is in the range of 0.002 to 0.70, and b: c is in the range of 100: 1 to 1: 100. Yes, a + b + c = 1.
In the above general formula (1), general formula (2) and general formula (3), M ¹ is scandium (Sc), yttrium (Y), lanthanum (La), gadolinium (Gd), indium (In), bismuth. (Bi) and at least one trivalent metal element selected from the group consisting of antimony (Sb),
M ² is at least one trivalent metal atom selected from the group consisting of erbium (Er), holmium (Ho) and thulium (Tm);
M ³ is at least one pentavalent metal atom selected from the group consisting of tantalum (Ta) and niobium (Nb).
_{However, YTaO 4: Er, Yb,} LaTaO 4: Er, Yb, GdTaO 4: Er, Yb, YTaO 4: Tm, Yb, YNbO 4: Er, Yb, and, YNbO _4: Tm, Yb is excluded. )
(XI) When producing an up-conversion phosphor made of ceramics represented by the general formula (1),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 0 to 99.8 atomic%, the metal atom of the activator raw material compound (B) and the metal atom of the photosensitizer raw material compound (C). The total is 0.2-100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(XII) When producing an up-conversion type phosphor composed of the ceramic represented by the general formula (2), the metal atom of the first raw material (a) of the base material (A), the activator raw material compound ( When the sum of the metal atoms of B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%,
The metal atom of the first raw material (a) of the base material (A) is 99.8 to 50.0 atomic%, the metal atom of the activator raw material compound (B) and the metal of the photosensitizer raw material compound (C). The total number of atoms is 0.2-50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(XIII) When manufacturing an up-conversion phosphor made of ceramics represented by the general formula (3),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
30 to 99.8 atomic% of metal atoms of the first raw material (a) of the base material (A), metal atoms of the activator raw material compound (B), and metal atoms of the photosensitizer raw material compound (C). The total is 0.2-70 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 100: 1 to 1: 100,
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
Mix so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals. The method for producing an upconversion phosphor according to claim 6 , wherein the coordination organic compound is citric acid. The metal of the first raw material (a) of the base material (A) is at least one trivalent metal element selected from the group consisting of yttrium (Y), lanthanum (La) and gadolinium (Gd) Item 8. A method for producing an up-conversion phosphor according to any one of Items 5 to 7 . The method for producing an upconversion phosphor according to any one of claims 5 to 8 , wherein the mixing is performed so as to satisfy any of the following conditions (I ") to (IX"):
(I ″) When manufacturing an up-conversion type phosphor made of a ceramic represented by the above general formula (1) and M ² being erbium (Er),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 0 to 80 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 20-100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:10 to 10: 1, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(II ″) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (1) and M ² being holmium (Ho),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 0 to 80 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 20-100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(III ″) When manufacturing an up-conversion type phosphor composed of ceramics represented by the above general formula (1) and M ² being thulium (Tm),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 0 to 80 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 20-100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(IV ″) When manufacturing an up-conversion type phosphor composed of ceramics represented by the above general formula (2) and M ² being erbium (Er),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total amount of metal atoms of the first raw material (a) of the base material (A) is 50 to 95 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 5 to 50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:10 to 10: 1, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(V ″) When manufacturing an up-conversion type phosphor composed of ceramics represented by the above general formula (2) and M ² being holmium (Ho),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total amount of metal atoms of the first raw material (a) of the base material (A) is 50 to 95 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 5 to 50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(VI ″) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (2) and M ² being thulium (Tm),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total amount of metal atoms of the first raw material (a) of the base material (A) is 50 to 95 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 5 to 50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(VII ″) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (3) and M ² being erbium (Er),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 30 to 99 atomic%, the metal atoms of the activator raw material compound (B) and the metal sensitizer raw material compound (C). 1-70 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:10 to 10: 1, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(VIII ″) In the case of producing an upconversion phosphor comprising the ceramic represented by the general formula (3) and M ² being holmium (Ho),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 30 to 99 atomic%, the metal atoms of the activator raw material compound (B) and the metal sensitizer raw material compound (C). 1-70 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(IX ″) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (3) and M ² being thulium (Tm),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 30 to 99 atomic%, the metal atoms of the activator raw material compound (B) and the metal sensitizer raw material compound (C). 1-70 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
It mixes so that the quantity of the said coordinating organic compound may be 1-10 times mole with respect to all the metals. The method for producing an up-conversion phosphor according to any one of claims 5 to 9 , wherein the mixing is performed so as to satisfy any of the following conditions (I ''') to (IX''') :
(I ′ ″) When manufacturing an up-conversion phosphor made of ceramics represented by the above general formula (1) and M ² being erbium (Er),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 0 to 75 atomic%, the total of the metal atom of the activator raw material compound (B) and the metal atom of the photosensitizer raw material compound (C) is 25 to 100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1: 5 to 5: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(II ″ ′) When manufacturing an up-conversion type phosphor composed of ceramics represented by the above general formula (1) and M ² being holmium (Ho),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 0 to 75 atomic%, the total of the metal atom of the activator raw material compound (B) and the metal atom of the photosensitizer raw material compound (C) is 25 to 100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 4, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(III ′ ″) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (1) and M ² being thulium (Tm),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The metal atom of the first raw material (a) of the base material (A) is 0 to 75 atomic%, the total of the metal atom of the activator raw material compound (B) and the metal atom of the photosensitizer raw material compound (C) is 25 to 100 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 5, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 490 to 910 relative to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(IV ′ ″) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (2) and M ² being erbium (Er),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 60 to 95 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 5-40 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1: 5 to 5: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(V ′ ″) When manufacturing an up-conversion type phosphor composed of ceramics represented by the above general formula (2) and M ² being holmium (Ho),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 60 to 95 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 5-40 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 4, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(VI ′ ″) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (2) and M ² being thulium (Tm),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 60 to 95 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 5-40 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 5, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). 70 to 130 in proportion to the total number of atoms of 100 atoms and metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(VII ′ ″) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (3) and M ² being erbium (Er),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 50 to 99 atomic%, the metal atoms of the activator raw material compound (B) and the metal sensitizer raw material compound (C). 1 to 50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1: 5 to 5: 2, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(VIII ′ ″) When manufacturing an up-conversion type phosphor composed of ceramics represented by the above general formula (3) and M ² being holmium (Ho),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total of the metal atoms of the first raw material (a) of the base material (A) is 50 to 99 atomic%, the metal atoms of the activator raw material compound (B) and the metal sensitizer raw material compound (C). 1 to 50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 4, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
Mixing so that the amount of the coordinating organic compound is 1 to 10 times mol of all metals;
(IX ′ ″) When manufacturing an up-conversion type phosphor made of ceramics represented by the above general formula (3) and M ² being thulium (Tm),
The total of the metal atoms of the first raw material (a) of the base material (A), the metal atoms of the activator raw material compound (B) and the metal atoms of the photosensitizer raw material compound (C) is 100 atomic%. When
The total amount of metal atoms of the first raw material (a) of the base material (A) is 50 to 90 atomic%, the metal atoms of the activator raw material compound (B) and the photosensitizer raw material compound (C). 10-50 atomic%,
The metal atom of the activator raw material compound (B): The metal atom of the photosensitizer raw material compound (C) is 1:20 to 1: 5, and
The number of M ³ atoms of the second raw material (a ′) of the base material (A) is the metal atom of the first raw material (a) of the base material (A), the metal of the activator raw material compound (B). A ratio of 23 to 43 with respect to 100 atoms and the total number of metal atoms of the photosensitizer raw material compound (C), and
It mixes so that the quantity of the said coordinating organic compound may be 1-10 times mole with respect to all the metals. At least one fluxing agent selected from the group consisting of boron compounds, alkali metal halides and alkaline earth metal halides is added to the ceramic precursor in an amount of 0.1% relative to 100% by weight of the up-conversion phosphor. The method for producing an upconversion phosphor according to any one of claims 5 to 10 , wherein the firing is performed in an amount of 1 to 50% by weight.

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