Oxide phosphor and light emitting device using the same

Abstract

To provide an oxide phosphor and a light emitting device using the same.SOLUTION: An oxide phosphor has a composition represented by the following formula (1): (Mg1-pM1p)q(Li1-rM2r)s(In1-tM3t)u(Ge1-vM4v)wOx:Cry,M5z (1) where M1 is selected from the group consisting of Ca, Sr, Ba, and Zn; M2 is selected from the group consisting of Na, K, Rb, and Cs; M3 is selected from the group consisting of Al, Ga, and Sc; M4 is selected from the group consisting of Si, Ti, Zr, Sn, and Hf; M5 is selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb; and 0≤p≤1.0, 0.1≤q≤0.9, 0≤r≤1.0, 0.05≤s≤0.45, 0≤t≤0.5, 0.05≤u≤0.45, 0≤v≤1.0, 0.8≤w≤1.3, 2.6≤x≤3.6, 0.002≤y≤0.5, 0≤z≤0.3, and 0.9≤q+s+u≤1.2 are satisfied.SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] The present disclosure relates to an oxide phosphor and a light-emitting device using the same. [Background technology]

[0002] Light-emitting devices having an emission intensity in the wavelength range from red light to near-infrared light are desired for use in, for example, infrared cameras, infrared communications, light sources for plant growth and cultivation, vein authentication which is a type of biometric authentication, food component analyzers that non-destructively measure the sugar content of agricultural products such as fruits and vegetables or foods, analytical instruments that non-destructively measure the presence of foreign matter in pharmaceuticals, etc. Light-emitting devices that emit light in the wavelength range from red light to near-infrared light as well as in the visible light range are also desired.

[0003] Such light emitting devices include light emitting devices that combine a light emitting diode (LED) and a phosphor. Furthermore, examples of phosphors that can be combined with light emitting devices include phosphors that have a relatively large emission spectrum with a high emission intensity in the wavelength range from red light to near-infrared light (hereinafter also referred to as "near-infrared light emitting phosphors").

[0004] Patent Document 1 describes a near-infrared emitting phosphor having an emission peak wavelength in the range of 680 nm to 760 nm, and a composition of, for example, CaYAlO4:Mn 4+ There is also a need for a near-infrared emitting phosphor that is suitable for each of the above-mentioned applications and has an emission spectrum with a wider full width at half maximum and an emission peak wavelength in a longer wavelength range. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2020-528486 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present disclosure is to provide an oxide phosphor having an emission peak wavelength in the wavelength range from red light to near-infrared light and a wide full width at half maximum of the emission spectrum, and a light-emitting device using the oxide phosphor. [Means for solving the problem]

[0007] The first aspect is an oxide phosphor having a composition represented by the following formula (1). (Mg 1-p M 1 p ) q (Li 1-r M 2 r ) s (In 1-t M 3 t ) u (Ge 1-v M 4 v ) w O x :Cr y ,M 5 z (1) (In the above formula (1), M 1 is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, and M 2 is at least one element selected from the group consisting of Na, K, Rb and Cs, and M 3 is at least one element selected from the group consisting of Al, Ga, and Sc, and M 4 is at least one element selected from the group consisting of Si, Ti, Zr, Sn and Hf, and M 5 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and p, q, r, s, t, u, v, w, x, y, and z satisfy the following conditions: 0≦p≦1.0, 0.1≦q≦0.9, 0≦r≦1.0, 0.05≦s≦0.45, 0≦t≦0.5, 0.05≦u≦0.45, 0≦v≦1.0, 0.8≦w≦1.3, 2.6≦x≦3.6, 0.002≦y≦0.5, 0≦z≦0.3, 0.9≦q+s+u≦1.2, respectively.

[0008] A second aspect is a light emitting device comprising the oxide phosphor and a light emitting element having an emission peak wavelength in the range of 365 nm to 650 nm, and irradiating the oxide phosphor. [Effects of the Invention]

[0009] According to the present disclosure, it is possible to provide an oxide phosphor having an emission peak wavelength in the wavelength range from red light to near-infrared light and a wide full width at half maximum of the emission spectrum, and a light emitting device using the same. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a schematic cross-sectional view showing an example of a first configuration example of a light emitting device. [Figure 2] FIG. 4 is a schematic cross-sectional view showing another example of the first configuration example of the light emitting device. [Figure 3A] FIG. 10 is a schematic plan view showing a second configuration example of the light emitting device. [Figure 3B] FIG. 10 is a schematic cross-sectional view showing a second configuration example of the light emitting device. [Figure 4] FIG. 1 is a diagram showing the emission spectra of oxide phosphors according to Examples 1 to 6. [Figure 5] FIG. 1 is a diagram showing the emission spectra of oxide phosphors according to Examples 7 to 11. [Figure 6] FIG. 1 is a diagram showing the emission spectra of oxide phosphors according to Examples 12 to 16. [Figure 7] FIG. 2 is a diagram showing the emission spectra of oxide phosphors according to Comparative Examples 1 and 2. DETAILED DESCRIPTION OF THE INVENTION

[0011] The oxide phosphor according to the present disclosure, a light-emitting device using the same, and a method for manufacturing the oxide phosphor are described below. However, the following embodiments are merely examples for embodying the technical concept of the present invention, and the present invention is not limited to the oxide phosphor and light-emitting device described below. Regarding visible light, the relationship between color names and chromaticity coordinates, the relationship between wavelength ranges of light and color names of monochromatic light, etc., conforms to JIS Z8110.

[0012] Light-emitting devices using phosphors are required to emit light in an optimal wavelength range depending on the visual target and usage conditions. For example, in medical settings, it is sometimes necessary to easily obtain information inside a living body. The living body contains light absorbers such as water, hemoglobin, and melanin. For example, hemoglobin has a high absorption rate for light in the visible wavelength range of less than 650 nm. Therefore, light-emitting devices that emit light in the visible wavelength range have difficulty transmitting light in the visible wavelength range inside the living body, making it difficult to obtain information inside the living body. If light in a wavelength range where absorption and scattering of light in biological tissue are reduced can be irradiated, it will be easier to obtain information deep inside the living body. Therefore, there is a demand for light-emitting devices that can emit light in a wavelength range known as the "biological window," which allows light to easily penetrate inside the living body. The wavelength range of approximately 650 nm to 950 nm is sometimes referred to as the "first biological window," the wavelength range of approximately 1000 nm to 1350 nm is sometimes referred to as the "second biological window," and the wavelength range of approximately 1500 nm to 1800 nm is sometimes referred to as the "third biological window." If it were possible to irradiate light in a wavelength range where the absorption and scattering of light by in vivo tissues is reduced, it would be easier to obtain information about deep tissues within the body. For example, if it were possible to measure increases or decreases in the oxygen concentration in blood by measuring the increase or decrease in light absorption by hemoglobin, which binds to oxygen, it would be possible to easily obtain information about deep tissues within the body by irradiating light from a light-emitting device. Furthermore, if information about deep tissues within the body could be obtained by irradiating light from a phosphor and a light-emitting element rather than by irradiation with X-rays or other radiation, it would be possible to obtain information about the body more safely. Therefore, phosphors used in light-emitting devices may be required to have a peak emission wavelength in the red to near-infrared wavelength range. The phosphor used in the light-emitting device may be one having a peak emission wavelength in the range of 680 nm to 1000 nm, or one having a peak emission wavelength in the range of 840 nm to 970 nm. Recently, there has been a demand for light-emitting devices that emit safe light in the wavelength range from red light to near-infrared light, which can more clearly visualize deep areas inside a living body.Furthermore, if a light-emitting device including a light-emitting element and a phosphor can pass a high current and emit high-power light, detection capabilities can be further improved, making it easier to obtain information from within a living body.

[0013] In the agricultural and food industries, there is a demand for nondestructive sugar content meters and rice taste meters that can nondestructively measure the sugar content and other properties of agricultural produce and fresh produce. Near-infrared spectroscopy is sometimes used as a nondestructive method for measuring the internal quality of fresh produce, such as sugar content, acidity, ripeness, and internal damage, as well as the surface quality, such as abnormal dryness, that appears on the surface of the fruit skin or the skin layer near the surface. Near-infrared spectroscopy irradiates fresh produce with light in the near-infrared wavelength range, receives the transmitted light that penetrates the fruit or vegetable, and receives the reflected light that is reflected by the fruit or vegetable, and measures the quality of the fruit or vegetable by measuring the decrease in light intensity (light absorption). Near-infrared spectroscopy analytical instruments used in the food industry use light sources such as tungsten lamps and xenon lamps. JIS K0134, General Rules for Near-Infrared Spectroscopy, defines near-infrared as the wavelength range from 700 nm to 2500 nm.

[0014] Furthermore, amid environmental changes such as climate change, there is a need for a stable supply of vegetables and other plants and for increased plant production efficiency. Plant factories, which allow for artificial management, can steadily supply safe vegetables to the market and are expected to be a next-generation industry. Such plant factories require light-emitting devices that can irradiate light that promotes plant growth. Plant responses to light can be divided into photosynthesis and photomorphogenesis. Photosynthesis, which utilizes light energy to split water, generate oxygen, and fix carbon dioxide into organic matter, is necessary for plant growth. Photomorphogenesis is a morphological response that uses light as a signal to germinate seeds, differentiate (germination, leaf formation, etc.), move (stomatal opening and closing, chloroplast movement), and refraction light. It has been shown that light in the wavelength range of 690 nm to 800 nm affects plant photoreceptors during photomorphogenesis. Therefore, light-emitting devices used in plant factories and the like are sometimes required to be able to emit light in a wavelength range that affects plant photoreceptors (chlorophyll a, chlorophyll b, carotenoids, phytochromes, cryptochromes, phototropins) and promotes plant growth.

[0015] Regarding the near-infrared light-emitting phosphors described above, there is room for improvement in the light-emitting properties of the phosphors so that light can be emitted in a manner suitable for the intended use when a light-emitting element such as a light-emitting diode (LED) or a laser diode (LD) that emits light in the purple to blue range is used as an excitation light source to form a light-emitting device.

[0016] In addition, there are cases where light emitting devices that emit light in the wavelength range of 365 nm to less than 700 nm are required, in addition to emitting light in the wavelength range from red light to near-infrared light. For example, there are cases where emission in the wavelength range of visible light is required not only to obtain internal information about living organisms or fruits and vegetables, but also to improve the visibility of the target object.

[0017] The oxide phosphor has a composition represented by the following formula (1). (Mg 1-p M 1 p ) q (Li 1-r M 2r ) s (In 1-t M 3 t ) u (Ge 1-v M 4 v ) w O x :Cr y ,M 5 z (1) (In the above formula (1), M 1 is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, and M 2 is at least one element selected from the group consisting of Na, K, Rb and Cs, and M 3 is at least one element selected from the group consisting of Al, Ga, and Sc, and M 4 is at least one element selected from the group consisting of Si, Ti, Zr, Sn and Hf, and M 5 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and p, q, r, s, t, u, v, w, x, y, and z satisfy the following conditions: 0≦p≦1.0, 0.1≦q≦0.9, 0≦r≦1.0, 0.05≦s≦0.45, 0≦t≦0.5, 0.05≦u≦0.45, 0≦v≦1.0, 0.8≦w≦1.3, 2.6≦x≦3.6, 0.002≦y≦0.5, 0≦z≦0.3, 0.9≦q+s+u≦1.2, respectively.

[0018] When the variable y in formula (1), which represents the molar ratio of the activator element Cr, is within the range of 0.002 or more and 0.5 or less (0.002≦y≦0.5) in 1 mole of the oxide phosphor composition, the oxide phosphor can have an emission peak wavelength in a wavelength range from red light to near-infrared light that is desirable depending on the intended use, and can obtain an emission spectrum with a relatively wide full width at half maximum. In the oxide phosphor, the variable y in formula (1), in 1 mole of the oxide phosphor composition, may be within the range of 0.005 or more and 0.40 or less (0.005≦y≦0.40), 0.010 or more and 0.30 or less (0.010≦y≦0.30), 0.015 or more and 0.20 or less (0.015≦y≦0.20), or 0.020 or more and 0.15 or less (0. 0.020≦y≦0.070(0.020≦y≦0.070)。 In the present specification, in the composition formula showing the composition of a phosphor containing an oxide phosphor, the part before the colon (:) represents the elements constituting the host crystal and their molar ratios, and the part after the colon (:) represents an activator element.

[0019] The oxide phosphor may contain, as needed, a first element M 1 is at least one element selected from the group consisting of Ca, Sr, Ba and Zn, and may be two or more elements selected from the group consisting of Ca, Sr, Ba and Zn. 1 The oxide phosphor may contain Mg, but not contain the first element M. 1 may be replaced by two or more first elements M 1 In the oxide phosphor, in the composition represented by the formula (1), all of Mg may be the first element M 1 The first element M 1In the case where Mg is Zn, all of Mg may be replaced with Zn. The oxide phosphor does not contain Mg, essentially contains Zn, and contains at least one first element M selected from the group consisting of Ca, Sr, and Ba in the composition represented by the formula (1). 1 may be replaced by two or more first elements M 1 may be replaced with .

[0020] The oxide phosphor contains Mg and the first element M in 1 mole of the composition of the oxide phosphor. 1 The variable q in the formula (1) representing the molar ratio of the total of Mg and the first element M is in the range of 0.1 to 0.9 (0.1≦q≦0.9). 1 When the variable q in the formula (1) representing the molar ratio of the sum of Mg and the first element M is within the range of 0.1 or more and 0.9 or less (0.1≦q≦0.9), it is possible to obtain an emission spectrum with a wider full width at half maximum and an emission peak wavelength in a range from red light to near-infrared light that is desirable depending on the intended use. 1 The variable q in the formula (1) representing the molar ratio of the sum of Mg and the first element M may be in the range of 0.2 or more and 0.9 or less (0.2≦q≦0.9), 0.3 or more (0.3≦q), or 0.4 or more (0.4≦q). In order to obtain an oxide phosphor with a stable crystal structure, the oxide phosphor contains Mg and the first element M in 1 mole of the oxide phosphor composition. 1 The variable q in the formula (1) representing the total molar ratio of may be in the range of 0.5 or more and 0.9 or less (0.5≦q≦0.9), or in the range of 0.6 or more and 0.9 or less (0.6≦q≦0.9).

[0021] The oxide phosphor may contain a first element M as needed in 1 mole of the oxide phosphor composition. 1 The molar ratio of is expressed by the product of the variables q and p in the formula (1), and the variable p is in the range of 0 to 1.0 (0≦p≦1.0). In the oxide phosphor, in 1 mole of the oxide phosphor composition, all of the Mg in the formula (1) is the first element M 1It may be replaced, or the variable p may be 1.0 (p = 1.0). In 1 mole of the composition of the oxide phosphor, a part of Mg in the formula (1) is the first atom M 1 is included, and the variable p in the formula (1) may be within the range greater than 0 and less than or equal to 1.0 (0 < p ≤ 1.0), may be within the range greater than or equal to 0 and less than 1.0 (0 ≤ p < 1.0), may be less than or equal to 0.9 (p ≤ 0.9), may be less than or equal to 0.8 (p ≤ 0.8), may be less than or equal to 0.7 (p ≤ 0.7), may be less than or equal to 0.6 (p ≤ 0.6), may be less than or equal to 0.5 (p ≤ 0.5), or may be within the range greater than or equal to 0 and less than or equal to 0.4 (0 ≤ p ≤ 0.4). In order to obtain an oxide phosphor with a stable crystal structure, in the composition represented by the formula (1), the total molar ratio of Mg and the first element M 1 represented by the variable q is within the range of 0.6 or more and 0.9 or less (0.6 ≤ q ≤ 0.9), and the variable p may be within the range of 0 or more and 0.4 or less (0 ≤ p ≤ 0.9). The oxide phosphor may not substantially contain the first element M 1 in the composition represented by the formula (1), and the variable p may be substantially 0 (p = 0). In this specification, when the numerical value of the variable representing the molar ratio of an element in the composition is "substantially 0", it means that the element is not intentionally included. Specifically, when the numerical value of the variable representing the molar ratio of an element in the composition is substantially 0, it refers to the case where it is 1000 mass ppm or less, also includes the case where it is 500 mass ppm or less, and also includes the case where it is 1 mass ppm or more.

[0022] The oxide phosphor may contain a second element M 2 as needed in the composition represented by the formula (1), and the second element M is at least one element selected from the group consisting of Na, K, Rb, and Cs, and two or more elements may be included. The oxide phosphor may have a part or all of Li replaced by the second element M 2 in the composition represented by the formula (1). The oxide phosphor may have a part or all of Li replaced by the second element M 2Even when Li is replaced by the second element M, it is possible to obtain an emission spectrum having an emission peak wavelength in a range from red light to near-infrared light that is desirable depending on the intended use. 2 may be replaced by a second element M 2 The oxide phosphor may be an oxide phosphor having a composition represented by the formula (1) in which all of Li is replaced by the second element M 2 may be replaced by a second element M 2 may also be Na.

[0023] The oxide phosphor contains Li and a second element M in 1 mole of the oxide phosphor composition. 2 When the variable s in formula (1), which represents the molar ratio of the sum of the above, is within the range of 0.05 to 0.45 (0.05≦s≦0.45), an emission spectrum with a broader full width at half maximum and an emission peak wavelength in a desired range depending on the intended use can be obtained in the wavelength range from red light to near-infrared light. The variable s in formula (1) of the oxide phosphor may be within the range of 0.10 to 0.45 (0.10≦s≦0.45), 0.15 to 0.45 (0.15≦s≦0.45), or 0.20 to 0.40 (0.20≦s≦0.40). To obtain an oxide phosphor with a more stable crystal structure, the variable s may be within the range of 0.25 to 0.40 (0.25≦s≦0.40).

[0024] The oxide phosphor contains Li and a second element M in 1 mole of the oxide phosphor composition. 2 The variable s in the formula (1) represents the total molar ratio of In and the third element M, which will be described later. 3 In the oxide phosphor, when the variable s in the formula (1) is the same as the variable u in the formula (1) or the difference between the variable s and the variable u is 0.05 or less, the oxide phosphor is preferably a phosphor containing Li and / or the second element M, each of which has a valence electron number of 1, in 1 mole of the oxide phosphor. 2 In and / or a third element M, which has 3 valence electrons 3is easily combined, the crystal structure of the oxide phosphor is stabilized, and in the wavelength range from red light to near-infrared light, it has an emission peak wavelength in a desirable range according to the intended use, and at the emission peak wavelength, it is possible to obtain an emission spectrum with high emission intensity. The oxide phosphor, in 1 mole of the composition of the oxide phosphor, contains Li and the second element M 2 When the variable s in the formula (1) representing the total molar ratio of is less than 0.05 or becomes greater than 0.45, In and / or the third element M 3 in the formula (1) is out of balance with the variable u representing the total molar ratio of, and also, Mg and / or the first element M 1 in the formula (1) is out of balance with the variable q representing the molar ratio of, so an oxide phosphor having a stable crystal structure cannot be obtained, and it does not emit fluorescence even when irradiated with excitation light, or the emission intensity becomes low.

[0025] The molar ratio of the second element M optionally contained in 1 mole of the composition of the oxide phosphor is represented by the product of the variable r and the variable s in the formula (1), and the variable r is within the range of 0 or more and 1.0 or less (0 ≦ r ≦ 1.0). The oxide phosphor, in 1 mole of the composition of the oxide phosphor, all of the Li in the formula (1) may be replaced by the second element M 2 , and the variable r may be 1.0 (r = 1.0). The oxide phosphor, in 1 mole of the composition of the oxide phosphor, contains the second atom M 2 in a part of the Li in the formula (1), and the variable r in the formula (1) may be within the range of more than 0 and 1.0 or less (0 < r ≦ 1.0), may be within the range of more than 0 and less than 1.0 (0 < t < 1.0), may be within the range of 0.1 or more and 0.9 or less (0.1 ≦ r ≦ 0.9), may be within the range of 0.2 or more and 0.8 or less (0.2 ≦ r ≦ 0.8), may be within the range of 0.3 or more and 0.7 or less (0.3 ≦ r ≦ 0.7), or may be within the range of 0.4 or more and 0.6 or less (0.4 ≦ r ≦ 0.6). The oxide phosphor, in the composition represented by the formula (1), is at least one element selected from the group consisting of Na, K, Rb, and Cs having an atomic number larger than that of Li in order to obtain a stable crystal structure, and is the second element M 2 ​​may not substantially include, and the variable r may be substantially 0 (r=0).

[0026] The oxide phosphor may contain a third element M 3 is at least one element selected from the group consisting of Al, Ga and Sc, and may contain two or more elements. 3 In order to obtain an oxide phosphor having a stable crystal structure in the composition represented by formula (1) and emitting fluorescence with an emission peak wavelength in a desired range in the wavelength range from red light to near-infrared light, the oxide phosphor may contain a third element M, which is at least one element selected from the group consisting of Al, Ga, and Sc, which has an atomic number smaller than that of In. 3 In the oxide phosphor, in the composition represented by the formula (1), the third element M is preferably substituted in a molar ratio that is at least half or less of the molar ratio of In. 3 may be replaced by .

[0027] The oxide phosphor contains In and a third element M in 1 mole of the oxide phosphor composition. 3 When the variable u in formula (1), which represents the molar ratio of the sum of the above, is within the range of 0.05 to 0.45 (0.05≦u≦0.45), it is possible to obtain an emission spectrum with a broader full width at half maximum and an emission peak wavelength in a desired range depending on the intended use in the wavelength range from red light to near-infrared light. The variable u in formula (1) of the oxide phosphor may be within the range of 0.10 to 0.45 (0.10≦u≦0.45), 0.15 to 0.45 (0.15≦u≦0.45), or 0.20 to 0.40 (0.20≦u≦0.40), or in order to obtain an oxide phosphor with a more stable crystal structure, it may be within the range of 0.25 to 0.40 (0.25≦u≦0.40).

[0028] The oxide phosphor contains In and a third element M in 1 mole of the oxide phosphor composition. 3The variable u in the formula (1) represents the total molar ratio of the above-mentioned Li and the second element M 2 In the oxide phosphor, when the variable u in the formula (1) is the same as the variable s in the formula (1) or the difference between the variable u and the variable s is 0.05 or less, the oxide phosphor contains In and / or a third element M having a valence electron number of 3 in 1 mole of the oxide phosphor. 3 However, Li and / or a second element M having one valence electron 2 The oxide phosphor has a peak emission wavelength in a range from red light to near-infrared light that is desirable depending on the intended use, and an emission spectrum with high emission intensity can be obtained at the peak emission wavelength. 3 When the variable u in the formula (1) representing the total molar ratio of Li and / or the second element M in the formula (1) is less than 0.05 or exceeds 0.45, 2 The balance with the variable s representing the total molar ratio of Mg and / or the first element M 1 This also disrupts the balance with the variable q, which represents the molar ratio of , and therefore an oxide phosphor with a stable crystal structure cannot be obtained, and the phosphor will not emit fluorescence even when irradiated with excitation light, or the emission intensity will be low.

[0029] The oxide phosphor may contain a third element M as needed in 1 mole of the oxide phosphor composition. 3 The molar ratio of In is expressed by the product of the variable t and the variable u in the formula (1), where the variable t is within the range of 0 to 0.5 (0≦v≦0.5), and all of In are the third element M 3In order to obtain an oxide phosphor with a stable crystal structure, the variable t in the formula (1) may be in the range of 0 or more and less than 0.5 (0≦t<0.5), in the range of 0 or more and 0.4 or less (0≦t≦0.4), in the range of 0 or more and 0.3 or less (0≦t≦0.3), in the range of 0 or more and 0.2 or less (0≦t≦0.2), or in the range of 0 or more and 0.1 or less (0≦t≦0.1) in 1 mole of the oxide phosphor composition. In order to obtain a stable crystal structure in the oxide phosphor, in the composition represented by the formula (1), a third element M which is at least one element selected from the group consisting of Al, Ga, and Sc having an atomic number smaller than that of In is added. 3 may not substantially include the variable t, and the variable t may be substantially 0 (t=0).

[0030] The oxide phosphor may contain a fourth element M 4 is at least one element selected from the group consisting of Si, Ti, Zr, Sn, and Hf. In order to obtain an emission spectrum with a wider full width at half maximum and an emission peak wavelength in a range desirable for the purpose of use in the wavelength range from red light to near-infrared light, the oxide phosphor may contain a fourth element M 4 may be either Si or Hf, and the fourth element M 4 may be Si.

[0031] The oxide phosphor contains Mg and the first element M in 1 mole of the composition of the oxide phosphor. 1 The variable q represents the total molar ratio of Li and the second element M 2 The variable s represents the total molar ratio of In and the third element M 3The sum (q + s + u) of the variable u representing the total molar ratio is within the range of 0.9 or more and 1.2 or less (0.9 ≦ q + s + u ≦ 1.2). In 1 mole of the composition of the oxide phosphor, in order to obtain an oxide phosphor with a stable crystal structure, the sum (q + s + u) of the variable q, the variable s, and the variable u may be within the range of more than 0.9 and 1.2 or less (0.9 < q + s + u ≦ 1.2), or may be within the range of 1.0 or more and 1.2 or less (1.0 ≦ q + s + u ≦ 1.2).

[0032] In 1 mole of the composition of the oxide phosphor, the oxide phosphor contains Ge and the fourth element M 4 If the variable w in the formula (1) representing the total molar ratio is within the range of 0.8 or more and 1.3 or less (0.8 ≦ w ≦ 1.3), in the wavelength range from red light to near-infrared light, the emission peak wavelength can be within a desirable range according to the intended use, and a broader emission spectrum with a larger full width at half maximum can be obtained. In the oxide phosphor, the variable w in the formula (1) may be within the range of 0.9 or more and 1.2 or less (0.9 ≦ w ≦ 1.2), or may be within the range of 1.0 or more and 1.2 or less (1.0 ≦ w ≦ 1.2). Ge and the fourth element M 4 The variable w in the formula (1) representing the total molar ratio of Ge and the fourth element M is preferably approximately the same value as the sum (q + s + u) of the variable q representing the total molar ratio of Mg and the first element M, the variable s representing the total molar ratio of Li and the second element M, and the variable u representing the total molar ratio of In and the third element M in order to obtain an oxide phosphor with a stable crystal structure. In the composition represented by the formula (1), in order to obtain a stable crystal structure, the oxide phosphor 1 The sum of the molar ratios of Mg and the first element M 2 The sum of the molar ratios of Li and the second element M 3 The variable w in the formula (1) representing the total molar ratio of In and the third element M may be 1.0 (w = 1.0). 4 In 1 mole of the composition of the oxide phosphor, the molar ratio of the fourth element M optionally contained is represented by the product of the variable v and the variable w in the formula (1), and the variable v is within the range of 0 or more and 1.0 or less (0 ≦ v ≦ 1.0). In 1 mole of the composition of the oxide phosphor, if all of the Ge in the formula (1) is the fourth element M

[0033] In 1 mole of the composition of the oxide phosphor, the fourth element M optionally contained 4 The molar ratio is represented by the product of the variable v and the variable w in the formula (1), and the variable v is within the range of 0 or more and 1.0 or less (0 ≦ v ≦ 1.0). In 1 mole of the composition of the oxide phosphor, if all of the Ge in the formula (1) is the fourth element M 4It may be replaced, and the variable v may be 1.0 (v = 1.0). In 1 mole of the composition of the oxide phosphor, a part of Ge in the formula (1) is the fourth atom M 4 is included, and the variable v in the formula (1) may be in the range greater than 0 and less than or equal to 1.0 (0 < v ≤ 1.0), or may be in the range greater than 0 and less than 1.0 (0 < v < 1.0). In order to obtain an oxide phosphor with a stable crystal structure, in 1 mole of the composition of the oxide phosphor, not all of Ge needs to be replaced by the fourth element M 4 and the variable v in the formula (1) may be in the range of 0 or more and 0.5 or less (0 ≤ v ≤ 0.5), may be in the range of 0 or more and less than 0.5 (0 ≤ v < 0.5), may be in the range of 0 or more and 0.4 or less (0 ≤ v ≤ 0.4), may be in the range of 0 or more and 0.3 or less (0 ≤ v ≤ 0.3), may be in the range of 0 or more and 0.2 or less (0 ≤ v ≤ 0.2), or may be in the range of 0 or more and 0.1 or less (0 ≤ v ≤ 0.1). The oxide phosphor is at least one element selected from the group consisting of Si or Ti having an atomic number smaller than Ge, and Zr, Sn, and Hf having an atomic number larger than Ge, as the fourth element M in the composition represented by the formula (1) in order to obtain a stable crystal structure 4 may not be substantially included, and the variable v may be substantially 0 (v = 0).

[0034] In 1 mole of the composition of the oxide phosphor, the variable x in the formula (1) representing the molar ratio of oxygen has an emission peak wavelength in a desirable range according to the purpose of use in the wavelength range from red light to near-infrared light. In order to obtain a wider full width at half maximum emission spectrum, it is in the range of 2.6 or more and 3.6 or less (2.6 ≤ x ≤ 3.6), may be in the range of 2.6 or more and 3.5 or less (2.6 ≤ x ≤ 3.5), may be in the range of 2.6 or more and 3.4 or less (2.6 ≤ x ≤ 3.4), may be in the range of 2.7 or more and 3.3 or less (2.7 ≤ x ≤ 3.3), may be in the range of 2.8 or more and 3.2 or less (2.8 ≤ x ≤ 3.2), may be in the range of 2.9 or more and 3.1 or less (2.9 ≤ x ≤ 3.1), or may be 3.0 (x = 3.0).

[0035] The oxide phosphor may contain a fifth element M 5 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er and Yb, and may be at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn and Nd.

[0036] The oxide phosphor has a composition represented by the formula (1) in which, in 1 mol of the oxide phosphor, a fifth element M, which is an activator element together with Cr and is contained as needed, is 5 The variable z representing the molar ratio is in the range of 0 to 0.3 (0≦z≦0.3), may be in the range of 0 to 0.2 (0≦z≦0.2), may be in the range of 0 to 0.1 (0≦z≦0.1), or may be 0.001 or more (0.001≦z). 5 may not substantially include, and the variable z may be substantially 0 (z=0).

[0037] In the emission spectrum of the oxide phosphor, the emission intensity at 1000 nm is preferably 10% or more, more preferably 15% or more, even more preferably 20% or more, even more preferably 30% or more, even more preferably 35% or more, and particularly preferably 37% or more, relative to 100% of the emission intensity at the emission peak wavelength. If the emission spectrum of the oxide phosphor is 5% or more relative to 100% of the emission intensity at the emission peak wavelength, the oxide phosphor can emit light with the emission intensity required for analysis in the wavelength range of 900 nm to 1100 nm, which is a near-infrared light range that can easily obtain information about living organisms and information about agricultural products, food, pharmaceuticals, etc. in a non-destructive manner, and can be used in light-emitting devices for analytical equipment in place of tungsten lamps or xenon lamps. In the emission spectrum of an oxide phosphor, it is preferable that the ratio of the emission intensity at 1000 nm to the 100% emission intensity at the emission peak wavelength is high, but even if the ratio of the emission intensity at 1000 nm is low, if the emission spectrum has a relatively wide full width at half maximum, it is possible to obtain light with the emission intensity required for analysis to obtain information about living organisms or non-destructively information about agricultural products, foods, and pharmaceuticals. When the full width at half maximum of the emission spectrum of an oxide phosphor is in the range of 150 nm to 220 nm, the emission intensity at 1000 nm may be 10% or more relative to the 100% emission intensity at the emission peak wavelength.

[0038] The oxide phosphor preferably has an emission spectrum having an emission peak wavelength with a full width at half maximum in the range of 150 nm to 220 nm. The oxide phosphor preferably converts the wavelength of excitation light from an excitation light source such as a light-emitting element to emit light having an emission peak wavelength in a desired range from red light to near-infrared light in its emission spectrum, a wide full width at half maximum, and an emission intensity required for analysis, etc.

[0039] If light having a wide full width at half maximum (FWHM) emission spectrum can be irradiated in a wavelength range that allows for non-destructive acquisition of information about living organisms and agricultural products, it becomes easier to obtain information about living organisms and agricultural products. Furthermore, the appearance of the color of an object when irradiated with light (hereinafter also referred to as "color rendering") is determined by an emission spectrum having a wide wavelength range, and a wide FWHM allows for the emission of light with excellent color rendering. For example, even when emitting light in a wavelength range that affects plant growth in a plant factory, it may be necessary to emit light that does not disrupt the spectral balance of the light to make it easier for workers to work. The oxide phosphor may have an emission spectrum with a peak wavelength of 160 nm or more, 165 nm or more, 170 nm or more, 175 nm or more, or 215 nm or less. The oxide phosphor may have an emission spectrum with a peak wavelength of 175 nm or more and 220 nm or less. In this specification, the full width at half maximum refers to the wavelength width that is 50% of the emission intensity at the emission peak wavelength that exhibits the maximum emission intensity in the emission spectrum.

[0040] The oxide phosphor preferably has an emission peak wavelength in the range of 830 nm to 930 nm in its emission spectrum. The oxide phosphor converts the wavelength of excitation light from an excitation light source such as a light-emitting element to emit light in the wavelength range from red to near-infrared. A light-emitting device equipped with an oxide phosphor emitting light in the wavelength range from red to near-infrared can replace a tungsten lamp or a xenon lamp. The oxide phosphor preferably has an emission spectrum with an emission intensity required for analysis in a wavelength range that makes it easy to obtain information about living organisms and agricultural products. When the oxide phosphor has an emission peak wavelength in the range of 830 nm to 930 nm in its emission spectrum, an emission spectrum with an emission intensity required for analysis in a wavelength range that makes it easy to obtain information about living organisms and information about agricultural products, foods, pharmaceuticals, etc. non-destructively can be obtained. The oxide phosphor may have an emission peak wavelength in the range of 860 nm to 930 nm or may have an emission peak wavelength in the range of 870 nm to 930 nm in its emission spectrum.

[0041] The oxide phosphor contains, in 1 mole of the oxide phosphor composition, Mg and the first element M in the formula (1). 1 When the variable q, which represents the total molar ratio of the above, is within the range of 0.6 or more and 0.9 or less (0.6≦q≦0.9) and the variable p is within the range of 0 or more and 0.4 or less (0≦p≦0.4), an oxide phosphor with a stable crystal structure can be obtained, and the emission spectrum preferably has an emission peak wavelength within the range of 860 nm or more and 930 nm or less.

[0042] The oxide phosphor contains, in 1 mole of the oxide phosphor composition, Mg and the first element M in the formula (1). 1 When the variable q, which represents the total molar ratio of the above, is within the range of 0.5 or more and 0.9 or less (0.5≦q≦0.9), an oxide phosphor having a stable crystal structure in the emission spectrum is obtained, and it is preferable that the emission spectrum has an emission peak wavelength in the range of 860 nm or more and 930 nm or less.

[0043] The oxide phosphor has a fourth element M in the formula (1) in 1 mole of the oxide phosphor. 4 When the variable v is substantially zero (v=0), an oxide phosphor having a stable crystal structure is obtained, and the emission spectrum preferably has an emission peak wavelength in the range of 870 nm to 930 nm.

[0044] The light emitting device includes an oxide phosphor having a composition represented by formula (1) and a light emitting element having an emission peak wavelength in the range of 365 nm to 650 nm and irradiating the oxide phosphor. The oxide phosphor can be used as a component constituting a wavelength conversion member together with a translucent material.

[0045] A semiconductor element can be used as a light-emitting element that irradiates an oxide phosphor. For example, nitride semiconductors can be selected as materials for light-emitting elements that emit green and blue light. In is used as a material for the semiconductor structure that constitutes the light-emitting element. X Al Y Ga 1-X-YN (0≦X≦1, 0≦Y≦1, X+Y≦1), etc. can be used. As a material for the light-emitting element that emits red light, for example, a gallium-aluminum-arsenic-based semiconductor or an aluminum-indium-gallium-phosphorus-based semiconductor can be selected. As the light-emitting element, it is preferable to use, for example, an LED chip or an LD chip.

[0046] The light-emitting element may have an emission peak wavelength in the range of 365 nm to 650 nm, or may have an emission peak wavelength in the range of 365 nm to 500 nm, or may have an emission peak wavelength in the range of 370 nm to 490 nm, or may have an emission peak wavelength in the range of 375 nm to 480 nm. The light-emitting element may also have an emission peak wavelength in the range of more than 500 nm to 650 nm, or may have an emission peak wavelength in the range of 510 nm to 650 nm, or may have an emission peak wavelength in the range of 520 nm to 650 nm. By using the light-emitting element as an excitation light source for the oxide phosphor, it is possible to construct a light-emitting device that emits a mixed color light of the light from the light-emitting element and the fluorescence from the phosphor containing the oxide phosphor in a desired wavelength range. The full width at half maximum of the emission peak in the emission spectrum of the light-emitting element can be, for example, 30 nm or less. It is preferable to use a light-emitting element using, for example, a nitride-based semiconductor. By using a light emitting element using a nitride semiconductor as an excitation light source, it is possible to obtain a light emitting device that is highly efficient, has high linearity of output relative to input, and is resistant to mechanical shocks.

[0047] The light emitting device essentially comprises a first phosphor containing the oxide phosphor described above, and may further comprise a phosphor having a different composition. In addition to the first phosphor, the light emitting device preferably comprises at least one phosphor selected from the group consisting of a second phosphor having a peak emission wavelength in the range of 455 nm or more and less than 495 nm, a third phosphor having a peak emission wavelength in the range of 495 nm or more and less than 610 nm, a fourth phosphor having a peak emission wavelength in the range of 610 nm or more and less than 700 nm, and a fifth phosphor having a peak emission wavelength in the range of 700 nm or more and less than 1050 nm, in the emission spectrum of each phosphor. The light emitting device comprises a light emitting element and the first phosphor containing the oxide phosphor described above, and at least one phosphor selected from the group consisting of the second phosphor, the third phosphor, the fourth phosphor, and the fifth phosphor, and thus can be used as a light source that emits light having an emission spectrum in a wavelength range that includes visible light to a portion of near-infrared light. The light-emitting device has an emission spectrum similar to that of conventionally used tungsten lamps and xenon lamps, and can be used as a light source that can be made smaller than tungsten lamps and xenon lamps. The compact light-emitting device can be installed in small mobile devices such as smartphones and smartwatches, and the information obtained from within the body can be used for health management, etc. The light emitting device can be used, for example, in a reflectance spectroscopic measuring device or a lighting device that is required to be capable of non-destructively measuring the inside of a living body or fruits and vegetables and that also has excellent color rendering properties.

[0048] The second phosphor, which has a different composition from the first phosphor containing the oxide phosphor described above, preferably contains at least one phosphor selected from the group consisting of a phosphate phosphor having a composition represented by the following formula (2a), an aluminate phosphor having a composition represented by the following formula (2b), and an aluminate phosphor having a composition represented by the following formula (2c), and may contain two or more phosphors. (Ca, Sr, Ba, Mg) 10 (PO4)6(F,Cl,Br,I)2:Eu (2a) (Ba,Sr,Ca)MgAl 10 O 17:Eu (2b) Sr4Al 14 O 25 :Eu (2c) In this specification, when a plurality of elements are separated by a comma (,) in a composition formula, it means that at least one of these elements is contained in the composition.

[0049] The third phosphor preferably contains at least one phosphor selected from the group consisting of a silicate phosphor having a composition represented by the following formula (3a), an aluminate phosphor or gallate phosphor having a composition represented by the following formula (3b), a β-sialon phosphor having a composition represented by the following formula (3c), a cesium lead halide phosphor having a composition represented by the following formula (3d), and a nitride phosphor having a composition represented by the following formula (3e), and may contain two or more phosphors. When the third phosphor contains two or more phosphors, it is preferable that each of the two or more third phosphors be a phosphor having a different emission peak wavelength in the range of 495 nm or more and less than 610 nm. (Ca,Sr,Ba)8MgSiO 16 (F,Cl,Br)2:Eu (3a) (Lu,Y,Gd,Tb)3(Al,Ga)5O 12 :Ce (3b) Si 6-z Al z O z N 8-z :Eu (0 <z≦4.2) (3c) CsPb(F,Cl,Br)3(3d) (La,Y,Gd)3Si6N 11 :Ce (3e)

[0050] The fourth phosphor preferably contains at least one phosphor selected from the group consisting of a nitride phosphor having a composition represented by the following formula (4a), a fluorogermanate phosphor having a composition represented by the following formula (4b), an oxynitride phosphor having a composition represented by the following formula (4c), a fluoride phosphor having a composition represented by the following formula (4d), a fluoride phosphor having a composition represented by the following formula (4e), a nitride phosphor having a composition represented by the following formula (4f), and a nitride phosphor having a composition represented by the following formula (4g), and may contain two or more phosphors. When the fourth phosphor contains two or more phosphors, it is preferable that each of the two or more fourth phosphors is a phosphor having an emission peak wavelength in a different range within the range of 610 nm or more and less than 700 nm. (Sr,Ca)AlSiN3:Eu (4a) 3.5MgO·0.5MgF2·GeO2:Mn (4b) (Ca,Sr,Mg) k Si 12-(m+n) Al m+n O n N 16-n :Eu (4c) (In the formula (4c), k, m, and n satisfy 0 < k ≤ 2.0, 2.0 ≤ m ≤ 6.0, and 0 ≤ n ≤ 2.0.) A 1 c1 [M 6 1-b1 Mn 4+ b1 F d1 (4d) (In the formula (4d), A 1 is at least one selected from the group consisting of K + , Li + , Na + , Rb + , Cs + and NH4 + , and among them, K + is preferable. M 6 contains at least one element selected from the group consisting of a Group 4 element and a Group 14 element, and among them, Si and Ge are preferable. b1 satisfies 0 < b1 < 0.2, and c1 is [M 6 1-b1 Mn4+ b1 F d1 is the absolute value of the charge of the ion, and d1 satisfies 5 < d1 < 7.) A 2 c2 [M 7 1-b2 Mn 4+ b2 F d2 (4e) (In the formula (4e), A 2 is at least one selected from the group consisting of K + , Li + , Na + , Rb + , Cs + and NH4 + , and among them, K + is preferred. M 7 includes group 13 elements, and may further include at least one element selected from the group consisting of group 4 elements and group 1​​​​​​​​​​​​​​​The fifth phosphor preferably contains at least one phosphor selected from the group consisting of a gallate phosphor having a composition represented by the following formula (5a), an aluminate phosphor having a composition represented by the following formula (5b), a gallate phosphor having a composition represented by the following formula (5c), an aluminate phosphor having a composition represented by the following formula (5d), and a phosphor having a composition represented by the following formula (5e) which is different in composition from the oxide phosphor, a phosphor having a composition represented by the following formula (5f) which is different in composition from the oxide phosphor, a phosphor having a composition represented by the following formula (5g) which is different in composition from the oxide phosphor, a phosphor having a composition represented by the following formula (5h) which is different in composition from the oxide phosphor, and a phosphor having a composition represented by the following formula (5i) which is different in composition from the oxide phosphor, and may contain two or more phosphors. Ga2O3:Cr (5a) Al2O3:Cr (5b) ZnGa2O4:Cr (5c) (Lu,Y,Gd,Tb)3(Al,Ga)5O 12 :Ce,Cr (5d) M 8 g M 9 h M 10 i M 11 5O j :Cr e , M 12 f (5e) (In the formula (5e), ​​M 8 is at least one element selected from the group consisting of Li, Na, Ka, Rb, and Cs, and M 9 is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and M 10 is at least one element selected from the group consisting of Ba, Al, Ga, In and rare earth elements, and M 11 is at least one element selected from the group consisting of Si, Ti, Ge, Zr, Sn, Hf and Pb, and M 12is at least one element selected from the group consisting of Eu, Ce, Tb, Pr, Nd, Sm, Yb, Ho, Er, Tm, Ni, and Mn, and e, f, g, h, i, and j satisfy 0 < e ≤ 0.2, 0 ≤ f ≤ 0.1, f < e, 0.7 ≤ g ≤ 1.3, 1.5 ≤ h ≤ 2.5, 0.7 ≤ i ≤ 1.3, 12.9 ≤ j ≤ 15.1.) (Mg 1-t1 M 13 t1 ) u1 (Ga 1-v1-x1-y1 M 14 v1 )2O w1 :Cr x1 ,M 15 y1 (5f) (In the formula (5f), M 13 is at least one element selected from the group consisting of Ca, Sr, Ba, Ni, and Zn, M 14 is at least one element selected from the group consisting of B, Al, Sc, and In, M 15 is at least one element selected from the group consisting of Eu, Ce, Tb, Pr, Nd, Sm, Yb, Ho, Er, Tm, and Mn, and t1, u1, v1, w1, x1, and y1 satisfy 0 ≤ t1 ≤ 0.8, 0.7 ≤ u1 ≤ 1.3, 0 ≤ v1 ≤ 0.8, 3.7 ≤ w1 ≤ 4.3, 0.02 < x1 ≤ 0.3, 0 ≤ y1 ≤ 0.2, y1 < x1.) (Li 1-t2 M 16 t2 ) u2 (Ga 1-v2 M 17 v2 )5O w2 :Cr x2 ,Ni y2 ,M 18 z2 (5g) (In the formula (5g), M 16 is at least one element selected from the group consisting of Na, K, Rb, and Cs, M 17 is at least one element selected from the group consisting of B, Al, Sc, In, and rare earth elements, M 18is at least one element selected from the group consisting of Si, Ge, Sn, Ti, Zr, Hf, Bi, V, Nb, and Ta, and t2, u2, v2, w2, x2, y2, and z2 satisfy 0≦t2≦1.0, 0.7≦u2≦1.6, 0≦v2<1.0, 7.85≦w2≦11.5, 0.05≦x2≦1.2, 0≦y2≦0.5, 0.25<x2 + y2≦1.2, y2<x2, 0≦z2≦0.5 respectively.) (Ga 1-u3 M 19 u3 )2(Ge 1-v3 M 20 v3 ) w3 O x3 :Cr y3 ,M 21 z3 (5h) (In the formula (5h), M 19 is at least one element selected from the group consisting of Al, Sc, and In, M 20 is at least one element selected from the group consisting of Si, Ti, Zr, Sn, and Hf, M 21 is at least one element selected from the group consisting of Ni, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and u3, v3, w3, x3, y3, and z3 satisfy 0≦u3≦1.0, 0≦v3≦0.5, 1.0≦w3≦3.0, 5≦x3≦9, 0.005≦y3≦1.0, 0≦z3≦0.5 respectively.) (Mg 1-s4 M 22 s4 )2(Al 1-t4 M 23 t4 ) u4 (Ge 1-v4 M 24 v4 ) w4 O x4 :Cr y4 ,M 25 z4 (5i) (In the formula (5i), M 22 is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, M 23is at least one element selected from the group consisting of Ga, Sc, and In, and M 24 is at least one element selected from the group consisting of Si, Ti, Zr, Sn and Hf, and M 25 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and s4, t4, u4, v4, w4, x4, y4, and z4 satisfy the following relationships: 0≦s4≦1.0, 0≦t4≦1.0, 1.5≦u4≦2.5, 0≦v4≦0.5, 3.0≦w4≦6.0, 11.0≦x4≦17.0, 0.005≦y4≦1.0, and 0≦z4≦0.5, respectively.

[0052] An example of a light emitting device will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a first configuration example of a light emitting device. Fig. 2 is a schematic cross-sectional view showing another example of the first configuration example of a light emitting device.

[0053] As shown in FIG. 1, the light emitting device 100 includes a molded body 40 having a recess, a light emitting element 10 serving as an excitation light source, and a wavelength conversion member 50 covering the light emitting element 10. The molded body 40 is formed by integrally molding a first lead 20, a second lead 30, and a resin portion 42 containing a thermoplastic resin or a thermosetting resin. In the molded body 40, at least the first lead 20 and the second lead 30 form the bottom surface of the recess, and at least the resin portion 42 forms the side surface of the recess. The light emitting element 10 is placed on the bottom surface of the recess of the molded body 40. The light emitting element 10 has a pair of positive and negative electrodes, which are electrically connected to the first lead 20 and the second lead 30 via wires 60, respectively. The light emitting element 10 is covered with the wavelength conversion member 50. The wavelength conversion member 50 includes a phosphor 70 that converts the wavelength of light emitted from the light emitting element 10, and a translucent material. The phosphor 70 essentially includes a first phosphor 71 containing an oxide phosphor. The phosphor 70 may include a phosphor having an emission peak wavelength in a wavelength range different from that of the first phosphor 71 and having a different composition from that of the first phosphor 71. As shown in FIG. 2 , the phosphor 70 preferably includes at least one phosphor selected from the group consisting of the second phosphor 72, the third phosphor 73, the fourth phosphor 74, and the fifth phosphor 75, each of which is described above, and may include two or more phosphors. The phosphor 70 essentially includes the first phosphor 71 and may also include the second phosphor 72, the third phosphor 73, the fourth phosphor 74, and the fifth phosphor 75. The wavelength conversion member 50 also functions as a member for protecting the light emitting element 10, the wire 60, the phosphor 70, and the like from the external environment. The light emitting device 100 emits light upon receiving external power via the first lead 20 and the second lead 30.

[0054] 3A and 3B show a second configuration example of a light-emitting device. FIG. 3A is a schematic plan view of the light-emitting device 200. FIG. 3B is a schematic cross-sectional view of the light-emitting device 200 taken along line III-III' in FIG. 3A. The light-emitting device 200 includes a light-emitting element 10 having an emission peak wavelength in the range of 365 nm to 650 nm, and a wavelength conversion member 51 including a wavelength converter 52 containing a first phosphor 71 that emits light upon excitation with light from the light-emitting element 10, and a light-transmitting body 53 disposed on the wavelength converter 52. The light-emitting element 10 is flip-chip mounted on the substrate 1 via bumps that are conductive members 61. The wavelength converter 52 of the wavelength conversion member 51 is disposed on the light-emitting surface of the light-emitting element 10 via an adhesive layer 80. The light-emitting element 10 and the wavelength conversion member 51 have their side surfaces covered with a light-reflective covering member 90. The wavelength converter 52 is excited by light from the light-emitting element 10 and essentially contains a first phosphor 71 containing an oxide phosphor. The wavelength converter 52 may contain at least one selected from the group consisting of a second phosphor, a third phosphor, a fourth phosphor, and a fifth phosphor. The light emitting element 10 can receive power from outside the light emitting device 200 via wiring and a conductive member 61 formed on the substrate 1, causing the light emitting device 200 to emit light. The light emitting device 200 may include a semiconductor element 11, such as a protective element, for protecting the light emitting element 10 from damage due to application of excessive voltage. The semiconductor element 11 may be mounted on the substrate 1 via the conductive member 61. The covering member 90 is disposed so as to cover, for example, the semiconductor element 11. Each component used in the light emitting device will be described below. For details, see, for example, the disclosure of JP 2014-112635 A.

[0055] The translucent material constituting the wavelength converter together with the phosphor may be at least one selected from the group consisting of resin, glass, and inorganic materials. The resin may be at least one selected from the group consisting of silicone resin, epoxy resin, phenolic resin, polycarbonate resin, acrylic resin, and modified resins thereof. Silicone resin and modified silicone resin are preferred because of their excellent heat resistance and light resistance. In addition to the phosphor and the translucent material, the wavelength converter may contain a filler, a colorant, and a light diffusing material as needed. Examples of fillers include silicon oxide, barium titanate, titanium oxide, and aluminum oxide.

[0056] The light-transmitting body can be a plate-shaped body made of a light-transmitting material such as glass or resin. Examples of glass include borosilicate glass and quartz glass. Examples of resin include silicone resin and epoxy resin. When the wavelength conversion member includes a substrate, the substrate is preferably made of an insulating material that is difficult to transmit light from the light-emitting element and external light. Examples of materials for the substrate include ceramics such as aluminum oxide and aluminum nitride, and resins such as phenolic resin, epoxy resin, polyimide resin, bismaleimide triazine resin (BT resin), and polyphthalamide (PPA) resin. When an adhesive layer is interposed between the light-emitting element and the wavelength conversion member, the adhesive constituting the adhesive layer is preferably made of a material that can optically connect the light-emitting element and the wavelength conversion member. The material constituting the adhesive layer is preferably at least one resin selected from the group consisting of epoxy resin, silicone resin, phenolic resin, and polyimide resin. The light-transmitting body does not have to be disposed in the wavelength conversion member.

[0057] Examples of semiconductor elements that may be provided in a light-emitting device as needed include transistors for controlling light-emitting elements and protective elements for preventing damage to light-emitting elements or performance degradation due to excessive voltage application. Zener diodes are examples of protective elements. When a light-emitting device includes a covering member, it is preferable to use an insulating material for the covering member. More specifically, examples include phenolic resin, epoxy resin, bismaleimide triazine resin (BT resin), polyphthalamide (PPA) resin, and silicone resin. Colorants, phosphors, and fillers may be added to the covering member as needed. The light-emitting device may use bumps as conductive members. Examples of materials for the bumps include Au or its alloys, and other conductive materials include eutectic solder (Au-Sn), Pb-Sn, and lead-free solder.

[0058] An example of a method for manufacturing a light emitting device of the first configuration example will be described. For details, the disclosure of JP 2010-062272 A can be referenced, for example. The method for manufacturing a light emitting device preferably includes a molded body preparation step, a light emitting element arrangement step, a wavelength conversion member forming composition arrangement step, and a resin package formation step. When an aggregate molded body having a plurality of recesses is used as the molded body, the resin package formation step may be followed by a singulation step of separating the molded body into individual resin packages of each unit area.

[0059] In the step of preparing a molded body, a plurality of leads are integrally molded using a thermosetting resin or a thermoplastic resin to prepare a molded body having a recess with a side surface and a bottom surface. The molded body may be a molded body made of an aggregate base including a plurality of recesses.

[0060] In the light-emitting element placement step, the light-emitting element is placed on the bottom surface of the recess of the molded body, and the positive and negative electrodes of the light-emitting element are connected to the first lead and the second lead by wires.

[0061] In the step of placing the composition for forming a wavelength conversion member, the composition for forming a wavelength conversion member is placed in the recess of the molded body.

[0062] In the resin package molding step, the wavelength conversion member-forming composition placed in the recesses of the molded body is cured to form a resin package, thereby manufacturing a light emitting device. When a molded body made of an aggregate substrate having multiple recesses is used, after the resin package formation step, the aggregate substrate having multiple recesses is separated into individual resin packages in each unit area in a singulation step, thereby manufacturing individual light emitting devices. In this manner, the light emitting device shown in FIG. 1 or 2 can be manufactured.

[0063] An example of a method for manufacturing the light emitting device of the second configuration example will be described. For details, reference can be made to the disclosures of, for example, Japanese Patent Application Laid-Open No. 2014-112635 or Japanese Patent Application Laid-Open No. 2017-117912. The method for manufacturing the light emitting device preferably includes a step of arranging a light emitting element, a step of arranging a semiconductor element as needed, a step of forming a wavelength conversion member including a wavelength converter, a step of bonding the light emitting element and the wavelength conversion member, and a step of forming a covering member.

[0064] For example, in the light-emitting element placement step, the light-emitting element is placed on a substrate. The light-emitting element and the semiconductor element are, for example, flip-chip mounted on the substrate. Next, in the wavelength conversion member formation step, the wavelength conversion element may be obtained by forming a plate-shaped, sheet-shaped, or layer-shaped wavelength conversion element on one surface of a translucent body using a printing method, an adhesive method, a compression molding method, or an electrodeposition method. For example, a printing method can be used to print a wavelength conversion member containing a phosphor and a resin serving as a binder or solvent on one surface of a translucent body to form a wavelength conversion member containing a wavelength conversion element. Next, in the bonding step between the light-emitting element and the wavelength conversion member, the wavelength conversion member is placed opposite the light-emitting surface of the light-emitting element and bonded to the light-emitting element with an adhesive layer. Next, in the coating member formation step, the side surfaces of the light-emitting element and the wavelength conversion member are covered with a coating member composition. This coating member is intended to reflect light emitted from the light-emitting element. If the light-emitting device also includes a semiconductor element, it is preferable that the semiconductor element be embedded in the coating member. In this manner, the light-emitting device shown in Figures 3A and 3B can be manufactured.

[0065] The method for producing an oxide phosphor includes: forming a first compound containing Mg and / or at least one first element M selected from the group consisting of Ca, Sr, Ba, and Zn; 1 a second compound containing Li and / or a third compound containing at least one second element M selected from the group consisting of Na, K, Rb, and Cs; 2 a fourth compound containing In, a fifth compound containing In, a seventh compound containing Ge, and / or at least one fourth element M selected from the group consisting of Si, Ti, Zr, Sn, and Hf. 4 an eighth compound containing Cr, a ninth compound containing Cr, and optionally at least one third element M selected from the group consisting of Al, Ga, and Sc. 3 and optionally at least one fifth element M selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb. 5 and a tenth compound containing Mg and / or the first element M in 1 mole of the oxide phosphor composition. 1 When the total molar ratio of the first element M is taken as the variable q, 1 The molar ratio of Mg is the product of the variable p and the variable q, where the variable p is a number between 0 and 1.0, and the variable q is a number between 0.1 and 0.9, and the molar ratio of Mg is the product of the number obtained by subtracting the variable p from 1 and the variable q, and Li and / or the second element M 2 When the total molar ratio of the second element M is set as the variable s, 2 The molar ratio of Li is the product of the variable r and the variable s, where the variable r is a value between 0 and 1.0, and the variable s is a value between 0.05 and 0.45, and the molar ratio of Li is the product of the value obtained by subtracting the variable r from 1 and the variable s, and the molar ratio of In and the third element M 3 When the total molar ratio of the third element M is set as the variable u, 3 The molar ratio of In is the product of the variable t and the variable u, where the variable t is a value of 0 or more and 0.5 or less, and the variable u is a value of 0.05 or more and 0.45 or less, and the molar ratio of In is the product of the value obtained by subtracting the variable t from 1 and the variable u, and Ge and / or a fourth element M 4 When the total molar ratio of the fourth element M is set as the variable w, 4the molar ratio of Ge is the product of the variable v and the variable w, where the variable v is a number between 0 and 1.0, and the variable w is a number between 0.8 and 1.3, the molar ratio of Ge is the product of the number obtained by subtracting the variable v from 1 and the variable w, the molar ratio of the sum of the variables q, s, and u is a number between 0.9 and 1.2, the molar ratio of Cr is the variable y, where the variable y is a number between 0.002 and 0.5, 5 The method includes preparing a raw material mixture by adjusting and mixing a first compound and / or a second compound, a third compound and / or a fourth compound, a fifth compound, a seventh compound and / or an eighth compound, a ninth compound, and optionally a sixth compound and optionally a tenth compound, so that the molar ratio of the first compound and / or the second compound is a variable z, and the variable z is a value between 0 and 0.3, and heat-treating the raw material mixture at a temperature between 800°C and 1400°C in an oxygen-containing atmosphere to obtain an oxide phosphor, wherein at least one selected from the group consisting of the first compound, the second compound, the third compound, the fourth compound, the fifth compound, the seventh compound, the eighth compound, and the ninth compound is preferably an oxide. The resulting oxide phosphor preferably has a molar ratio of each element of the oxide phosphor in 1 mole of the oxide phosphor composition in the same range as the composition used to obtain the raw material mixture.

[0066] The raw materials for producing the oxide phosphor include a first compound containing Mg and / or a first element M 1 a second compound containing Li and / or a third compound containing Li and / or a second element M 2 a fourth compound containing In, a fifth compound containing In, a seventh compound containing Ge and / or a fourth element M 4 and a ninth compound containing Cr, and optionally a third element M 3 and a sixth compound containing a fifth element M 5 The raw materials for producing the oxide phosphor may include a first compound containing Mg and a tenth compound containing the first element M 1 The raw materials for producing the oxide phosphor may contain at least one compound selected from the group consisting of a third compound containing Li and a second compound containing the second element M. 2The raw materials for producing the oxide phosphor may contain at least one compound selected from the group consisting of a seventh compound containing Ge and a fourth element M 4 The composition may contain at least one compound selected from the group consisting of an eighth compound containing the compound. The first compound, the second compound, the third compound, the fourth compound, the fifth compound, the sixth compound, the seventh compound, the eighth compound, the ninth compound, and the tenth compound may each be an oxide, a carbonate, a chloride, or a hydrate thereof. At least one compound selected from the group consisting of the first compound, the second compound, the third compound, the fourth compound, the fifth compound, the seventh compound, the eighth compound, and the ninth compound may be an oxide, and two or more compounds may be oxides. The third element M, which is optionally contained, 3 A sixth compound containing a fifth element M 5 The tenth compound may be an oxide. The first, second, third, fourth, fifth, seventh, eighth, and ninth compounds are preferably powders. The sixth and tenth compounds may be powders.

[0067] Examples of the first compound containing Mg include MgO, MgCO3, and MgCl2. 1 Examples of the second compound containing the second element M include CaO, CaCO3, CaCl2, SrO, SrCO3, SrCl2, BaO, BaCO3, BaCl2, ZnO, ZnCO3, and ZnCl2. Examples of the third compound containing Li include Li2O, LiCl, and Li2CO3. 2 Examples of the fourth compound containing In include Na2O, NaCl, Na2CO3, K2O, KCl, K2CO3, Rb2O, RbCl, Rb2CO3, Cs2O, CsCl, and Cs2CO3. Examples of the fifth compound containing In include In2O3 and InCl3. Examples of the seventh compound containing Ge include GeO2 and GeCl4. The fourth element M 4Examples of the eighth compound containing Cr include SiO2, TiO2, TiCl4, ZrO2, ZrCl4, SnO2, SnCl2, HfO2, and HfCl4. Examples of the ninth compound containing Cr include Cr2O3, Cr2(CO3)3, and CrCl3. The first, second, third, fourth, fifth, seventh, eighth, and ninth compounds may be hydrates.

[0068] 3rd element M 3 Examples of the sixth compound include Al2O3, AlCl3, Ga2O3, GaCl3, Sc2O3, and ScCl3. The sixth compound may be a hydrate.

[0069] 5th element M 5 Examples of the tenth compound include NiO, NiCl2, CeO2, CeCl3, Ce2(CO3)3, Eu2O3, EuCl3, Fe2O3, Fe3O4, FeCl2, FeCl3, FeCO3, Fe2(CO3)3, MnO, MnO2, Mn2O3, Mn3O4, Nd2(CO3)3, Nd2O3, NdCl3, Tm2O3, TmCl3, Ho2O3, HoCl3, Er2O3, ErCl3, Yb2O3, and YbCl3. The sixth compound may be a hydrate.

[0070] The raw material mixture is preferably prepared by adjusting and mixing each raw material so as to have a composition represented by the following formula (1): In the oxide phosphor obtained by the production method, each element of the oxide phosphor preferably has the same composition as the composition represented by the following formula (1) for obtaining the raw material mixture, per mole of the oxide phosphor composition. (Mg 1-p M 1 p ) q (Li 1-r M 2 r ) s (In 1-t M 3 t ) u (Ge 1-v M 4 v ) w O x:Cr y ,M 5 z (1) (In the above formula (1), M 1 is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, and M 2 is at least one element selected from the group consisting of Na, K, Rb and Cs, and M 3 is at least one element selected from the group consisting of Al, Ga, and Sc, and M 4 is at least one element selected from the group consisting of Si, Ti, Zr, Sn and Hf, and M 5 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and p, q, r, s, t, u, v, w, x, y, and z satisfy the following conditions: 0≦p≦1.0, 0.1≦q≦0.9, 0≦r≦1.0, 0.05≦s≦0.45, 0≦t≦0.5, 0.05≦u≦0.45, 0≦v≦1.0, 0.8≦w≦1.3, 2.6≦x≦3.6, 0.002≦y≦0.5, 0≦z≦0.3, 0.9≦q+s+u≦1.2, respectively.

[0071] The raw material mixture has a composition represented by the formula (1), in which a part of Mg is a first element M 1 may be replaced by Mg, and all Mg may be replaced by the first element M 1 Among these, Zn may be substituted, and Ca and at least one element selected from the group consisting of Sr, Ba, and Zn may be used as the first element M. 1 and Zn and at least one first element M selected from the group consisting of Ca, Sr, and Ba. 1 In the raw material mixture, in the composition represented by the formula (1), a part of Li in the oxide phosphor may be replaced by the second element M 2 Li may be replaced by the second element M 2 may be replaced by, and all Li may be replaced by the second atom M 2 In the raw material mixture, in the composition represented by the formula (1), a part of In is replaced by the third element M 3The raw material mixture may be a mixture of Ge and M in which a part of Ge is replaced by a fourth element M in the composition represented by the formula (1). 4 All of the Ge can be replaced by the fourth element M 4 may be replaced by the fourth element M 4 Among these, Si may be substituted.

[0072] The raw material mixture is preferably a mixture of a ninth compound containing Cr, in which y satisfies 0.020≦y≦0.070 in the composition represented by the formula (1). The raw material mixture is preferably a mixture of a fifth compound containing In, in which u satisfies 0.25≦u≦0.40, and a third element M, which is optionally contained, in the composition represented by the formula (1). 3 The raw material mixture is preferably mixed with a sixth compound containing the first element M in the composition represented by the formula (1) so that p satisfies 0≦p<1.0. 1 The raw material mixture is preferably a mixture of a first compound containing Mg and a second compound containing a first element M, so that p satisfies 0≦p≦0.4 and q satisfies 0.6≦q≦0.9 in the composition represented by the formula (1). 1 The raw material mixture may be mixed with a first compound containing Mg and / or a first element M such that q satisfies 0.5≦q≦0.9 in the composition represented by formula (1). 1 The raw material mixture may contain a seventh compound containing Ge and a fourth element M in the composition represented by formula (1) so that v satisfies 0≦v<0.5. 4 The raw material mixture may contain an eighth compound containing a fourth element M 4 The raw material mixture may not contain the eighth compound containing the second element M in the composition represented by the formula (1) so that r=0. 2 It is also possible to omit the fourth compound containing

[0073] The first and / or second compounds, the third and / or fourth compounds, the fifth compound, the seventh and / or eighth compounds, the ninth compound, the sixth compound which may be included as needed, and the tenth compound which may be included as needed are mixed wet or dry so that the elements contained in each raw material compound satisfy the above-mentioned composition, thereby obtaining a raw material mixture. The measured compounds may be mixed using a mixer. The mixer may be a ball mill, which is commonly used industrially, or a vibration mill, a roll mill, a jet mill, or the like.

[0074] The raw material mixture may contain a flux. The inclusion of a flux in the raw material mixture further promotes the reaction between the raw materials and allows the solid-state reaction to proceed more uniformly, resulting in a phosphor with larger particle size and superior luminescence characteristics. When the heat treatment temperature for obtaining the phosphor is approximately the same as the temperature at which the liquid phase of the compound used as the flux is formed, the flux promotes the reaction between the raw materials. Examples of the flux include boric acid, a borate containing at least one element selected from the group consisting of alkaline earth metal elements and alkali metal elements, and a halide containing at least one element selected from the group consisting of alkaline earth metal elements and alkali metal elements. Among halides, fluorides can be used as the flux. Examples of the flux that can be used include boric acid (H3BO3) and lithium fluoride (LiF).

[0075] The raw material mixture can be placed in a crucible or boat made of carbon such as graphite, boron nitride (BN), alumina (Al2O3), tungsten (W), molybdenum (Mo), or other materials, and heat-treated in a furnace.

[0076] The heat treatment of the raw material mixture is carried out in an oxygen-containing atmosphere. There are no particular restrictions on the oxygen content in the atmosphere. The oxygen content in the oxygen-containing atmosphere is preferably 5% by volume or more, more preferably 10% by volume or more, and even more preferably 15% by volume or more. The heat treatment is preferably carried out in an air atmosphere (oxygen content of 20% by volume or more). If the oxygen-free atmosphere has an oxygen content of less than 1% by volume, an oxide phosphor having the desired composition may not be obtained.

[0077] The temperature at which the raw material mixture is heat-treated is within the range of 800° C. to 1400° C., preferably within the range of 850° C. to 1300° C., more preferably within the range of 870° C. to 1290° C., and more preferably within the range of 900° C. to 1280° C. If the heat treatment temperature is 800° C. to 1400° C., thermal decomposition is suppressed, and a phosphor having the desired composition and a stable crystal structure is obtained.

[0078] In the heat treatment, a holding time may be set at a predetermined temperature. The holding time may be, for example, 0.5 to 48 hours, 1 to 40 hours, 2 to 30 hours, 3 to 20 hours, or 5 to 10 hours. By setting the holding time to 0.5 to 48 hours, crystal growth can be promoted.

[0079] The pressure of the heat treatment atmosphere may be standard atmospheric pressure (0.101 MPa, air atmosphere), 0.101 MPa or higher, or a pressurized atmosphere of 0.11 MPa to 200 MPa. The heat-treated product obtained by heat treatment is prone to decomposition of its crystalline structure when the heat treatment temperature is high, but decomposition of the crystalline structure can be suppressed when a pressurized atmosphere is used.

[0080] The heat treatment time can be appropriately selected depending on the heat treatment temperature and the pressure of the atmosphere during the heat treatment, and is preferably 0.5 to 20 hours. Even when two or more stages of heat treatment are performed, the heat treatment time for each stage is preferably 0.5 to 20 hours. If the heat treatment time is 0.5 to 20 hours, decomposition of the resulting heat-treated product is suppressed, and a phosphor with a stable crystal structure and desired emission intensity can be obtained. Furthermore, production costs can be reduced and the manufacturing time can be relatively shortened. The heat treatment time is more preferably 1 to 10 hours, and even more preferably 1.5 to 9 hours.

[0081] The heat-treated product obtained by the heat treatment may be subjected to post-treatments such as pulverization, dispersion, solid-liquid separation, drying, etc. Solid-liquid separation can be carried out by an industrially commonly used method such as filtration, suction filtration, pressure filtration, centrifugation, decantation, etc. Drying can be carried out by an industrially commonly used device such as a vacuum dryer, a hot air heating dryer, a conical dryer, a rotary evaporator, etc. [Example]

[0082] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0083] oxide phosphor Example 1 The raw materials used were 2.90 g of MgO as the first compound, 0.33 g of Li2CO3 as the third compound, 1.25 g of In2O3 as the fifth compound, 9.41 g of GeO2 as the seventh compound, and 0.18 g of Cr2O3 as the ninth compound. The molar ratio of each element in 1 mole of the resulting oxide phosphor was Mg 0.8 Li 0.1 In 0.1 Ge1O3:Cr 0.026The raw materials were mixed for 10 minutes using an agate mortar and agate pestle to obtain a raw material mixture. The obtained raw material mixture was placed in an alumina crucible and heat-treated for 8 hours in an air atmosphere (oxygen 20% by volume) at 1220°C and standard atmospheric pressure (0.101 MPa). After the heat treatment, the obtained heat-treated product was pulverized to obtain an oxide phosphor of Example 1 having the composition shown in Table 1, which is the molar ratio of the charged composition. In the composition of the oxide phosphor of Example 1 shown in Table 1, the variable p in the formula (1) is 0 (p=0), the variable q is 0.8 (q=0.8), the variable r is 0 (r=0), the variable s is 0.1 (s=0.1), the variable t is 0 (t=0), the variable u is 0.1 (u=0.1), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.026 (y=0.026), and the variable z is 0 (z=0). In the composition formula, there may be elements without numerical values, and the molar ratio of elements without numerical values ​​is 1.

[0084] Example 2 The raw materials used were 2.18g of MgO as the first compound, 0.66g of Li2CO3 as the third compound, 2.50g of In2O3 as the fifth compound, 9.41g of GeO2 as the seventh compound, and 0.18g of Cr2O3 as the ninth compound. Each element in 1 mole of the resulting oxide phosphor composition was measured so that the molar ratio of each element in the charged composition was Mg 0.6 Li 0.2 In 0.2 Ge1O3:Cr 0.026 The rest was measured out so that the molar ratio of the charged composition was 0. The oxide phosphor of Example 2 having the composition shown in Table 1, which is the molar ratio of the charged composition, was obtained in the same manner as in Example 1. In the composition of the oxide phosphor of Example 2 shown in Table 1, the variable p in the formula (1) is 0 (p=0), the variable q is 0.6 (q=0.6), the variable r is 0 (r=0), the variable s is 0.2 (s=0.2), the variable t is 0 (t=0), the variable u is 0.2 (u=0.2), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.026 (y=0.026), and the variable z is 0 (z=0).

[0085] Example 3 The raw materials used were 1.82g of MgO as the first compound, 0.83g of Li2CO3 as the third compound, 3.13g of In2O3 as the fifth compound, 9.41g of GeO2 as the seventh compound, and 0.18g of Cr2O3 as the ninth compound. The molar ratio of each element in 1 mole of the resulting oxide phosphor was Mg 0.5 Li 0.25 In 0.25 Ge1O3:Cr 0.026 The rest was measured out so that the molar ratio of the charged composition was 0. The oxide phosphor of Example 3 having the composition shown in Table 1, which is the molar ratio of the charged composition, was obtained in the same manner as in Example 1. In the composition of the oxide phosphor of Example 3 shown in Table 1, the variable p in the formula (1) is 0 (p=0), the variable q is 0.5 (q=0.5), the variable r is 0 (r=0), the variable s is 0.25 (s=0.25), the variable t is 0 (t=0), the variable u is 0.25 (u=0.25), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.026 (y=0.026), and the variable z is 0 (z=0).

[0086] Example 4 The raw materials used were 1.46 g of MgO as the first compound, 1.00 g of Li2CO3 as the third compound, 3.76 g of In2O3 as the fifth compound, 9.41 g of GeO2 as the seventh compound, and 0.18 g of Cr2O3 as the ninth compound. The molar ratio of each element in 1 mole of the resulting oxide phosphor was Mg 0.4 Li 0.3 In 0.3 Ge1O3:Cr 0.026The rest was measured out so that the molar ratio of the charged composition was 0. The oxide phosphor of Example 4 having the composition shown in Table 1 was obtained in the same manner as in Example 1. In the composition of the oxide phosphor of Example 4 shown in Table 1, the variable p in the formula (1) is 0 (p=0), the variable q is 0.4 (q=0.4), the variable r is 0 (r=0), the variable s is 0.3 (s=0.3), the variable t is 0 (t=0), the variable u is 0.3 (u=0.3), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.026 (y=0.026), and the variable z is 0 (z=0).

[0087] Example 5 The raw materials used were 0.73 g of MgO as the first compound, 1.33 g of Li2CO3 as the third compound, 5.01 g of In2O3 as the fifth compound, 9.41 g of GeO2 as the seventh compound, and 0.18 g of Cr2O3 as the ninth compound. Each element in 1 mole of the resulting oxide phosphor composition was measured so that the molar ratio of each element in the charged composition was Mg 0.2 Li 0.4 In 0.4 Ge1O3:Cr 0.026 The rest was measured out so that the molar ratio of the charged composition was 0. The oxide phosphor of Example 5 having the composition shown in Table 1, which is the molar ratio of the charged composition, was obtained in the same manner as in Example 1. In the composition of the oxide phosphor of Example 5 shown in Table 1, the variable p in the formula (1) is 0 (p=0), the variable q is 0.2 (q=0.2), the variable r is 0 (r=0), the variable s is 0.4 (s=0.4), the variable t is 0 (t=0), the variable u is 0.4 (u=0.4), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.026 (y=0.026), and the variable z is 0 (z=0).

[0088] Example 6 The raw materials used were 0.36 g of MgO as the first compound, 1.50 g of Li2CO3 as the third compound, 5.63 g of In2O3 as the fifth compound, 9.41 g of GeO2 as the seventh compound, and 0.18 g of Cr2O3 as the ninth compound. Each element in 1 mole of the resulting oxide phosphor composition was measured so that the molar ratio of each element in the charged composition was Mg 0.1 Li 0.45 In 0.45 Ge1O3:Cr 0.026 The rest was measured out so that the molar ratio of the charged composition was 0. The oxide phosphor of Example 6 having the composition shown in Table 1, which is the molar ratio of the charged composition, was obtained in the same manner as in Example 1. In the composition of the oxide phosphor of Example 6 shown in Table 1, the variable p in the formula (1) is 0 (p=0), the variable q is 0.1 (q=0.1), the variable r is 0 (r=0), the variable s is 0.45 (s=0.45), the variable t is 0 (t=0), the variable u is 0.45 (u=0.45), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.026 (y=0.026), and the variable z is 0 (z=0).

[0089] Example 7 The raw materials used were 1.82 g of MgO (the first compound), 0.83 g of Li2CO3 (the third compound), 3.13 g of In2O3 (the fifth compound), 9.41 g of GeO2 (the seventh compound), and 0.30 g of Cr2O3 (the ninth compound). The molar ratio of each element in 1 mole of the resulting oxide phosphor was Mg 0.5 Li 0.25 In 0.25 Ge1O3:Cr 0.044The rest was measured out so that the molar ratio of the charged composition was 0. The oxide phosphor of Example 7 having the composition shown in Table 1, which is the molar ratio of the charged composition, was obtained in the same manner as in Example 1. In the composition of the oxide phosphor of Example 7 shown in Table 1, the variable p in the formula (1) is 0 (p=0), the variable q is 0.5 (q=0.5), the variable r is 0 (r=0), the variable s is 0.25 (s=0.25), the variable t is 0 (t=0), the variable u is 0.25 (u=0.25), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.044 (y=0.044), and the variable z is 0 (z=0).

[0090] Example 8 The raw materials used were 2.18 g of MgO as the first compound, 0.66 g of Li2CO3 as the third compound, 2.50 g of In2O3 as the fifth compound, 9.41 g of GeO2 as the seventh compound, and 0.36 g of Cr2O3 as the ninth compound. The molar ratio of each element in 1 mole of the resulting oxide phosphor was Mg 0.6 Li 0.2 In 0.2 Ge1O3:Cr 0.052 The rest was measured out so that the molar ratio of the charged composition was 0. The oxide phosphor of Example 8 having the composition shown in Table 1 was obtained in the same manner as in Example 1. In the composition of the oxide phosphor of Example 8 shown in Table 1, the variable p in the formula (1) is 0 (p=0), the variable q is 0.6 (q=0.6), the variable r is 0 (r=0), the variable s is 0.2 (s=0.2), the variable t is 0 (t=0), the variable u is 0.2 (u=0.2), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.052 (y=0.052), and the variable z is 0 (z=0).

[0091] Example 9 The raw materials used were 2.18 g of MgO (first compound), 0.66 g of Li2CO3 (third compound), 2.50 g of In2O3 (fifth compound), 9.41 g of GeO2 (seventh compound), and 0.45 g of Cr2O3 (ninth compound). The molar ratio of each element in 1 mole of the resulting oxide phosphor was Mg 0.6 Li 0.2 In 0.2 Ge1O3:Cr 0.065 The rest was measured out so that the molar ratio of the charged composition was 0. The oxide phosphor of Example 9 having the composition shown in Table 1 was obtained in the same manner as in Example 1. In the composition of the oxide phosphor of Example 9 shown in Table 1, the variable p in the formula (1) is 0 (p=0), the variable q is 0.6 (q=0.6), the variable r is 0 (r=0), the variable s is 0.2 (s=0.2), the variable t is 0 (t=0), the variable u is 0.2 (u=0.2), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.065 (y=0.065), and the variable z is 0 (z=0).

[0092] Example 10 As a raw material, the first element M 1 The raw materials were weighed so that the second compound containing Zn, ZnO, was 3.66 g, the third compound, Li2CO3, was 0.83 g, the fifth compound, In2O3, was 3.13 g, the seventh compound, GeO2, was 9.41 g, and the ninth compound, Cr2O3, was 0.18 g. The molar ratio of each element in 1 mole of the resulting oxide phosphor was 1.06 g. 0.5 Li 0.25 In 0.25 Ge1O3:Cr 0.026 The oxide phosphor of Example 10 having the composition shown in Table 1, which is the molar ratio of the charged composition, was obtained in the same manner as in Example 1, except that the heat treatment temperature was set to 1100°C. In the composition of the oxide phosphor of Example 10 shown in Table 1, the element M in the formula (1) 1is Zn, the variable p is 1 (p=1), the variable q is 0.5 (q=0.5), the variable r is 0 (r=0), the variable s is 0.25 (s=0.25), the variable t is 0 (t=0), the variable u is 0.25 (u=0.25), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.026 (y=0.026), and the variable z is 0 (z=0).

[0093] Example 11 As raw materials, 1.82 g of the first compound MgO and 1.82 g of the second element M 2 The raw materials used were 1.19 g of Na2CO3, the fourth compound containing Na, 3.13 g of In2O3, the fifth compound, 9.41 g of GeO2, the seventh compound, and 0.18 g of Cr2O3, the ninth compound. The molar ratio of each element in 1 mole of the resulting oxide phosphor was Mg 0.5 Na 0.25 In 0.25 Ge1O3:Cr 0.026 The other components were weighed out so that the molar ratio of the charged composition was the same as in Example 1, and an oxide phosphor of Example 11 having the composition shown in Table 1 was obtained. In the composition of the oxide phosphor of Example 11 shown in Table 1, the element M in the formula (1) 2 is Na, the variable p is 0 (p=0), the variable q is 0.5 (q=0.5), the variable r is 1.0 (r=1.0), the variable s is 0.25 (s=0.25), the variable t is 0 (t=0), the variable u is 0.25 (u=0.25), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.026 (y=0.026), and the variable z is 0 (z=0).

[0094] Example 12 The raw materials were 1.82 g of MgO as the first compound, 0.83 g of Li2CO3 as the third compound, 3.13 g of In2O3 as the fifth compound, and 4th element M 4The raw materials were weighed so that the eighth compound SiO2 containing Mg was 5.41 g and the ninth compound Cr2O3 was 0.18 g. The molar ratio of each element in 1 mole of the resulting oxide phosphor was Mg 0.5 Li 0.25 In 0.25 SiO:Cr 0.026 The oxide phosphor of Example 12 having the composition shown in Table 1, which is the molar ratio of the charged composition, was obtained in the same manner as in Example 1, except that the heat treatment temperature was set to 1270°C. In the composition of the oxide phosphor of Example 12 shown in Table 1, the element M in the formula (1) 4 is Si, the variable p is 0 (p=0), the variable q is 0.5 (q=0.5), the variable r is 0 (r=0), the variable s is 0.25 (s=0.25), the variable t is 0 (t=0), the variable u is 0.25 (u=0.25), the variable v is 1.0 (v=1.0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.026 (y=0.026), and the variable z is 0 (z=0).

[0095] Example 13 The raw materials were 1.82 g of MgO as the first compound, 0.83 g of Li2CO3 as the third compound, 3.13 g of In2O3 as the fifth compound, 7.06 g of GeO2 as the seventh compound, and 4th element M 4 The raw materials were weighed so that the eighth compound containing Si, SiO2, was 1.36 g and the ninth compound, Cr2O3, was 0.18 g. The molar ratio of each element in 1 mole of the resulting oxide phosphor was Mg 0.5 Li 0.25 In 0.25 Ge 0.75 Si 0.25 O3:Cr 0.026 The other components were weighed out so that the molar ratio of the charged composition was the same as in Example 1, and an oxide phosphor of Example 13 having the composition shown in Table 1 was obtained. In the composition of the oxide phosphor of Example 13 shown in Table 1, the element M in the formula (1) 4is Si, the variable p is 0 (p=0), the variable q is 0.5 (q=0.5), the variable r is 0 (r=0), the variable s is 0.25 (s=0.25), the variable t is 0 (t=0), the variable u is 0.25 (u=0.25), the variable v is 0.25 (v=0.25), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.026 (y=0.026), and the variable z is 0 (z=0).

[0096] Example 14 As raw materials, 1.27 g of the first compound MgO and 1.27 g of the first element M 1 The raw materials used were 1.10 g of ZnO, the second compound containing Zn, 0.83 g of Li2CO3, the third compound, 3.13 g of In2O3, the fifth compound, 9.41 g of GeO2, the seventh compound, and 0.18 g of Cr2O3, the ninth compound. The molar ratio of each element in 1 mole of the resulting oxide phosphor was Mg 0.35 Zn 0.15 Li 0.25 In 0.25 Ge1O3:Cr 0.026 The oxide phosphor of Example 14 having the composition shown in Table 1, which is the molar ratio of the charged composition, was obtained in the same manner as in Example 1, except that the heat treatment temperature was set to 1200°C. In the composition of the oxide phosphor of Example 14 shown in Table 1, the element M in the formula (1) 1 is Zn, the variable p is 0.3 (p=0.3), the variable q is 0.5 (q=0.5), the variable r is 0 (r=0), the variable s is 0.25 (s=0.25), the variable t is 0 (t=0), the variable u is 0.25 (u=0.25), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.026 (y=0.026), and the variable z is 0 (z=0).

[0097] Example 15 As raw materials, 1.27 g of the first compound MgO and 1.27 g of the first element M 1The raw materials used were 1.35g of CaCO3, the second compound containing Ca, 0.83g of Li2CO3, the third compound, 3.13g of In2O3, the fifth compound, 9.41g of GeO2, the seventh compound, and 0.18g of Cr2O3, the ninth compound. The molar ratio of each element in 1 mole of the resulting oxide phosphor was Mg 0.35 Ca 0.15 Li 0.25 In 0.25 Ge1O3:Cr 0.026 The oxide phosphor of Example 15 having the composition shown in Table 1, which is the molar ratio of the charged composition, was obtained in the same manner as in Example 1, except that the heat treatment temperature was set to 1200°C. In the composition of the oxide phosphor of Example 15 shown in Table 1, the element M in the formula (1) 1 is Ca, the variable p is 0.3 (p=0.3), the variable q is 0.5 (q=0.5), the variable r is 0 (r=0), the variable s is 0.25 (s=0.25), the variable t is 0 (t=0), the variable u is 0.25 (u=0.25), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 3.0 (x=3.0), the variable y is 0.026 (y=0.026), and the variable z is 0 (z=0).

[0098] Example 16 As raw materials, 1.27 g of the first compound MgO and 1.27 g of the first element M 1 The raw materials used were 1.99g of SrCO3, the second compound containing Sr, 0.83g of Li2CO3, the third compound, 3.13g of In2O3, the fifth compound, 9.41g of GeO2, the seventh compound, and 0.18g of Cr2O3, the ninth compound. The molar ratio of each element in 1 mole of the resulting oxide phosphor was Mg 0.35 Sr 0.15 Li 0.25 In 0.25 Ge1O3:Cr 0.026The other components were weighed out so that the molar ratio of the charged composition was the same as in Example 1, and an oxide phosphor of Example 16 having the composition shown in Table 1 was obtained. In the composition of the oxide phosphor of Example 16 shown in Table 1, the element M in the formula (1) 1 is Sr, variable p is 0.3 (p=0.3), variable q is 0.5 (q=0.5), variable r is 0 (r=0), variable s is 0.25 (s=0.25), variable t is 0 (t=0), variable u is 0.25 (u=0.25), variable v is 0 (v=0), variable w is 1.0 (w=1.0), variable x is 3.0 (x=3.0), variable y is 0.026 (y=0.026), and variable z is 0 (z=0).

[0099] Comparative Example 1 The raw materials used were 3.63 g of MgO as the first compound, 9.41 g of GeO2 as the seventh compound, and 0.18 g of Cr2O3 as the ninth compound. The molar ratio of each element in 1 mole of the resulting oxide phosphor was Mg1Ge1O3:Cr 0.026 The other components were weighed out so that the amount of the oxide phosphor of Comparative Example 1 was the same as that of Example 1, and the oxide phosphor of Comparative Example 1 had the composition shown in Table 1, which was the molar ratio of the charged composition. The oxide phosphor of Comparative Example 1 contained Li and / or the second element M in 1 mole of the composition. 2 , does not contain In, and does not have the composition represented by the formula (1).

[0100] Measurement of emission spectrum and emission characteristics The emission spectrum of each oxide phosphor in the Examples and Comparative Examples was measured using a quantum efficiency measurement system (QE-2000, manufactured by Otsuka Electronics Co., Ltd.). The emission peak wavelength of the excitation light from the semiconductor light-emitting element used in the quantum efficiency measurement system was 450 nm. From the obtained emission spectrum of each phosphor, the relative emission intensity, emission peak wavelength, and full width at half maximum were determined as emission characteristics. That is, the emission peak wavelength (nm) and the full width at half maximum (FWHM) (nm) of the emission spectrum at the emission peak wavelength of each phosphor were determined. Furthermore, for the emission spectrum of each oxide phosphor, the emission intensity at 1000 nm was calculated relative to the emission intensity at the emission peak wavelength (100%). The emission intensity of the oxide phosphor in Example 1 was set to 100%, and the relative emission intensity (%) of each oxide phosphor in Examples other than Example 1 and Comparative Examples was calculated. The results are shown in Table 1. Figures 4 to 6 show the emission spectra of the oxide phosphors in Examples 1 to 16, and Figure 7 shows the emission spectra of the oxide phosphors in Comparative Examples 1 and 2.

[0101] [Table 1]

[0102] As shown in Table 1 or FIGS. 4 to 6, the oxide phosphors according to Examples 1 to 16 have emission peak wavelengths in the range of 830 nm or more and 930 nm or less in their emission spectra, and can emit light required for analysis in the wavelength range from red light to near-infrared light, more specifically in the wavelength range of near-infrared light.

[0103] The oxide phosphors according to Examples 1 to 9 contain Mg, Li, In, Ge, and Cr in 1 mole of the oxide phosphor composition, and the first element M 1 , second element M 2 , third element M 3 , the fourth element M 4 and the fifth element M 5In the oxide phosphors according to Examples 1 to 9, the variable y representing the molar ratio of Cr, which is an activator element in the formula (1), is in the range of 0.020 to 0.070 (0.020≦y≦0.070) per mole of composition, and in the emission spectrum, the emission peak wavelength is on the longer wavelength side in the range of 880 nm to 930 nm in the wavelength range of near-infrared light, and the full width at half maximum is widened to 160 nm to 220 nm. In the oxide phosphors according to Examples 3 to 5 and 7, the variable y representing the molar ratio of Cr, which is an activator element in the formula (1), is in the range of 0.020 to 0.070 (0.020≦y≦0.070) per mole of composition, and in the emission spectrum, the emission peak wavelength is on the longer wavelength side in the range of 880 nm to 930 nm in the wavelength range of near-infrared light, and the full width at half maximum is widened to 160 nm to 220 nm. 3 The variable u (third element M 3 Since it does not contain In and the second element M 3 The molar ratio of the total of In and In (variable u representing the molar ratio of In) is within the range of 0.25 to 0.40 (0.25≦u≦0.40), the full width at half maximum of the emission spectrum is relatively broad, within the range of 180 nm to 220 nm, and the emission intensity at 1000 nm is 45% or more of the 100% emission intensity at the emission peak wavelength, and light having the emission intensity required for analysis can be emitted in the near-infrared wavelength range.

[0104] In the oxide phosphor according to Example 10, in 1 mol of the composition of the oxide phosphor, all of Mg is the first element M 1 In the near-infrared wavelength range, the emission peak wavelength is in the long wavelength range of 880 nm to 930 nm, and the full width at half maximum is wide, from 160 nm to 220 nm.

[0105] In the oxide phosphor according to Example 11, all of Li is converted into the second element M in 1 mole of the oxide phosphor. 2 In the near-infrared wavelength range, the emission peak wavelength is in the longer wavelength range of 920 nm to 930 nm, the full width at half maximum is wider, from 200 nm to 220 nm, and the emission intensity at 1000 nm is 65% or more of the 100% emission intensity at the emission peak wavelength.

[0106] The oxide phosphors according to Examples 12 and 13 are composed of oxide phosphors in which all or part of Ge is a fourth element M 4 In the near-infrared wavelength range, the emission peak wavelength is in the longer wavelength range of 850 nm to 930 nm, the full width at half maximum is wider, from 180 nm to 220 nm, and the emission intensity at 1000 nm is 25% or more of the 100% emission intensity at the emission peak wavelength.

[0107] In the oxide phosphors according to Examples 14 to 16, a part of Mg is converted into the first element M in 1 mole of the oxide phosphor. 1 is replaced by at least one selected from the group consisting of Zn, Ca and Sr, and the variable p in formula (1) is within the range of 0 or more and 0.4 or less (0≦p≦0.4), and the variable q is within the range of 0.6 or more and 0.9 or less (0.6≦q≦0.9). In the oxide phosphors according to Examples 14 to 16, in the wavelength range of near-infrared light, the emission peak wavelength is on the longer wavelength side, within the range of 880 nm or more and 930 nm or less, the full width at half maximum is widened to 160 nm or more and 220 nm or less, and the emission intensity at 1000 nm is 30% or more of the emission intensity at the emission peak wavelength of 100%.

[0108] The oxide phosphor according to Comparative Example 1 contains Li and / or a second element M in 1 mole of the oxide phosphor. 2 It does not contain In and does not have the composition represented by the formula (1). The oxide phosphor of Comparative Example 1 had a low relative luminous intensity of 15%.

[0109] Embodiments according to the present disclosure include the following oxide phosphors and light-emitting devices using the same. Embodiments according to the present disclosure preferably include a method for producing the oxide phosphors.

[0110] [Section 1] An oxide phosphor having a composition represented by the following formula (1): (Mg 1-p M 1 p ) q (Li 1-r M2 r ) s (In 1-t M 3 t ) u (Ge 1-v M 4 v ) w O x :Cr y ,M 5 z (1) (In the above formula (1), M 1 is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, and M 2 is at least one element selected from the group consisting of Na, K, Rb and Cs, and M 3 is at least one element selected from the group consisting of Al, Ga, and Sc, and M 4 is at least one element selected from the group consisting of Si, Ti, Zr, Sn and Hf, and M 5 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and p, q, r, s, t, u, v, w, x, y, and z satisfy the following conditions: 0≦p≦1.0, 0.1≦q≦0.9, 0≦r≦1.0, 0.05≦s≦0.45, 0≦t≦0.5, 0.05≦u≦0.45, 0≦v≦1.0, 0.8≦w≦1.3, 2.6≦x≦3.6, 0.002≦y≦0.5, 0≦z≦0.3, 0.9≦q+s+u≦1.2, respectively. [Section 2] Item 2. The oxide phosphor according to item 1, wherein in formula (1), y satisfies 0.020≦y≦0.070. [Section 3] Item 3. The oxide phosphor according to item 1 or 2, wherein in formula (1), u satisfies 0.25≦u≦0.40. [Section 4] 4. The oxide phosphor according to any one of items 1 to 3, wherein in formula (1), p satisfies 0≦p<1.0. [Section 5] 5. The oxide phosphor according to any one of items 1 to 4, wherein in formula (1), v satisfies 0≦v<0.5. [Section 6] Item 5. The oxide phosphor according to item 4, wherein v=0 in formula (1). [Section 7] Item 7. The oxide phosphor according to item 6, wherein r=0 in formula (1). [Section 8] 4. The oxide phosphor according to any one of items 1 to 3, wherein in formula (1), p and q satisfy 0≦p≦0.4 and 0.6≦q≦0.9, respectively. [Section 9] 4. The oxide phosphor according to claim 1, wherein in said formula (1), q satisfies 0.5≦q≦0.9. [Section 10] Item 10. The oxide phosphor according to any one of items 1 to 9, wherein the full width at half maximum of an emission spectrum having an emission peak wavelength is in the range of 150 nm to 220 nm. [Section 11] Item 8. The oxide phosphor according to Item 6 or 7, wherein the full width at half maximum of an emission spectrum having an emission peak wavelength is in the range of 175 nm to 220 nm. [Section 12] Item 12. The oxide phosphor according to any one of items 1 to 11, wherein the oxide phosphor has an emission spectrum with a peak wavelength in the range of 830 nm to 930 nm. [Section 13] Item 8. The oxide phosphor according to Item 6 or 7, wherein the oxide phosphor has an emission spectrum with an emission peak wavelength in the range of 870 nm to 930 nm. [Section 14] Item 9. The oxide phosphor according to item 8, wherein the oxide phosphor has an emission spectrum with an emission peak wavelength in the range of 860 nm to 930 nm. [Section 15] Item 10. The oxide phosphor according to item 9, wherein the oxide phosphor has an emission spectrum with a peak wavelength in the range of 860 nm to 930 nm. [Section 16] Item 6. The oxide phosphor according to any one of Items 2 to 5, wherein in the emission spectrum, the emission intensity at 1000 nm is 37% or more relative to 100% emission intensity at the emission peak wavelength. [Section 17] Item 17. The oxide phosphor according to any one of items 1 to 16, a light-emitting element having an emission peak wavelength in the range of 365 nm to 650 nm, which irradiates the oxide phosphor; [Section 18] A first compound containing Mg and / or a first element M 1 a second compound containing Li and / or a third compound containing Li and / or a second element M 2 a fourth compound containing In, a fifth compound containing In, a seventh compound containing Ge and / or a fourth element M 4 and a ninth compound containing Cr, and optionally a third element M 3 and optionally a fifth element M 5 and a tenth compound comprising: Mg and / or the first element M in 1 mole of the oxide phosphor composition 1 When the total molar ratio of the first element M is taken as the variable q, 1 The molar ratio of Mg is the product of the variable p and the variable q, where the variable p is a number between 0 and 1.0, and the variable q is a number between 0.1 and 0.9, and the molar ratio of Mg is the product of the number obtained by subtracting the variable p from 1 and the variable q, and Li and / or the second element M 2 When the total molar ratio of the second element M is set as the variable s, 2 The molar ratio of Li is the product of the variable r and the variable s, where the variable r is a value between 0 and 1.0, and the variable s is a value between 0.05 and 0.45, and the molar ratio of Li is the product of the value obtained by subtracting the variable r from 1 and the variable s, and the molar ratio of In and the third element M 3 When the total molar ratio of the third element M is set as the variable u, 3 The molar ratio of In is the product of the variable t and the variable u, where the variable t is a value of 0 or more and 0.5 or less, and the variable u is a value of 0.05 or more and 0.45 or less, and the molar ratio of In is the product of the value obtained by subtracting the variable t from 1 and the variable u, and Ge and / or a fourth element M 4 When the total molar ratio of the fourth element M is set as the variable w, 4the molar ratio of Ge is the product of the variable v and the variable w, where the variable v is a number between 0 and 1.0, and the variable w is a number between 0.8 and 1.3, the molar ratio of Ge is the product of the number obtained by subtracting the variable v from 1 and the variable w, the molar ratio of the sum of the variables q, s, and u is a number between 0.9 and 1.2, the molar ratio of Cr is the variable y, where the variable y is a number between 0.002 and 0.5, 5 preparing a raw material mixture by adjusting and mixing the first compound and / or the second compound, the third compound and / or the fourth compound, the fifth compound, the seventh compound and / or the eighth compound, the ninth compound, and optionally the sixth compound and optionally the tenth compound so that the molar ratio of the first compound and / or the second compound, the third compound and / or the fourth compound, the fifth compound, the seventh compound and / or the eighth compound, the ninth compound, and optionally the sixth compound and the tenth compound is a value of 0 or more and 0.3 or less; and heat-treating the raw material mixture in an oxygen-containing atmosphere at a temperature in the range of 800°C to 1400°C to obtain an oxide phosphor. [Section 19] Item 19. The method for producing an oxide phosphor according to item 18, wherein the raw material mixture is prepared by adjusting and mixing each raw material so as to have a composition represented by the following formula (1): (Mg 1-p M 1 p ) q (Li 1-r M 2 r ) s (In 1-t M 3 t ) u (Ge 1-v M 4 v ) w O x :Cr y ,M 5 z (1) (In the above formula (1), M 1 is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, and M 2 is at least one element selected from the group consisting of Na, K, Rb and Cs, and M 3 is at least one element selected from the group consisting of Al, Ga, and Sc, and M4 is at least one element selected from the group consisting of Si, Ti, Zr, Sn and Hf, and M 5 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and p, q, r, s, t, u, v, w, x, y, and z satisfy the following conditions: 0≦p≦1.0, 0.1≦q≦0.9, 0≦r≦1.0, 0.05≦s≦0.45, 0≦t≦0.5, 0.05≦u≦0.45, 0≦v≦1.0, 0.8≦w≦1.3, 2.6≦x≦3.6, 0.002≦y≦0.5, 0≦z≦0.3, 0.9≦q+s+u≦1.2, respectively. [Industrial Applicability]

[0111] The oxide phosphor according to the present disclosure can also be used in medical light-emitting devices for obtaining information from within a living body, light-emitting devices that are mounted on small mobile devices such as smartphones and smartwatches to manage health conditions, light-emitting devices used in medical devices, light-emitting devices for analytical devices that non-destructively measure internal information about agricultural products such as fruits and vegetables and rice, foods, and pharmaceuticals, light-emitting devices for plant cultivation that affect the photoreceptors of plants, and light-emitting devices for reflectance spectroscopy measurement devices used to measure film thickness, etc. [Explanation of symbols]

[0112] 10: light-emitting element, 11: semiconductor element, 20: first lead, 30: second lead, 40: molded body, 42: resin part, 50, 51: wavelength conversion member, 52: wavelength conversion member, 53: light-transmitting body, 60: wire, 61: conductive member, 70: phosphor, 71: first phosphor, 72: second phosphor, 73: third phosphor, 74: fourth phosphor, 75: fifth phosphor, 80: adhesive layer, 90: covering member, 100, 200: light-emitting device.

Claims

1. An oxide phosphor having a composition represented by the following formula (1): (Mg １－ｐ M １ ｐ ) ｑ (Li １－ｒ M ２ ｒ ) ｓ (In １－ｔ M ３ ｔ ) ｕ (Ge １－ｖ M ４ ｖ ) ｗ O ｘ :Cr ｙ ,M ５ ｚ (1) (In the above formula (1), M １ is at least one element selected from the group consisting of Ca, Sr, Ba and Zn, M ２ is at least one element selected from the group consisting of Na, K, Rb and Cs, M ３ is at least one element selected from the group consisting of Al, Ga, and Sc, and M ４ is at least one element selected from the group consisting of Si, Ti, Zr, Sn and Hf, M ５ is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and p, q, r, s, t, u, v, w, x, y, and z each satisfy 0≦p≦1.0, 0.1≦q≦0.9, 0≦r≦1.0, 0.05≦s≦0.45, 0≦t≦0.5, 0.05≦u≦0.45, 0≦v≦1.0, 0.8≦w≦1.3, 2.6≦x≦3.6, 0.002≦y≦0.5, 0≦z≦0.3, and 0.9≦q+s+u≦1.

2.

2. The oxide phosphor according to claim 1 , wherein in the formula (1), y satisfies 0.020≦y≦0.

070.

3. The oxide phosphor according to claim 1 , wherein in the formula (1), u satisfies 0.25≦u≦0.

40.

4. The oxide phosphor according to claim 1 , wherein in the formula (1), p satisfies 0≦p<1.

0.

5. The oxide phosphor according to claim 1 , wherein in the formula (1), v satisfies 0≦v<0.

5.

6. The oxide phosphor according to claim 4 , wherein v=0 in formula (1).

7. The oxide phosphor according to claim 6 , wherein in formula (1), r=0.

8. 2. The oxide phosphor according to claim 1, wherein in said formula (1), p and q satisfy 0≦p≦0.4 and 0.6≦q≦0.9, respectively.

9. The oxide phosphor according to claim 1 , wherein in the formula (1), q satisfies 0.5≦q≦0.

9.

10. 2. The oxide phosphor according to claim 1, wherein the full width at half maximum of an emission spectrum having an emission peak wavelength is within a range of 150 nm to 220 nm.

11. The oxide phosphor according to claim 6 , wherein the full width at half maximum of an emission spectrum having an emission peak wavelength is within a range of 175 nm to 220 nm.

12. The oxide phosphor according to claim 1 , wherein the oxide phosphor has an emission peak wavelength in the range of 830 nm to 930 nm in an emission spectrum.

13. The oxide phosphor according to claim 6 , wherein the oxide phosphor has an emission peak wavelength in the range of 870 nm to 930 nm in an emission spectrum.

14. The oxide phosphor according to claim 8 , wherein the oxide phosphor has an emission peak wavelength in the range of 860 nm to 930 nm in an emission spectrum.

15. The oxide phosphor according to claim 9 , wherein the oxide phosphor has an emission peak wavelength in the range of 860 nm to 930 nm in an emission spectrum.

16. 3. The oxide phosphor according to claim 2, wherein in an emission spectrum, an emission intensity at 1000 nm is 37% or more relative to an emission intensity of 100% at an emission peak wavelength.

17. The oxide phosphor according to any one of claims 1 to 16, A light emitting device comprising: a light emitting element having an emission peak wavelength in the range of 365 nm to 650 nm, which irradiates the oxide phosphor.

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