Oxide phosphor and light-emitting device

Abstract

An oxide phosphor and a light emitting device are provided. The present invention provides an oxide phosphor having a composition represented by the following formula (1): (Li 1-s M 1 s )(Mg 1-t M 2 t ) u (Ga 1-v M 3 v ) w O x :Cr y ,M 4 z (1) (In formula (1), M 1 is at least one selected from the group consisting of Na, K, Rb and Cs, M 2 is at least one selected from the group consisting of Ca, Sr, Ba and Zn, M 3 is at least one selected from the group consisting of Al and Sc, M 4 is at least one selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, 0≦s≦0.5, 0≦t≦1.0, 0.03≦u≦10, 0≦v≦1.0, 5.1≦w≦25, 0.005≦u / w≦0.4, 8.2≦x≦48, when Li is 1, or Li and M 1 When the sum of these is 1, the following conditions are satisfied: 0.02≦y≦0.5, 0≦z≦0.3, y>z.)

Description

[Technical Field]

[0001] The present disclosure relates to oxide phosphors and light-emitting devices. [Background technology]

[0002] Light-emitting devices having an emission intensity in the wavelength range from red light to near-infrared light are desirable for use as light sources for plant growth and cultivation, for example. In addition to the uses mentioned above, light-emitting devices having an emission intensity in the wavelength range from red light to near-infrared light are desirable for use in infrared cameras, infrared communications, vein authentication, which is a type of biometric authentication, food component analysis equipment that non-destructively measures the sugar content of foods such as fruits and vegetables, etc. Light-emitting devices that emit light in the wavelength range from red light to near-infrared light as well as in the wavelength range of visible light are also desirable. Such light emitting devices include light emitting devices that combine a light emitting diode (LED) and a phosphor.

[0003] Patent Document 1 describes a phosphor that can be used in the above-mentioned light-emitting device, which has an emission peak wavelength in the wavelength range of 680 nm to 760 nm and has a composition of CaYAlO4:Mn 4+ As a phosphor suitable for each of the above-mentioned applications, for example, a phosphor that emits red to near-infrared light and emits light with higher luminous intensity may be required. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2020-528486 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present disclosure is to provide an oxide phosphor and a light emitting device that emit light having an emission peak wavelength in the wavelength range from red light to near-infrared light when irradiated with excitation light. [Means for solving the problem]

[0006] The first aspect is an oxide phosphor having a composition represented by the following formula (1). (Li 1-s M 1 s )(Mg 1-t M 2 t ) u (Ga 1-v M 3 v ) w O x :Cr y ,M 4 z (1) (In the above formula (1), M 1 is at least one element selected from the group consisting of Na, K, Rb and Cs, and M 2 is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, and M 3 is at least one element selected from the group consisting of Al and Sc, and M 4 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb; s, t, u, v, w, and x are, respectively, 0≦s≦0.5, 0≦t≦1.0, 0.03≦u≦10, 0≦v≦1.0, 5.1≦w≦25, 0.005≦u / w≦0.4, and 8.2≦x≦48; y and z are, respectively, when Li is taken as 1 or when Li and M are taken as 1 When the sum of the above is 1, the above Li or the above Li and the above M 1 The sum of the above satisfies 0.02≦y≦0.5, 0≦z≦0.3, and y>z.)

[0007] 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, which irradiates the oxide phosphor. [Effects of the Invention]

[0008] According to one aspect of the present disclosure, it is possible to provide an oxide phosphor and a light emitting device that emit light having an emission peak wavelength in the wavelength range from red light of 700 nm to 1500 nm inclusive, inclusive, to near-infrared light, when irradiated with excitation light. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of a first configuration example of a light emitting device. [Figure 2] FIG. 2 is a schematic cross-sectional view showing another example of the first configuration example of the light emitting device. [Figure 3] FIG. 3 is a schematic plan view showing a second configuration example of the light emitting device. [Figure 4] FIG. 4 is a schematic cross-sectional view showing a second configuration example of the light emitting device. [Figure 5] FIG. 5 is a diagram showing the emission spectra of the oxide phosphors according to Examples 1 and 2 and the emission spectra of the oxide phosphors according to Comparative Examples 1 and 2. As shown in FIG. [Figure 6] FIG. 6 is a diagram showing the emission spectra of the oxide phosphors according to Examples 3 and 4. [Figure 7] FIG. 7 is a diagram showing the emission spectra of the oxide phosphors according to Examples 5 and 6. [Figure 8] FIG. 8 is a diagram showing the emission spectra of the oxide phosphors according to Examples 7 and 8. [Figure 9] FIG. 9 is a diagram showing the emission spectrum of the oxide phosphor according to Example 9. [Figure 10] FIG. 10 is a diagram showing the emission spectra of the oxide phosphors according to Examples 10 and 11. [Figure 11] FIG. 11 is a diagram showing the emission spectra of the oxide phosphors according to Examples 12 and 13. [Figure 12] FIG. 12 is a diagram showing the emission spectra of the oxide phosphors according to Examples 14 and 15. [Figure 13] FIG. 13 is a diagram showing the emission spectra of the oxide phosphors according to Examples 16 to 18. [Figure 14]FIG. 14 is a diagram showing the emission spectra of the oxide phosphors according to Examples 19 and 20. [Figure 15] FIG. 15 is a diagram showing the emission spectra of the oxide phosphors according to Examples 21 to 23 and the emission spectra of the oxide phosphors according to Comparative Examples 1 and 3. As shown in FIG. [Figure 16] FIG. 16 is a diagram showing the emission spectra of the oxide phosphors according to Examples 24 to 26. [Figure 17] FIG. 17 is a diagram showing the emission spectra of the oxide phosphors according to Examples 27 to 29. [Figure 18] FIG. 18 is a diagram showing the emission spectra of the oxide phosphors according to Examples 30 to 32. [Figure 19] FIG. 19 is a diagram showing the emission spectrum of the oxide phosphor according to Example 33. [Figure 20] FIG. 20 is a diagram showing the emission spectra of the oxide phosphors according to Examples 34 and 35. [Figure 21] FIG. 21 is a diagram showing the emission spectra of the oxide phosphors according to Examples 36 and 37. DETAILED DESCRIPTION OF THE INVENTION

[0010] The oxide phosphor and light-emitting device according to the present disclosure will be described below. However, the embodiments shown below are merely examples for embodying the technical concept of the present invention, and the present invention is not limited to the oxide phosphor, light-emitting device, and method for manufacturing the oxide phosphor described below. Note that, for visible light, the relationship between color names and chromaticity coordinates, the relationship between light wavelength ranges and color names of monochromatic light, etc., conforms to JIS Z8110.

[0011] 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 a phosphor that emits light having a peak emission wavelength in the range of 680 nm to 1500 nm, preferably in the range of 700 nm to 1500 nm, or a phosphor that emits light having a peak emission wavelength in the range of 700 nm to 1400 nm, when excited by light from a light-emitting element that irradiates light having a peak emission wavelength in the range of 365 nm to 650 nm.Recently, there has been a demand for light-emitting devices that emit light in the wavelength range from red light to near-infrared light, which is highly safe and can more clearly visualize deep areas inside a living body.Furthermore, in a light-emitting device including a light-emitting element and a phosphor, if the device is equipped with a phosphor with high luminescence intensity that can emit high-power light, detection capabilities can be further improved, making it easier to obtain information inside the living body.

[0012] In the agricultural and food industries, there is a demand for nondestructive saccharometers that can nondestructively measure the sugar content of agricultural produce and fruits and vegetables, as well as measuring instruments (e.g., Taste Meter (registered trademark)) that can nondestructively test the taste of, for example, rice. Near-infrared spectroscopy is sometimes used as a nondestructive method for measuring the internal quality of fruits and vegetables, 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 and vegetable peel or the surface layer near the surface. Near-infrared spectroscopy irradiates fruits and vegetables with light in the near-infrared wavelength range, receives the transmitted light that penetrates the fruit and vegetables, and receives the reflected light that is reflected by the fruit and vegetable, and measures the quality of the fruit and vegetable based on the decrease in light intensity (light absorption). Near-infrared spectroscopy analytical devices used in such food industries use light sources such as tungsten lamps and xenon lamps. JIS K0134, General Rules for Near-Infrared Spectroscopic Analysis, states that near-infrared refers to the wavelength range from 700 nm to 2500 nm.

[0013] 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.

[0014] Regarding the near-infrared light-emitting phosphors mentioned above, when a light-emitting element such as a light-emitting diode (LED) or laser diode (LD) that emits violet to blue light is used as an excitation light source to form a light-emitting device, a phosphor with high emission intensity is required so that emission suitable for the application can be achieved and detection can be performed with higher accuracy.

[0015] 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, along with light in the wavelength range from red light to near-infrared light. For example, there are cases where light 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.

[0016] The oxide phosphor has a composition represented by the following formula (1). (Li 1-s M 1 s )(Mg 1-t M 2t ) u (Ga 1-v M 3 v ) w O x :Cr y ,M 4 z (1) (In the above formula (1), M 1 is at least one element selected from the group consisting of Na, K, Rb and Cs, and M 2 is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, and M 3 is at least one element selected from the group consisting of Al and Sc, and M 4 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb; s, t, u, v, w, and x are, respectively, 0≦s≦0.5, 0≦t≦1.0, 0.03≦u≦10, 0≦v≦1.0, 5.1≦w≦25, 0.005≦u / w≦0.4, and 8.2≦x≦48; y and z are, respectively, when Li is taken as 1 or when Li and M are taken as 1 When the sum of the above is 1, the above Li or the above Li and the above M 1 The sum of the above satisfies 0.02≦y≦0.5, 0≦z≦0.3, and y>z.)

[0017] The oxide phosphor has a composition obtained by combining an oxide phosphor having a composition represented by the following formula (1a) with an oxide phosphor having a composition represented by the following formula (1b) in a range of 0.03 mol to 10 mol when the oxide phosphor having the composition represented by the formula (1a) is taken as 1 mol. (Li 1-at M a1 at ) au (Ga 1-av M a2 av )5O aw :Cr ax ,Ni ay , (1a) In the above formula (1a), M a1 is at least one element selected from the group consisting of Na, K, Rb and Cs, and Ma2 is at least one element selected from the group consisting of Al and Sc, and at, au, av, aw, ax, and ay are 0≦at≦1.0, 0.7≦au≦1.6, 0≦av<1.0, 7.85≦aw≦11.5, 0.05≦ax≦1.2, 0≦ay≦0.5, and 0.25, respectively.<ax+ay≦1.2、ax> Meet ay. (Mg 1-bt M b1 bt ) bu (Ga 1-bv-bx-by M b2 bv )2O bw :Cr bx ,M b3 by (1b) In the above formula (1b), M b1 is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, and M b2 is at least one element selected from the group consisting of Al and Sc, and M b3 are Ce, Eu, Mn, Nd, Tm, Ho, Er and Yb and bt, bu, bv, bw, bx, and by satisfy the following: 0≦bt≦1.0, 0.7≦bu≦1.3, 0≦bv≦0.8, 3.7≦bw≦4.3, 0.02≦bx≦0.3, 0≦by≦0.2, and bx>by.

[0018] In this specification, unless otherwise specified, the term "molar ratio" refers to the ratio of each element in 1 mole of the chemical composition of a phosphor. In this specification, in a composition formula, multiple elements separated by a comma (,) mean that at least one of these multiple elements is contained in the composition. Also, in this specification, in a composition formula representing the composition of a phosphor, the parts before the colon (:) represent the elements constituting the host crystal and their molar ratio, and the parts after the colon (:) represent the activator element.

[0019] The oxide phosphor having a composition represented by the formula (1a) and the oxide phosphor having a composition represented by the formula (1b) each have the same cubic crystal structure but different space groups. The oxide phosphor having a composition represented by the formula (1a) has a cubic crystal structure and a space group P4132 or P4332 (space group 213 or 212 in the International Tables for Crystallography). The oxide phosphor having a composition represented by the formula (1b) has a cubic crystal structure and a space group Fd3m (space group 227 in the International Tables for Crystallography). Note that "Fd3m" may have a "-" symbol over the number 3, as shown below. TIFF2026044359000002.tif22170

[0020] The oxide phosphor having a composition represented by the formula (1) has a composition obtained by combining 1 mole of an oxide phosphor having a composition represented by the formula (1a) with 0.03 to 10 moles of an oxide phosphor having a composition represented by the following formula (1b), and emits light with a higher luminous intensity when irradiated with excitation light. The oxide phosphor having a composition represented by the formula (1), which is obtained by combining 1 mole of an oxide phosphor having a composition represented by the formula (1a) with 0.03 to 10 moles of an oxide phosphor having a composition represented by the formula (1b), emits light with a higher luminous intensity. It is presumed that the reason why the oxide phosphor having a composition represented by the formula (1) emits light with a higher luminous intensity is that the lattice length differs between the Mg side and the Li side contained in the composition of the oxide phosphor, changing the coordination length around the activator element Cr, and the activator element Cr is appropriately positioned in the crystal structure, allowing the oxide phosphor to emit light with a higher luminous intensity. Furthermore, the compound serving as a source of Li contained in the composition represented by formula (1a) and the compound serving as a source of Mg contained in the composition represented by formula (1b) have different melting points, and it is presumed that when the raw materials are mixed to produce the oxide phosphor represented by formula (1), the compound with the lower melting point acts as a flux for the compound with the higher melting point, thereby promoting particle growth of the oxide phosphor. The oxide phosphor having the composition represented by formula (1) preferably has a composition in which 1 mole of the oxide phosphor having the composition represented by formula (1a) is combined with 0.03 moles or more and 5 moles or less of the oxide phosphor having the composition represented by formula (1b) per mole of the oxide phosphor having the composition represented by formula (1a), more preferably 0.05 moles or more and 4.5 moles or less, and may have a composition in which 0.1 moles or more are combined, or may have a composition in which 0.2 moles or more are combined.

[0021] The oxide phosphor having the composition represented by the formula (1) contains Cr, which is an activator element in the formula (1). The oxide phosphor has a molar ratio of Cr when Li is set to 1 or when Li and M are set to 1. 1 When the sum of Li or Li and M is 1, 1With respect to the sum of y and y, the range of y is preferably 0.02 or more and 0.5 or less (0.02≦y≦0.5), more preferably 0.03 or more and 0.48 or less (0.03≦y≦0.48), more preferably 0.05 or more and 0.47 or less (0.05≦y≦0.47), and even more preferably 0.1 or more and 0.46 or less (0.1≦y≦0.46). When the variable y, which represents the molar ratio of Cr, the activator element, in the formula (1) is 0.02 or more and 0.5 or less (0.02≦y≦0.5), the oxide phosphor can emit light with higher luminescence intensity in the wavelength range from red light to near-infrared light when irradiated with excitation light.

[0022] The oxide phosphor having the composition represented by formula (1) preferably emits light having a peak emission wavelength in the range of 700 nm to 1500 nm in the emission spectrum of the oxide phosphor upon irradiation with excitation light, more preferably 705 nm to 1400 nm, even more preferably 710 nm to 1300 nm, and particularly preferably 720 nm to 1250 nm. When the oxide phosphor emits light having a peak emission wavelength in the range of 700 nm to 1500 nm in the emission spectrum upon irradiation with excitation light, it can be used in light-emitting devices for obtaining information from within a living body, for non-destructively obtaining information on agricultural products, fruits and vegetables, and the like, and for promoting the growth of plants such as vegetables.

[0023] When irradiated with excitation light, the oxide phosphor having the composition represented by formula (1) preferably emits light having an emission peak wavelength with a full width at half maximum of 150 nm to 280 nm, more preferably 180 nm to 270 nm, and even more preferably 185 nm to 260 nm. In this specification, the full width at half maximum refers to the wavelength width in the emission spectrum where the emission intensity is 50% of the emission intensity at the emission peak wavelength exhibiting the maximum emission intensity. Light is absorbed and scattered in vivo, and in order to measure subtle changes in the propagation behavior of light in blood within the body, it is preferable to irradiate light having an emission peak wavelength with a wide full width at half maximum. Furthermore, even in non-destructive measurement of information on agricultural produce, fruits, and vegetables, it is preferable to irradiate light having an emission peak wavelength with a wide full width at half maximum of the emission spectrum in order to obtain information on the interior of the agricultural produce, fruits, and vegetables. Furthermore, in terms of how the color of an object appears when irradiated with light (hereinafter also referred to as "color rendering"), it is desirable for the light to have an emission spectrum in a wide wavelength range, and a wider full width at half maximum enables the emission of light with excellent color rendering. For example, even when used in a work environment such as a factory, it may be required to emit light that does not disrupt the spectral balance of light so that workers can work easily.

[0024] The oxide phosphor having the composition represented by the formula (1) is 1 is at least one element selected from the group consisting of Na, K, Rb and Cs, and may be at least one element selected from the group consisting of Na, K and Rb, or may contain two or more elements. 1 The variable s representing the molar ratio satisfies the range of 0 or more and 0.5 or less (0≦s≦0.5), may satisfy the range of 0 or more and 0.3 or less (0≦s≦0.3), or may be 0 (s=0).

[0025] The oxide phosphor is a compound represented by the formula (1) in which the element M 2 In the formula (1), the element M may be at least one element selected from the group consisting of Ca, Sr and Ba, excluding Zn, and may contain two or more elements.2 is at least one element selected from the group consisting of Ca, Sr and Ba, the element M 2 In the variables t and u that represent the molar ratio of the above, the variable t is within the range of 0 or more and 1.0 or less (0≦t≦1.0), may be within the range of 0 or more and 0.5 or less (0≦t≦0.5), may be within the range of 0 or more and 0.3 or less (0≦t≦0.3), or may be within the range of 0.01 or more and 0.3 or less (0.01≦t≦0.3).

[0026] The oxide phosphor has a composition represented by the formula (1) in which the element M 2 is at least one element selected from the group consisting of Ca, Sr and Ba, excluding Zn, element M 2 In the variables t and u representing the molar ratio, the variable t may be within the range of 0 to 0.2 (0≦t≦0.2), 0 to 0.1 (0≦t≦0.1), 0 to 0.05 (0≦t≦0.05), or 0 (t=0). In the formula (1), the variable u represents the number of moles of the oxide phosphor having the composition represented by the formula (1b) relative to 1 mole of the oxide phosphor having the composition represented by the formula (1a). In the formula (1), the element M 2 When the variable t representing the formula (1) is 0 (t=0), the variable u preferably satisfies the range of 0.03 to 5 (0.03≦u≦5), more preferably satisfies the range of 0.05 to 4.5 (0.05≦u≦4.5), and even more preferably satisfies the range of 0.05 to 4 (0.05≦u≦4). The oxide phosphor having the composition represented by the formula (1) is obtained by adding the element M 2 When the variable t representing the above is 0 (t=0), if the variable u is within the range of 0.03 to 5 (0.03≦u≦5), irradiation with excitation light will produce light in the wavelength range from red light to near-infrared light, with a higher luminescence intensity.

[0027] In the oxide phosphor having the composition represented by the formula (1), when the number of moles of the oxide phosphor having the composition represented by the formula (1b) is changed relative to 1 mole of the oxide phosphor having the composition represented by the formula (1a), the molar ratio of Ga or the element M 3 or the molar ratio of Ga and element M 3 The variable w, which represents the total molar ratio of the elements M and M, also changes. 3 or the molar ratio of Ga and element M 3 The variable w, which represents the molar ratio of the sum of the above, is within the range of 5.1 or more and 25 or less (5.1≦w≦25), may be within the range of 5.1 or more and 15 or less (5.1≦w≦15), may be within the range of 5.1 or more and 13 or less (5.1≦w≦13), or may be within the range of 5.4 or more and 13 or less (5.4≦w≦13). When the variable w in formula (1) is within the range of 5.1 or more and 25 or less (5.1≦w≦25), the oxide phosphor having the composition represented by formula (1) can emit light with higher luminescence intensity in the wavelength range from red light to near-infrared light when irradiated with excitation light.

[0028] The oxide phosphor has a composition represented by the formula (1) in which the element M 3 is at least one element selected from the group consisting of Al and Sc, and may be two elements. 3 The oxide phosphor may be a phosphor having an element M in the formula (1). 3 In the variables v and w that represent the molar ratio of the above, the variable v is within the range of 0 or more and 1.0 or less (0≦v≦1.0), may be within the range of 0 or more and 0.8 or less (0≦v≦0.3), may be within the range of 0 or more and 0.5 or less (0≦v≦0.5), may be within the range of 0 or more and 0.3 or less (0≦v≦0.3), or may be 0 (v=0).

[0029] The oxide phosphor is a compound represented by the formula (1) in which Mg or Mg and M 2 The variable u represents the molar ratio of Ga or Ga and M 3The ratio u / w of the variable u to the variable w, which represents the molar ratio of the sum of the above, satisfies the range of 0.005 to 0.4 (0.005≦u / w≦0.4), may satisfy the range of 0.008 to 0.35 (0.008≦u / w≦0.35), or may satisfy the range of 0.009 to 0.32 (0.009≦u / w≦0.32). When the ratio u / w of the variable u to the variable w in formula (1) satisfies the range of 0.005 to 0.4 (0.005≦u / w≦0.4), the oxide phosphor can emit light with a wavelength in the red to near-infrared range and with a higher luminescence intensity when irradiated with excitation light.

[0030] In the oxide phosphor, the variable x representing the molar ratio of oxygen (O) in formula (1) varies depending on the number of moles of the oxide phosphor having the composition represented by formula (1b) combined with 1 mole of the oxide phosphor having the composition represented by formula (1a). In the oxide phosphor, the variable x representing the molar ratio of oxygen (O) in formula (1) satisfies the range of 8.2 to 48 (8.2≦x≦48). When the variable x in formula (1) is within the range of 8.2 to 48 (8.2≦x≦48), the oxide phosphor can be an oxide phosphor having the composition represented by formula (1), in which 1 mole of the oxide phosphor having the composition represented by formula (1a) is combined with 0.05 moles to 10 moles of the oxide phosphor having the composition represented by formula (1b).

[0031] The oxide phosphor having the composition represented by the formula (1) is 4 In the composition represented by the formula (1), the oxide phosphor contains the element M 4 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er and Yb. 4 However, the oxide phosphor may contain at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb in addition to Ni. 4 But Ni is also acceptable.

[0032] The oxide phosphor is a compound represented by the formula (1) in which the element M 4 The variable z, which represents the molar ratio of Li to M, is 1 When the sum of these is taken as 1, z satisfies the range of 0 or more and 0.3 or less (0≦z≦0.3), may satisfies the range of 0 or more and 0.2 or less (0≦z≦0.2), or may satisfies the range of 0 or more and 0.1 or less (0≦z≦0.1). 4 does not contain Ni, element M 4 The oxide phosphor may not contain the element M in the formula (1), or z may satisfy 0 (z=0). 4 If contains more than one element, the variable z is 4 The oxide phosphor is an oxide phosphor containing an element M which is an activator element in the formula (1). 4 The variable z, which represents the molar ratio of Cr, is smaller than the variable y, which represents the molar ratio of Cr, an activator element (y>z). In the oxide phosphor, the variables y and z in formula (1) preferably fall within the range of 1.5 to 50 (1.5≦y / z≦50), may fall within the range of 2.0 to 40 (2.0≦y / z≦40), or may fall within the range of 2.5 to 30 (2.5≦y / z≦30).

[0033] The oxide phosphor is a compound represented by the formula (1) in which the element M 2 In the variables t and u that represent the molar ratio of the above, when the variable t is 0 (t=0), the variable u preferably satisfies the range of 0.05 to 4 (0.05≦u≦4), and the variable w preferably satisfies the range of 5.4 to 13 (5.4≦w≦13). The oxide phosphor having the composition represented by the formula (1) is obtained by adding the element M 2 When the variable t representing the above is 0 (t=0), if the variable u is within the range of 0.05 or more and 5 or less (0.05≦u≦4) and the variable w is within the range of 5.4 or more and 13 or less (5.4≦w≦13), then when irradiated with excitation light, light in the wavelength range from red light to near-infrared light and with higher luminescence intensity can be emitted.

[0034] The oxide phosphor is a compound represented by the formula (1) in which the element M 1 The variable s representing the molar ratio of element M is 0 (s=0). 2 In the variables t and u representing the molar ratios, when the variable t is 0 (t=0), the variable u preferably satisfies the range of 0.2 or more and 4.5 or less (0.2≦u≦4.5), and the variable w preferably satisfies the range of 5.4 or more and 13 or less (5.4≦w≦13). In the oxide phosphor having the composition represented by the formula (1), when the variable s is 0 (s=0) and the variable t is 0 (t=0) in the formula (1), if the variable u satisfies the range of 0.2 or more and 4.5 or less (0.2≦u≦4.5) and the variable w satisfies the range of 5.4 or more and 13 or less (5.4≦w≦13), the oxide phosphor can emit light with a wavelength range from red light to near-infrared light and with a higher luminous intensity when irradiated with excitation light.

[0035] The oxide phosphor is a compound represented by the formula (1) in which the element M 4 is Ni, element M 4 The variable z, which represents the molar ratio of Li to M, is 1 When the sum of these is taken as 1, it is preferable that z is in the range of 0.001 or more and 0.2 or less (0.001≦z≦0.2), and more preferable that z is in the range of 0.002 or more and 0.1 or less (0.002≦z≦0.1). 4 is Ni and the variable z is within the range of 0.001 or more and 0.2 or less (0.001≦z≦0.2), Cr first absorbs the energy of the excitation light, and the energy absorbed by Cr is transferred to Ni, which is then efficiently excited, thereby emitting light having an emission peak wavelength in the wavelength range from red light to near-infrared light and an emission spectrum with a wide full width at half maximum.

[0036] The oxide phosphor is a compound represented by the formula (1) in which the element M 2In the variables t and u that represent the molar ratio of the above, the variable t may be within the range of 0.4 or more and 0.6 or less (0.4≦t≦0.6), and the variable u may be within the range of 0.2 or more and 5 or less (0.2≦u≦5). The oxide phosphor having the composition represented by the formula (1) may be formed by adding the element M 2 When the variable t is within the range of 0.4 or more and 0.6 or less (0.4≦t≦0.6) and the variable u is within the range of 0.2 or more and 5 or less (0.2≦u≦5), the oxide phosphor can emit light having an emission spectrum with an emission peak wavelength within the range of 820 nm or more and 860 nm or less when irradiated with excitation light. 2 When the variable t is within the range of 0.4 or more and 0.6 or less (0.4≦t≦0.6) and the variable u is within the range of 0.2 or more and 5 or less (0.2≦u≦5), the oxide phosphor emits light having an emission peak wavelength and a full width at half maximum of an emission spectrum within the range of 200 nm or more and 280 nm or less. 2 When the variable t is in the range of 0.4 or more and 0.6 or less (0.4≦t≦0.6) and the variable u is in the range of 0.2 or more and 5 or less (0.2≦u≦5), the oxide phosphor may emit light having an emission peak wavelength in the range of 830 nm or more and 850 nm or less when irradiated with excitation light. 2 When the variable t is within the range of 0.4 or more and 0.6 or less (0.4≦t≦0.6) and the variable u is within the range of 0.2 or more and 5 or less (0.2≦u≦5), the light has an emission peak wavelength within a desired range, and it is easy to obtain information about living organisms and information about agricultural products, fruits and vegetables, etc. non-destructively, and it is possible to emit light with excellent color rendering properties.

[0037] The oxide phosphor is a compound represented by the formula (1) in which the element M 2 The oxide phosphor may contain Zn. 2 contains Zn, element M 2 represents the molar ratio of element M 2In the variables t and u representing the molar ratio of the element M, the variable t may be within the range of 0.4 or more and 0.6 or less (0.4≦t≦0.6), and the variable u may be within the range of 0.2 or more and 5 or less (0.2≦u≦5). 2 The oxide phosphor may contain Zn, the variable t satisfies 1.0 (t=1.0), and may not contain Mg. 2 may contain Zn and at least one element selected from the group consisting of Ca, Sr and Ba.

[0038] The oxide phosphor is a compound represented by the formula (1) in which the element M 2 is Zn, the variable t satisfies 1.0 (t=1.0), and Mg may not be contained. 2 is Zn and the variable t satisfies 1.0 (t=1.0), it is preferable that the material emits light having an emission spectrum with an emission peak wavelength in the range of 700 nm to 860 nm when irradiated with excitation light.

[0039] 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 with excitation light. The oxide phosphor is preferably contained in a wavelength conversion member, and the wavelength conversion member may contain a translucent material.

[0040] A semiconductor element can be used as a light-emitting element that irradiates an oxide phosphor with excitation light. 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-Y N (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.

[0041] 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.

[0042] 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 1600 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 or 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.

[0043] 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.

[0044] 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)

[0045] 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 Group 4 elements and Group 14 elements, 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 14 elements. The group 13 element is preferably Al, and the group 14 element is preferably Si. b2 satisfies 0 < b2 < 0.2, and c2 is [M 7 1-b2 Mn 4+ b2 F d2 is the absolute value of the charge of the ion, and d2 satisfies 5 < d2 < 7.) (Ba,Sr,Ca)2Si5N8:Eu (4f) (Sr,Ca)Li(Al,Ga)3N4:Eu (4g)

[0046] The fifth phosphor includes a gallate phosphor having a composition represented by the following formula (5a), an aluminate phosphor having a composition represented by the following formula (5b), and a phosphor having a composition represented by the following formula (5c) which is different in composition from the oxide phosphor, a phosphor having a composition represented by the following formula (5d) which is different in composition from the oxide phosphor, 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, and a phosphor having a composition represented by the following formula (5h) which is different in composition from the oxide phosphor. a phosphor having a composition represented by the following formula (5i) which is different from the oxide phosphor, a phosphor having a composition represented by the following formula (5j) which is different from the oxide phosphor, a phosphor having a composition represented by the following formula (5k) which is different from the oxide phosphor, a phosphor having a composition represented by the following formula (5l) which is different from the oxide phosphor, a phosphor having a composition represented by the following formula (5m) which is different from the oxide phosphor, and a phosphor having a composition represented by the following formula (5n) which is different from the oxide phosphor, and the phosphor may contain two or more types of phosphors.

[0047] ZnGa2O4:Cr (5a) (Lu,Y,Gd,Tb)3(Al,Ga)5O 12 :Ce,Cr (5b)

[0048] M 8 g M 9 h M 10 i M 11 5O j :Cr e , M 12 f (5c) (In the above formula (5c), M 8 is at least one element selected from the group consisting of Li, Na, K, Rb, and Cs, and M 9is 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 B, 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 12 is 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.)

[0049] (Ga 1-u4 M 13 u4 )2(Ge 1-v4 M 14 v4 ) w4 O x4 :Cr y4 ,M 15 z4 (5d) (In the formula (5d), M 13 is at least one element selected from the group consisting of Al, Sc, and In, and M 14 is at least one element selected from the group consisting of Si, Ti, Zr, Sn, and Hf, and M 15 is at least one element selected from the group consisting of Ni, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and u4, v4, w4, x4, y4, and z4 satisfy 0 ≤ u4 ≤ 1.0, 0 ≤ v4 ≤ 0.5, 1.0 ≤ w4 ≤ �.0, 5 ≤ x4 ≤ 9, 0.005 ≤ y4 ≤ 1.0, 0 ≤ z4 ≤ 0.5.)

[0050] (Mg 1-s5 M 16 s5 )2(Al 1-t5 M 17 t5 ) u5 (Ge 1-v5 M 18 v5 )w5 O x5 :Cr y5 ,M 19 z5 (5e) (In the formula (5e), ​​M 16 is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, and M 17 is at least one element selected from the group consisting of Ga, Sc, and In, and M 18 is at least one element selected from the group consisting of Si, Ti, Zr, Sn and Hf, and M 19 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and s5, t5, u5, v5, w5, x5, y5, and z5 satisfy the following relationships: 0≦s5≦1.0, 0≦t5≦1.0, 1.5≦u5≦2.5, 0≦v5≦0.5, 3.0≦w5≦6.0, 11.0≦x5≦17.0, 0.005≦y5≦1.0, and 0≦z5≦0.5, respectively.

[0051] M 20 x6 (Al 1-y6 M 21 y6 ) z6 O x6+3 / 2z6 :Cr v6 ,M 22 w6 (5f) (In the above formula (5f), M 20 is at least one element selected from the group consisting of alkaline earth metal elements, and M 21 is at least one element selected from the group consisting of Group 13 elements excluding Al, and M 22 is at least one element selected from the group consisting of Mn, Eu, Ce, Tb, Pr, Nd, Sm, Yb, Ho, Er, and Tm, and v6, w6, x6, y6, and z6 satisfy the following relationships: 0.004≦v6≦0.8, 0≦w6≦0.4, 0.004≦v6+w6≦0.8, 1.0≦x6≦4.0, 0≦y6≦0.7, 4.0≦z6≦1.50, respectively.

[0052] M 23 t7 M24 u7 (Ge 1-v7 M 25 v7 )6O w7 :Cr x7 ,M 26 y7 (5g) (In the formula (5g), M 23 is at least one element selected from the group consisting of Li, Na, K, Rb, and Cs, and M 24 is at least one element selected from the group consisting of Ca, Sr, Mg, Ba, and Zn, and M 25 is at least one element selected from the group consisting of Si, Ti, Zr, Sn, Hf, and Pb, and M 26 is at least one element selected from the group consisting of Eu, Ce, Tb, Pr, Nd, Sm, Yb, Ho, Er, Tm, Ni, and Mn, and t7, u7, v7, w7, x7, and y7 satisfy 1.5 ≤ t7 ≤ 2.5, 0.7 ≤ u7 ≤ 1.3, 0 ≤ v7 ≤ 0.4, 12.9 ≤ w7 ≤ 15.1, 0 < x7 ≤ 0.2, 0 ≤ y7 ≤ 0.10, and y7 < x7 respectively.)

[0053] (Li 1-u8 M 27 u8 )4(Ge 1-v8 M 28 v8 ) w8 O x8 :Cr y8 ,M 29 z8 (5h) (In the formula (5h), M 27 is at least one element selected from the group consisting of Na, K, Rb, and Cs, and M 28 is at least one element selected from the group consisting of Si, Ti, Zr, Sn, and Hf, and M 29 is at least one element selected from the group consisting of Ni, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and u8, v8, w8, x8, y8, and z8 satisfy 0 ≤ u8 ≤ 0.3, 0 ≤ v8 ≤ 0.5, 3.5 ≤ w8 ≤ 15, 9 ≤ x8 ≤ 32, 0.005 ≤ y8 ≤ 1.0, and 0 ≤ z8 ≤ 0.5 respectively.)

[0054] (Li 1-u9 M 30 u9 )2M 31 v9 M 32 w9 O x9 :Cr y9 ,M 33 z9 (5i) (In the above formula (5i), M 30 is at least one element selected from the group consisting of Na, K, Rb and Cs, and M 31 is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and M 32 is at least one element selected from the group consisting of Si, Ge, Ti, Zr, Sn and Hf, and M 33 is at least one element selected from the group consisting of Ni, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and u9, v9, w9, x9, y9, and z9 satisfy the following relationships: 0≦u9≦1.0, 0.8≦v9≦3.0, 1.8≦w9≦6, 5.4≦x9≦16, 0.005≦y9≦1.0, and 0≦z9≦0.5, respectively.

[0055] (Mg 1-p10 M 34 p10 ) q10 (Li 1-r10 M 35 r10 ) s10 (In 1-t10 M 36 t10 ) u10 (Ge 1-v10 M 37 v10 ) w10 O x10 :Cr y10 ,M 38 z10 (5j) (In the above formula (5j), M 34 is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, and M 35is at least one element selected from the group consisting of Na, K, Rb and Cs, and M 36 is at least one element selected from the group consisting of Al, Ga, and Sc, and M 37 is at least one element selected from the group consisting of Si, Ti, Zr, Sn and Hf, and M 38 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and p10, q10, r10, s10, t10, u10, v10, w10, x10, y10, and z10 satisfy the following relationships: 0≦p10≦1.0, 0.1≦q10≦0.9, 0≦r10≦1.0, 0.05≦s10≦0.45, 0≦t10≦0.5, 0.05≦u10≦0.45, 0≦v10≦1.0, 0.8≦w10≦1.3, 2.6≦x10≦3.6, 0.02≦y10≦0.5, 0≦z10≦0.3, 0.9≦q10+s10+u10≦1.2, respectively.

[0056] (Li 1-q11 M 39 q11 ) r11 (Mg 1-s11 M 40 s11 ) t11 (Ta 1-u11-v11 Nb u11 M 41 v11 ) w11 O x11 :Cr y11 ,M 42 z11 (5k) (In the above formula (5k), M 39 is at least one element selected from the group consisting of Na, K, Rb and Cs, and M 40 is at least one element selected from the group consisting of Zn, Ca, Sr and Ba, and M 41 is at least one element selected from the group consisting of P, V, Sb and Bi, and M 42is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and q11, r11, s11, t11, u11, v11, w11, x11, y11, and z11 satisfy the following relationships: 0≦q11≦0.5, 0.5≦r11≦3.5, 0≦s11≦0.5, 1.8≦t11≦3.2, 0≦u11≦1.0, 0≦v11≦0.3, 0≦u11+v11≦1.0, 0.8≦w11≦1.2, 5.1≦x11≦6.9, 0.002≦y11≦0.5, and 0≦z11≦0.3, respectively.

[0057] (Ga 1-v12 M 43 v12 )2O3:Cr x12 (5l) (In the above formula (5l), M 43 is at least one element selected from the group consisting of Al, In and rare earth elements, and v12 and x12 satisfy 0≦v12≦1.0 and 0.02≦x12≦0.3, respectively.

[0058] (Li 1-t13 M 44 t13 ) u13 (Ga 1-v13 M 45 v13 )5O w13 :Cr x13 ,Ni y13 ,M 46 z13 (5m) (In the above formula (5m), M 44 is at least one element selected from the group consisting of Na, K, Rb and Cs, and M 45 is at least one element selected from the group consisting of B, Al, In and rare earth elements, and M 46is at least one element selected from the group consisting of Si, Ge, Sn, Ti, Zr, Hf, Bi, V, Nd, and Ta, and t13, u13, v13, w13, x13, y13, and z13 are 0≦t13≦1.0, 0.7≦u13≦1.6, 0≦v13<1.0, 7.85≦w13≦11.5, 0.05≦x13≦1.2, 0≦y13≦0.5, 0.25<x13+y13≦1.2、x13> y13, 0≦z13≦0.5.)

[0059] (Mg 1-t14 M 47 t14 ) u14 (Ga 1-v14-x14-y14 M 48 v14 )2O w14 :Cr x14 ,M 49 y14 (5n) (In the formula (5n), M 47 is at least one element selected from the group consisting of Ca, Sr, Ba, Ni and Zn, and M 48 is at least one element selected from the group consisting of B, Al, In and Sc, and M 49 is at least one element selected from the group consisting of Eu, Ce, Tb, Pr, Nd, Sm, Yb, Ho, Er, Tm, and Mn, and t14, u14, v13, w14, x14, and y14 are 0≦t14≦0.8, 0.7≦u14≦1.3, 0≦v14<0.8, 3.7≦w14≦4.3, and 0.02, respectively.<x14≦0.3、0≦y14≦0.2、x14> Satisfies y14.)

[0060] 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.

[0061] 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 preferably 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 oxide phosphor included in the first phosphor 71 contains an oxide phosphor having a composition represented by the formula (1). The phosphor 70 may include a phosphor having a different composition from 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.

[0062] 3 and 4 show a second configuration example of a light-emitting device. FIG. 3 is a schematic plan view of the light-emitting device 200. FIG. 4 is a schematic cross-sectional view of the light-emitting device 200 shown in FIG. 3 taken along line III-III'. 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. The wavelength conversion member 51 includes a wavelength converter 52 containing a first phosphor 71 that emits light upon excitation by light from the light-emitting element 10, and a light-transmitting member 53 disposed on the emission surface side of the wavelength converter 52. The light-emitting element 10 is flip-chip mounted on the substrate 12 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 essentially includes a first phosphor 71 containing an oxide phosphor that is excited by light from the light-emitting element 10 and includes phosphor particles containing a host crystal containing Ga and oxygen, an activator element, and first compound particles and / or second compound particles disposed on the surfaces of the phosphor particles. The oxide phosphor contained in the first phosphor 71 contains at least one type of phosphor particle selected from the group consisting of phosphor particles having a composition represented by formula (1), phosphor particles having a composition represented by formula (2), and phosphor particles having a composition represented by formula (3). The oxide phosphor contained in the first phosphor may include two or more types of oxide phosphors, each containing phosphor particles having a different composition. The wavelength converter 52 may include at least one type 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 12, 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 being destroyed by application of an excessive voltage. The semiconductor element 11 may be mounted on a substrate 12 via a conductive member 61. A covering member 90 is disposed so as to cover the semiconductor element 11, for example. Each member used in the light emitting device will be described below. For details, the disclosure of JP 2014-112635 A can be referenced, for example.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] An example of a method for manufacturing the light emitting device of the first configuration example will be described. For details, see, for example, the disclosure of Japanese Patent Application Laid-Open No. 2010-062272. The method for manufacturing the 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.

[0067] 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 side and bottom surfaces. The molded body may be a molded body made of an aggregate base including a plurality of recesses.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] For example, in the step of arranging the light-emitting element, the light-emitting element is arranged on a substrate. The light-emitting element and the semiconductor element are, for example, flip-chip mounted on the substrate. Next, in the step of forming a wavelength conversion member containing a wavelength converter, the wavelength converter may be obtained by forming a plate-shaped, sheet-shaped, or layer-shaped wavelength converter 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 converter. Next, in the step of adhering 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 step of forming a covering member, the side surfaces of the light-emitting element and the wavelength conversion member are covered with a covering member composition. This covering 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 covering member. In this manner, the light-emitting device shown in Figures 3 and 4 can be manufactured.

[0073] The method for producing an oxide phosphor comprises the steps of: mixing a first compound containing Li with a second compound containing Mg and / or an element M; 2 a third compound containing Ga or a fourth compound containing M 3 and a sixth compound containing Cr; and heat-treating the raw material mixture in an oxygen-containing atmosphere at a temperature in the range of 1200°C to 1700°C to obtain an oxide phosphor.

[0074] The raw material mixture contains a second compound or element Mg containing 2 The raw material mixture may contain either a fourth compound containing Ga or a third compound containing element M. 3 The compound may contain either one of the fifth compounds including: The raw material mixture may contain element M as needed. 1 and optionally an element M 4 and an eighth compound comprising:

[0075] The raw material mixture is prepared by adjusting the molar ratio of Li or Li and M in 1 mole of the composition of the resulting oxide phosphor. 1 When the total molar ratio of Mg or element M is 1, 2 or the molar ratio of Mg and element M 2 The second compound containing Mg and / or the element M are added so that the total molar ratio u is in the range of 0.05 to 10 (0.05≦u≦10). 2 The raw material mixture preferably contains Mg and the element M. 2 When the total molar ratio of element M is 1, 2 The raw material mixture may be prepared by adjusting the molar ratio t of Mg and element M to be in the range of 0 to 1.0 (0≦t≦1.0). 2 When the total molar ratio of element M is 1, 2 When the molar ratio t is greater than 0, the raw material mixture contains 2 When the total molar ratio of Mg and element M2 is 1, the amount of element M 2 When the molar ratio t is 1.0, the raw material mixture does not need to contain the second compound containing Mg.

[0076] The raw material mixture is prepared by adjusting the molar ratio of Li or Li and M in 1 mole of the composition of the resulting oxide phosphor. 1 When the total molar ratio of the elements M is 1, the molar ratio of Ga or M 3 or the molar ratio of Ga and element M 3 the fourth compound containing Ga and / or the element M so that the total molar ratio w is in the range of 5.1 to 25 (5.1≦w≦25). 3 The raw material mixture is preferably prepared and mixed with a fifth compound containing Ga and the element M. 3 When the total molar ratio of element M is 1, 3 The raw material mixture may be prepared by adjusting the molar ratio v of Ga and element M to be in the range of 0 to 1.0 (0≦v≦1.0). 3 When the total molar ratio of element M is 1, 3 When the molar ratio v of element M exceeds 0, the raw material mixture 3 The fifth compound may contain Ga and the element M. 3 When the total molar ratio of element M is 1, 3 When the molar ratio t is 1.0, the raw material mixture does not need to contain the fourth compound containing Ga.

[0077] The raw material mixture is prepared by adjusting the molar ratio of Li or Li and M in 1 mole of the composition of the resulting oxide phosphor. 1 When the total molar ratio of the elements M is 1, the molar ratio of Ga or M 3 or the molar ratio of Ga and element M 3 The molar ratio of Mg to the total molar ratio w of elements M 2 or the molar ratio of Mg and element M 2 The second compound containing Mg and the element M are mixed so that the total molar ratio u (u / w) is in the range of 0.005 to 0.4 (0.005≦u / w≦0.4). 2 and a fourth compound containing Ga and an element M. 3 and a fifth compound selected from the group consisting of:

[0078] The raw material mixture is prepared by adjusting the molar ratio of Li or Li and M in 1 mole of the composition of the resulting oxide phosphor. 1 When the total molar ratio of Li and M is 1, the molar ratio of Li or Li and M 1 It is preferable to adjust and mix the raw materials so that the molar ratio y of Cr is in the range of 0.02 or more and 0.5 or less (0.02≦y≦0.5) with respect to the total molar ratio of the above.

[0079] The raw material mixture contains Li and element M 1 When the total molar ratio of element M is 1, 1 The element M may be added as necessary so that the mole s of the compound falls within the range of 0 to 0.5 (0≦s≦0.5). 1 A seventh compound containing Li and element M may be prepared and mixed. 1 When the total molar ratio of element M is 1, 1 When the molar ratio s of element M exceeds 0, the raw material mixture 1 A seventh compound may be included, comprising:

[0080] The raw material mixture is prepared by adjusting the molar ratio of Li or Li and M in 1 mole of the composition of the resulting oxide phosphor. 1 When the total molar ratio of Li and M is 1, the molar ratio of Li or Li and M 1 The molar ratio of element M 4 The element M may be added as necessary so that the molar ratio z is 0 or more and 0.3 or less (0≦z≦0.3). 4 The eighth compound containing the element M may be prepared and mixed. 4 When the molar ratio z of element M exceeds 0, the raw material mixture 4 The raw material mixture may contain an eighth compound containing the element M in a molar ratio y of Cr. 4 If necessary, the element M 4 An eighth compound containing the following may be prepared and mixed.

[0081] The raw materials are a first compound containing Li, a second compound containing Mg, and / or an element M. 2 a third compound containing Ga, a fourth compound containing Ga, and / or an element M 3a fifth compound containing Cr, a sixth compound containing Cr, and an element M contained as needed 1 and a seventh compound containing, as required, an element M 4 The eighth compound containing the following is preferably an oxide, a carbonate, a chloride, or a hydrate thereof.

[0082] The raw materials are a first compound containing Li, a second compound containing Mg, and / or an element M. 2 a third compound containing Ga, a fourth compound containing Ga, and / or an element M 3 a fifth compound containing Cr, a sixth compound containing Cr, and an element M contained as needed 1 and a seventh compound containing, as required, an element M 4 The eighth compound containing the compound may be mixed using a mixer to obtain a raw material mixture. 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.

[0083] 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 generated, the flux promotes the reaction between the raw materials. A halide containing at least one element selected from the group consisting of rare earth elements, alkaline earth metal elements, and alkali metal elements can be used as the flux. Among halides, fluoride can be used as the flux. When the elements contained in the flux are the same as at least some of the elements constituting the oxide phosphor, the flux can be added as part of the raw materials for the oxide phosphor having the desired composition so that the composition of the oxide phosphor becomes the desired composition. Alternatively, the flux can be added after the raw materials are mixed to obtain the desired composition.

[0084] 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.

[0085] The heat treatment is preferably 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.

[0086] The heat treatment temperature is within the range of 1200° C. to 1700° C., preferably 1250° C. to 1650° C., and more preferably 1300° C. to 1600° C. If the heat treatment temperature is 1200° C. to 1700° C., thermal decomposition is suppressed, and an oxide phosphor having the desired composition and a stable crystal structure can be obtained.

[0087] In the heat treatment, a holding time may be set at a predetermined temperature. The holding time may be, for example, 0.5 hours to 48 hours, 1 hour to 40 hours, or 2 hours to 30 hours. By setting the holding time to 0.5 hours to 48 hours, crystal growth can be promoted.

[0088] The pressure of the heat treatment atmosphere may be standard atmospheric pressure (0.101 MPa), or may be 0.101 MPa or higher, or may be a pressurized atmosphere in the range 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 the heat treatment is performed in a pressurized atmosphere.

[0089] 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.

[0090] 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]

[0091] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0092] Example 1 The raw materials were 0.74g of Li2CO3, 0.16g of MgO, 10.1g of Ga2O3, and 0.31g of Cr2O3 (the composition was LiMg 0.2 Ga 5.4 O 8.8 :Cr 0.20 In the present specification, in the feed composition or the composition represented by formula (1), the molar ratio of an element for which no numerical value for the molar ratio is given is 1. In addition, the molar ratio of Cr or the element M in the feed composition or the composition represented by formula (1) 4The molar ratio of is the molar ratio to Li when Li is taken as 1. The raw materials are weighed out so that the molar ratio of is 1 / 2 of the total weight of the raw materials is 1 / 2, and mixed for approximately 10 minutes using an agate mortar and pestle to obtain a raw material mixture. The obtained raw material mixture is placed in an alumina crucible and heat-treated for 6 hours in an air atmosphere (20% oxygen by volume) at 1500°C and standard atmospheric pressure (0.101 MPa). After the heat treatment, the heat-treated product is pulverized to obtain the oxide phosphor of Example 1 having the same molar ratio as that in the starting composition. The oxide phosphor according to Example 1 and the oxide phosphors according to Examples 2 to 37 described below have the compositions shown in Table 1 and are represented by the formula (1). For the oxide phosphor according to Example 1, the variable s in the formula (1) is 0 (s=0), 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 5.4 (w=5.4), the variable x is 8.8 (x=8.8), the variable y is 0.20 (y=0.20), and the variable z is 0 (z=0).

[0093] Example 2 The raw materials were 0.74g of Li2CO3, 0.16g of MgO, 10.1g of Ga2O3, and 0.40g of Cr2O3 (the composition was LiMg 0.2 Ga 5.4 O 8.8 :Cr 0.26 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 2 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 2, the variable s in the formula (1) is 0 (s=0), 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 5.4 (w=5.4), the variable x is 8.8 (x=8.8), the variable y is 0.26 (y=0.26), and the variable z is 0 (z=0).

[0094] Example 3 The raw materials were 0.74g of Li2CO3, 0.28g of MgO, 10.7g of Ga2O3, and 0.31g of Cr2O3 (the composition was LiMg0.35 Ga 5.7 O 9.4 :Cr 0.20 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 3 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 3, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 0.35 (u=0.35), the variable v is 0 (v=0), the variable w is 5.7 (w=5.7), the variable x is 9.4 (x=9.4), the variable y is 0.20 (y=0.20), and the variable z is 0 (z=0).

[0095] Example 4 The raw materials were 0.74g of Li2CO3, 0.28g of MgO, 10.7g of Ga2O3, and 0.40g of Cr2O3 (the composition was LiMg 0.35 Ga 5.7 O 9.4 :Cr 0.26 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 4 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 4, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 0.35 (u=0.35), the variable v is 0 (v=0), the variable w is 5.7 (w=5.7), the variable x is 9.4 (x=9.4), the variable y is 0.26 (y=0.26), and the variable z is 0 (z=0).

[0096] Example 5 The raw materials were 0.74g of Li2CO3, 0.41g of MgO, 11.2g of Ga2O3, and 0.31g of Cr2O3 (the composition was LiMg 0.5 GaO 10 :Cr 0.20 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 5 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 5, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 0.5 (u=0.5), the variable v is 0 (v=0), the variable w is 6 (w=6), the variable x is 10 (x=10), the variable y is 0.20 (y=0.20), and the variable z is 0 (z=0).

[0097] Example 6 The raw materials were 0.74g of Li2CO3, 0.41g of MgO, 11.2g of Ga2O3, and 0.40g of Cr2O3 (the composition was LiMg 0.5 GaO 10 :Cr 0.26 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 6 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 6, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 0.5 (u=0.5), the variable v is 0 (v=0), the variable w is 6 (w=6), the variable x is 10 (x=10), the variable y is 0.26 (y=0.26), and the variable z is 0 (z=0).

[0098] Example 7 The raw materials were 0.74g of Li2CO3, 0.62g of MgO, 12.1g of Ga2O3, and 0.31g of Cr2O3 (the composition was LiMg 0.75 Ga 6。5 O 11 :Cr 0.20 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 7 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 7, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 0.75 (u=0.75), the variable v is 0 (v=0), the variable w is 6.5 (w=6.5), the variable x is 11 (x=11), the variable y is 0.20 (y=0.20), and the variable z is 0 (z=0).

[0099] Example 8 The raw materials were 0.74g of Li2CO3, 0.62g of MgO, 12.1g of Ga2O3, and 0.40g of Cr2O3 (the composition was LiMg 0.75 Ga 6.5 O 11 :Cr 0.26 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 8 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 8, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 0.75 (u=0.75), the variable v is 0 (v=0), the variable w is 6.5 (w=6.5), the variable x is 11 (x=11), the variable y is 0.26 (y=0.26), and the variable z is 0 (z=0).

[0100] Example 9 The raw materials were 0.74g of Li2CO3, 0.81g of MgO, 13.1g of Ga2O3, and 0.06g of Cr2O3 (the composition was LiMgGa7O 12 :Cr 0.04 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 9 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 9, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 1 (u=1), the variable v is 0 (v=0), the variable w is 7 (w=7), the variable x is 12 (x=12), the variable y is 0.04 (y=0.04), and the variable z is 0 (z=0).

[0101] Example 10 The raw materials were 0.74g of Li2CO3, 0.81g of MgO, 13.1g of Ga2O3, and 0.20g of Cr2O3 (the composition was LiMgGa7O 12 :Cr 0.13) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 10 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 10, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 1 (u=1), the variable v is 0 (v=0), the variable w is 7 (w=7), the variable x is 12 (x=12), the variable y is 0.13 (y=0.13), and the variable z is 0 (z=0).

[0102] Example 11 The raw materials were 0.74g of Li2CO3, 0.81g of MgO, 13.1g of Ga2O3, and 0.31g of Cr2O3 (the composition was LiMgGa7O 12 :Cr 0.20 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 11 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 11, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 1 (u=1), the variable v is 0 (v=0), the variable w is 7 (w=7), the variable x is 12 (x=12), the variable y is 0.20 (y=0.20), and the variable z is 0 (z=0).

[0103] Example 12 The raw materials were 0.74g of Li2CO3, 0.81g of MgO, 13.1g of Ga2O3, and 0.40g of Cr2O3 (the composition was LiMgGa7O 12 :Cr 0.26 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 12 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 12, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 1 (u=1), the variable v is 0 (v=0), the variable w is 7 (w=7), the variable x is 12 (x=12), the variable y is 0.26 (y=0.26), and the variable z is 0 (z=0).

[0104] Example 13 The raw materials were 0.74g of Li2CO3, 0.81g of MgO, 13.1g of Ga2O3, and 0.51g of Cr2O3 (the composition was LiMgGa7O 12 :Cr 0.33 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 13 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 13, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 1 (u=1), the variable v is 0 (v=0), the variable w is 7 (w=7), the variable x is 12 (x=12), the variable y is 0.33 (y=0.33), and the variable z is 0 (z=0).

[0105] Example 14 The raw materials were 0.74g of Li2CO3, 0.81g of MgO, 13.1g of Ga2O3, and 0.62g of Cr2O3 (the composition was LiMgGa7O 12 :Cr 0.40 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 14 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 14, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 1 (u=1), the variable v is 0 (v=0), the variable w is 7 (w=7), the variable x is 12 (x=12), the variable y is 0.40 (y=0.40), and the variable z is 0 (z=0).

[0106] Example 15 The raw materials were 0.74g of Li2CO3, 0.81g of MgO, 13.1g of Ga2O3, and 0.72g of Cr2O3 (the composition was LiMgGa7O 12 :Cr 0.46 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 15 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 15, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 1 (u=1), the variable v is 0 (v=0), the variable w is 7 (w=7), the variable x is 12 (x=12), the variable y is 0.46 (y=0.46), and the variable z is 0 (z=0).

[0107] Example 16 The raw materials were 0.74g of Li2CO3, 1.2g of MgO, 15.0g of Ga2O3, and 0.31g of Cr2O3 (the composition was LiMg 1.5 GaO 14 :Cr 0.20 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 16 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 16, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 1.5 (u=1.5), the variable v is 0 (v=0), the variable w is 8 (w=8), the variable x is 14 (x=14), the variable y is 0.20 (y=0.20), and the variable z is 0 (z=0).

[0108] Example 17 The raw materials were 0.74g of Li2CO3, 1.2g of MgO, 15.0g of Ga2O3, and 0.40g of Cr2O3 (the composition was LiMg 1.5 GaO 14 :Cr 0.26 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 17 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 17, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 1.5 (u=1.5), the variable v is 0 (v=0), the variable w is 8 (w=8), the variable x is 14 (x=14), the variable y is 0.26 (y=0.26), and the variable z is 0 (z=0).

[0109] Example 18 The raw materials were 0.74g of Li2CO3, 1.6g of MgO, 16.8g of Ga2O3, and 0.20g of Cr2O3 (the composition was LiMg2Ga9O 16 :Cr 0.13 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 18 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 18, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 2 (u=2), the variable v is 0 (v=0), the variable w is 9 (w=9), the variable x is 16 (x=16), the variable y is 0.13 (y=0.13), and the variable z is 0 (z=0).

[0110] Example 19 The raw materials were 0.74g of Li2CO3, 1.6g of MgO, 16.8g of Ga2O3, and 0.40g of Cr2O3 (the composition was LiMg2Ga9O 16 :Cr 0.26 ) to obtain a raw material mixture, the same procedure as in Example 1 is carried out to obtain an oxide phosphor of Example 19 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 19, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 2 (u=2), the variable v is 0 (v=0), the variable w is 9 (w=9), the variable x is 16 (x=16), the variable y is 0.26 (y=0.26), and the variable z is 0 (z=0).

[0111] Example 20 The raw materials were 0.74g of Li2CO3, 3.2g of MgO, 24.3g of Ga2O3, and 0.20g of Cr2O3 (the composition was LiMg4Ga 13 O 24 :Cr 0.13 ) to obtain a raw material mixture, the same procedure as in Example 1 is carried out to obtain an oxide phosphor of Example 19 having the same molar ratio as the molar ratio in the charged composition. In the oxide phosphor of Example 19, the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 4 (u=4), the variable v is 0 (v=0), the variable w is 13 (w=13), the variable x is 24 (x=24), the variable y is 0.13 (y=0.13), and the variable z is 0 (z=0).

[0112] Example 21 The raw materials were 0.74g of Li2CO3, 1.6g of ZnO, 13.1g of Ga2O3, and 0.20g of Cr2O3 (the composition was LiZnGa7O 12 :Cr 0.13 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 21 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Example 21 is an oxide phosphor in which the variable s in the formula (1) is 0 (s=0) and the element M 2 is Zn, the variable t is 1 (t=1), the variable u is 1 (u=1), the variable v is 0 (v=0), the variable w is 7 (w=7), the variable x is 12 (x=12), the variable y is 0.13 (y=0.13), and the variable z is 0 (z=0).

[0113] Example 22 The raw materials were 0.74g of Li2CO3, 1.6g of ZnO, 13.1g of Ga2O3, and 0.31g of Cr2O3 (the composition was LiZnGa7O 12 :Cr 0.20 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 22 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Example 22 is a phosphor in which the variable s in the formula (1) is 0 (s=0), and the element M 2 is Zn, the variable t is 1 (t=1), the variable u is 1 (u=1), the variable v is 0 (v=0), the variable w is 7 (w=7), the variable x is 12 (x=12), the variable y is 0.20 (y=0.20), and the variable z is 0 (z=0).

[0114] Example 23 The raw materials were 0.74g of Li2CO3, 1.6g of ZnO, 13.1g of Ga2O3, and 0.40g of Cr2O3 (the composition was LiZnGa7O 12 :Cr 0.26 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 23 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Example 23 is an oxide phosphor in which the variable s in the formula (1) is 0 (s=0) and the element M 2 is Zn, the variable t is 1 (t=1), the variable u is 1 (u=1), the variable v is 0 (v=0), the variable w is 7 (w=7), the variable x is 12 (x=12), the variable y is 0.26 (y=0.26), and the variable z is 0 (z=0).

[0115] Example 24 The raw materials were 0.74g of Li2CO3, 3.2g of ZnO, 16.8g of Ga2O3, and 0.20g of Cr2O3 (the composition was LiZn2Ga9O 16 :Cr 0.13 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 24 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Example 24 is a phosphor in which the variable s in the formula (1) is 0 (s=0), and the element M 2 is Zn, the variable t is 1 (t=1), the variable u is 2 (u=2), the variable v is 0 (v=0), the variable w is 9 (w=9), the variable x is 16 (x=16), the variable y is 0.13 (y=0.13), and the variable z is 0 (z=0).

[0116] Example 25 The raw materials were 0.74g of Li2CO3, 3.2g of ZnO, 16.8g of Ga2O3, and 0.31g of Cr2O3 (the composition was LiZn2Ga9O 16 :Cr 0.20 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 25 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Example 25 is an oxide phosphor in which the variable s in the formula (1) is 0 (s=0) and the element M 2 is Zn, the variable t is 1 (t=1), the variable u is 2 (u=2), the variable v is 0 (v=0), the variable w is 9 (w=9), the variable x is 16 (x=16), the variable y is 0.20 (y=0.20), and the variable z is 0 (z=0).

[0117] Example 26 The raw materials were 0.74g of Li2CO3, 3.2g of ZnO, 16.8g of Ga2O3, and 0.40g of Cr2O3 (the composition was LiZn2Ga9O 16 :Cr 0.26 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 26 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Example 26 is an oxide phosphor in which the variable s in the formula (1) is 0 (s=0) and the element M 2 is Zn, the variable t is 1 (t=1), the variable u is 2 (u=2), the variable v is 0 (v=0), the variable w is 9 (w=9), the variable x is 16 (x=16), the variable y is 0.26 (y=0.26), and the variable z is 0 (z=0).

[0118] Example 27 The raw materials were 0.74g of Li2CO3, 6.5g of ZnO, 24.3g of Ga2O3, and 0.20g of Cr2O3 (the composition was LiZn4Ga 13 O 24 :Cr 0.13) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 27 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Example 27 is an oxide phosphor in which the variable s in the formula (1) is 0 (s=0) and the element M 2 is Zn, the variable t is 1 (t=1), the variable u is 4 (u=4), the variable v is 0 (v=0), the variable w is 13 (w=13), the variable x is 24 (x=24), the variable y is 0.13 (y=0.13), and the variable z is 0 (z=0).

[0119] Example 28 The raw materials were 0.74g of Li2CO3, 6.5g of ZnO, 24.3g of Ga2O3, and 0.31g of Cr2O3 (the composition was LiZn4Ga 13 O 24 :Cr 0.20 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 28 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Example 28 is a phosphor in which the variable s in the formula (1) is 0 (s=0), and the element M 2 is Zn, the variable t is 1 (t=1), the variable u is 4 (u=4), the variable v is 0 (v=0), the variable w is 13 (w=13), the variable x is 24 (x=24), the variable y is 0.20 (y=0.20), and the variable z is 0 (z=0).

[0120] Example 29 The raw materials were 0.74g of Li2CO3, 6.5g of ZnO, 24.3g of Ga2O3, and 0.40g of Cr2O3 (the composition was LiZn4Ga 13 O 24 :Cr 0.26 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 29 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Example 29 is a phosphor in which the variable s in the formula (1) is 0 (s=0) and the element M 2is Zn, the variable t is 1 (t=1), the variable u is 4 (u=4), the variable v is 0 (v=0), the variable w is 13 (w=13), the variable x is 24 (x=24), the variable y is 0.26 (y=0.26), and the variable z is 0 (z=0).

[0121] Example 30 The raw materials were 0.74g of Li2CO3, 0.41g of MgO, 0.80g of ZnO, 13.1g of Ga2O3, and 0.31g of Cr2O3 (the composition of the raw material was LiMg 0.5 Zn 0.5 Ga7O 12 :Cr 0.20 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 30 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Example 30 is an oxide phosphor in which the variable s in the formula (1) is 0 (s=0) and the element M 2 is Zn, the variable t is 0.5 (t=0.5), the variable u is 1 (u=1), the variable v is 0 (v=0), the variable w is 7 (w=7), the variable x is 12 (x=12), the variable y is 0.20 (y=0.20), and the variable z is 0 (z=0).

[0122] Example 31 The raw materials were 0.74g of Li2CO3, 0.81g of MgO, 1.6g of ZnO, 16.8g of Ga2O3, and 0.31g of Cr2O3 (the composition was Li(Mg 0.5 Zn 0.5 )2Ga9O 16 :Cr 0.20 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 31 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Example 31 is an oxide phosphor in which the variable s in the formula (1) is 0 (s=0) and the element M 2is Zn, the variable t is 0.5 (t=0.5), the variable u is 2 (u=2), the variable v is 0 (v=0), the variable w is 9 (w=9), the variable x is 16 (x=16), the variable y is 0.20 (y=0.20), and the variable z is 0 (z=0).

[0123] Example 32 The raw materials were 0.74g of Li2CO3, 1.6g of MgO, 3.2g of ZnO, 24.3g of Ga2O3, and 0.31g of Cr2O3 (the composition was Li(Mg 0.5 Zn 0.5 )4Ga 13 O 24 :Cr 0.20 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 32 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Example 32 is an oxide phosphor in which the variable s in the formula (1) is 0 (s=0), and the element M 2 is Zn, the variable t is 0.5 (t=0.5), the variable u is 4 (u=4), the variable v is 0 (v=0), the variable w is 13 (w=13), the variable x is 24 (x=24), the variable y is 0.20 (y=0.20), and the variable z is 0 (z=0).

[0124] Example 33 The raw materials were 0.74g of Li2CO3, 0.81g of MgO, 13.1g of Ga2O3, 0.65g of Cr2O3, and 0.07g of NiO (the composition was LiMgGa7O 12 :Cr 0.42 ,Ni 0.05 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 33 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Example 33 is an oxide phosphor in which the variable s in the formula (1) is 0 (s=0), the variable t is 0 (t=0), the variable u is 1 (u=1), the variable v is 0 (v=0), the variable w is 7 (w=7), the variable x is 12 (x=12), the variable y is 0.42 (y=0.42), and the element M 4is Ni and the variable z is 0.05 (z=0.05).

[0125] Example 34 The raw materials were 0.74g of Li2CO3, 0.08g of MgO, 9.7g of Ga2O3, and 0.31g of Cr2O3 (the composition was LiMg 0.1 Ga 5.2 O 8.4 :Cr 0.20 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 34 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor of Example 34 has the following in formula (1): variable s is 0 (s=0), variable t is 0 (t=0), variable u is 0.1 (u=0.1), variable v is 0 (v=0), variable w is 5.2 (w=5.2), variable x is 8.4 (x=8.4), variable y is 0.20 (y=0.20), and variable z is 0 (z=0).

[0126] Example 35 The raw materials were 0.74g of Li2CO3, 0.08g of MgO, 9.7g of Ga2O3, and 0.40g of Cr2O3 (the composition was LiMg 0.1 Ga 5.2 O 8.4 :Cr 0.26 ) to obtain a raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor of Example 35 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor of Example 35 has the following in formula (1): variable s is 0 (s=0), variable t is 0 (t=0), variable u is 0.1 (u=0.1), variable v is 0 (v=0), variable w is 5.2 (w=5.2), variable x is 8.4 (x=8.4), variable y is 0.26 (y=0.26), and variable z is 0 (z=0).

[0127] Example 36 The raw materials were 0.74g of Li2CO3, 0.04g of MgO, 9.5g of Ga2O3, and 0.31g of Cr2O3 (the composition was LiMg 0.05Ga 5.1 O 8.2 :Cr 0.20 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 36 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor of Example 36 has the following in formula (1): variable s is 0 (s=0), variable t is 0 (t=0), variable u is 0.05 (u=0.05), variable v is 0 (v=0), variable w is 5.1 (w=5.1), variable x is 8.2 (x=8.2), variable y is 0.20 (y=0.20), and variable z is 0 (z=0).

[0128] Example 37 The raw materials were 0.74g of Li2CO3, 0.04g of MgO, 9.5g of Ga2O3, and 0.40g of Cr2O3 (the composition was LiMg 0.05 Ga 5.1 O 8.2 :Cr 0.26 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Example 37 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor of Example 37 has the following in formula (1): variable s is 0 (s=0), variable t is 0 (t=0), variable u is 0.05 (u=0.05), variable v is 0 (v=0), variable w is 5.1 (w=5.1), variable x is 8.2 (x=8.2), variable y is 0.26 (y=0.26), and variable z is 0 (z=0).

[0129] Comparative Example 1 The raw materials were 0.74g of Li2CO3, 9.4g of Ga2O3, and 0.26g of Cr2O3 (the composition was LiGa5O8:Cr 0.17 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor according to Comparative Example 1 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Comparative Example 1 does not have the composition represented by the formula (1), and does not contain Mg or the element M 2 does not contain The oxide phosphor of Comparative Example 1 has a composition represented by the formula (1a), in which the variable at is 0 (at=0), the variable au is 1 (au=1), the variable av is 0 (av=0), the variable aw is 8 (aw=8), the variable ax is 0.17 (ax=0.17), and the variable ay is 0 (ay=0).

[0130] Comparative Example 2 The raw materials were 2.0g of MgO, 9.4g of Ga2O3, and 0.68g of Cr2O3 (the composition was MgGa2O4:Cr 0.18 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor according to Comparative Example 2 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Comparative Example 2 does not have the composition represented by the formula (1) and does not contain Li in its composition. The oxide phosphor of Comparative Example 2 has a composition represented by the formula (1b), in which bt is 0 (bt=0), bu is 1 (bu=1), bv is 0 (bv=0), bw is 4 (bw=4), bx is 0.18 (bx=0.18), and by is 0 (by=0).

[0131] Comparative Example 3 The raw materials were 4.9g of ZnO, 11.2g of Ga2O3, and 0.18g of Cr2O3 (the composition was ZnGa2O4:Cr 0.04 ) to obtain a raw material mixture in the same manner as in Example 1, to obtain an oxide phosphor of Comparative Example 3 having the same molar ratio as the molar ratio in the charged composition. The oxide phosphor according to Comparative Example 3 does not have the composition represented by the formula (1) and does not contain Li in its composition. The oxide phosphor according to Comparative Example 3 has a composition represented by the formula (1b), and in the formula (1b), the element M b1 is Zn, bt is 1 (bt=1), bu is 1 (bu=1), bv is 0 (bv=0), bw is 4 (bw=4), bx is 0.04 (bx=0.04), and by is 0 (by=0).

[0132] Measurement of emission spectrum, emission peak wavelength, full width at half maximum (FWHM), and relative emission intensity The emission spectrum of each oxide phosphor of 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 light-emitting element, which is a semiconductor 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. For the oxide phosphors of Examples 1 to 37 and Comparative Examples 2 and 3, the relative emission intensity (%) was determined, with the emission intensity at the emission peak wavelength of the oxide phosphor of Comparative Example 1 set to 100%. The results are shown in the table. The emission spectra of each oxide phosphor of the Examples and Comparative Examples are also shown in the figures.

[0133] [Table 1]

[0134] The oxide phosphors according to Examples 1 to 37 have the composition represented by the formula (1) and can emit light having an emission peak wavelength in the wavelength range of red light to near-infrared light of 700 nm or more and 1500 nm or less when irradiated with excitation light.

[0135] As shown in the emission spectra of each oxide phosphor in Figures 5 to 21, the oxide phosphors of Examples 1 to 37 emit light having an emission peak wavelength in the wavelength range from red light of 700 nm to 1500 nm inclusive to near-infrared light when irradiated with excitation light.

[0136] The oxide phosphors according to Examples 1 to 8 and 10 to 37 emit light having an emission peak wavelength with a full width at half maximum of 150 nm to 280 nm when irradiated with excitation light. To obtain information about living organisms, such as subtle changes in the propagation behavior of light in blood, or information about the inside of agricultural produce and vegetables, it is preferable to irradiate light with a wide full width at half maximum. Furthermore, the oxide phosphors according to Examples 1 to 8 and 10 to 37 can emit light with superior color rendering properties as the full width at half maximum is wider. In Example 9, the molar ratio of the activator element Cr in the composition represented by formula (1) is 0.04, and because the molar ratio of Cr is small, the full width at half maximum is smaller than 150 nm.

[0137] The oxide phosphor according to Comparative Example 1 has the composition represented by the formula (1a) above, and the oxide phosphors according to Comparative Examples 2 and 3 have the composition represented by the formula (1b) above.

[0138] The oxide phosphors of Examples 1 to 14, 16 to 20, and 34 to 37 emit light with higher luminous intensity when irradiated with excitation light, compared to the luminous intensity obtained by dividing the sum of the luminous intensity of the oxide phosphor of Comparative Example 1 and the luminous intensity of the oxide phosphor of Comparative Example 2 by 2.

[0139] The oxide phosphors of Examples 21 to 29 and 30 to 33 emit light with higher luminous intensity when irradiated with excitation light, compared to the luminous intensity obtained by dividing the sum of the luminous intensity of the oxide phosphor of Comparative Example 1 and the luminous intensity of the oxide phosphor of Comparative Example 3 by 2.

[0140] The oxide phosphors of Examples 34 to 37 emit light having a higher luminous intensity when irradiated with excitation light than the oxide phosphor of Comparative Example 1 having a composition represented by Formula (1a) and the oxide phosphors of Comparative Examples 2 and 3 having a composition represented by Formula (1b), even when combined in a ratio of 0.05 mol to 0.1 mol of an oxide phosphor having a composition represented by Formula (1b) for 1 mol of an oxide phosphor having a composition represented by Formula (1a).

[0141] In the oxide phosphor of Example 15, the molar ratio of Cr, which is an activation element, in the composition represented by formula (1) is large at 0.46, and the luminescence intensity is lower than that of the oxide phosphor of Comparative Example 1 due to concentration quenching.

[0142] The oxide phosphor of Example 29 has a composition represented by the formula (1), in which Mg is an element M 2 In this example, 1 mole of an oxide phosphor having a composition expressed by the formula (1a) is replaced with Zn, and 4 moles of an oxide phosphor having a composition expressed by the formula (1b) are combined with 1 mole of an oxide phosphor having a composition expressed by the formula (1a). It is presumed that the lattice length in the crystal structure differs between the Li side, the Mg side, and the Zn side, causing distortion in the crystal structure. When irradiated with excitation light, the full width at half maximum in the emission spectrum becomes larger than 150 nm, but the emission intensity is slightly lower than that of the oxide phosphor of Comparative Example 1.

[0143] The oxide phosphor according to Example 33 contains, in the composition represented by the formula (1), an element M which acts as an activator together with Cr. 4 The oxide phosphor of Comparative Example 1 has a slightly lower emission intensity than the oxide phosphor of Comparative Example 1.

[0144] The oxide phosphor according to Comparative Example 1 has the composition represented by the formula (1a) above, and the oxide phosphors according to Comparative Examples 2 and 3 have the composition represented by the formula (1b) above.

[0145] Embodiments according to the present disclosure include the following oxide phosphor, light-emitting device, and method for producing the oxide phosphor.

[0146] [Section 1] An oxide phosphor having a composition represented by the following formula (1): (Li 1-s M 1 s )(Mg 1-t M 2 t ) u (Ga 1-v M 3 v ) w Ox :Cr y ,M 4 z (1) (In the above formula (1), M 1 is at least one element selected from the group consisting of Na, K, Rb and Cs, and M 2 is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, and M 3 is at least one element selected from the group consisting of Al and Sc, and M 4 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb; s, t, u, v, w, and x are, respectively, 0≦s≦0.5, 0≦t≦1.0, 0.03≦u≦10, 0≦v≦1.0, 5.1≦w≦25, 0.005≦u / w≦0.4, and 8.2≦x≦48; y and z are, respectively, when Li is taken as 1 or when Li and M are taken as 1 When the sum of the above is 1, the above Li or the above Li and the above M 1 The sum of the above satisfies 0.02≦y≦0.5, 0≦z≦0.3, and y>z.) [Section 2] In the formula (1), y is the sum of Li and M when Li is 1 or when Li and M are 1. 1 When the sum of the above is 1, the above Li or the above Li and the above M 1 Item 2. The oxide phosphor according to item 1, wherein 0.03≦y≦0.48 is satisfied for the total of [Section 3] In the formula (1), y is the sum of Li and M when Li is 1 or when Li and M are 1. 1 When the sum of the above is 1, the above Li or the above Li and the above M 1 Item 3. The oxide phosphor according to item 1 or 2, wherein 0.1≦y≦0.46 is satisfied for the total of [Section 4] 4. The oxide phosphor according to claim 1, wherein in said formula (1), t and u satisfy t=0 and 0.03≦u≦5, respectively. [Section 5] 4. The oxide phosphor according to claim 1, wherein in said formula (1), t, u, and w satisfy t=0, 0.05≦u≦4, and 5.4≦w≦13, respectively. [Section 6] 4. The oxide phosphor according to any one of items 1 to 3, wherein in formula (1), s, t, u, and w satisfy s=0, t=0, 0.2≦u≦4, and 5.4≦w≦13, respectively. [Section 7] In the above formula (1), M 2 4. The oxide phosphor according to any one of items 1 to 3, wherein is at least one element selected from the group consisting of Ca, Sr, and Ba, and t satisfies 0.01≦t≦0.3. [Section 8] Item 8. The oxide phosphor according to any one of items 1 to 7, wherein the oxide phosphor emits light having an emission peak wavelength in the range of 700 nm to 1500 nm in an emission spectrum when irradiated with excitation light. [Section 9] Item 9. The oxide phosphor according to any one of items 1 to 8, wherein the oxide phosphor emits light having an emission peak wavelength and a full width at half maximum of an emission spectrum in the range of 150 nm to 280 nm when irradiated with excitation light. [Section 10] In the above formula (1), M 4 Item 2. The oxide phosphor according to item 1, wherein is Ni and z satisfies 0.001≦z≦0.2 when Li is taken as 1. [Section 11] Item 10. The oxide phosphor according to any one of Items 1 to 3 and Items 8 or 9, which recites any one of Items 1 to 3, wherein in the formula (1), t and u satisfy 0.4≦t≦0.6 and 0.2≦u≦5, respectively. [Section 12] Item 12. The oxide phosphor according to item 11, wherein the oxide phosphor emits light having an emission peak wavelength in the range of 820 nm to 860 nm in an emission spectrum when irradiated with excitation light. [Section 13] Item 12. The oxide phosphor according to item 11, wherein the oxide phosphor emits light having an emission peak wavelength and a full width at half maximum of an emission spectrum in the range of 200 nm to 280 nm when irradiated with excitation light. [Section 14] In the above formula (1), M 2Item 10. The oxide phosphor according to any one of Items 1 to 3 and Items 8 and 9, which refer to Items 1 to 3, wherein contains Zn and t satisfies t=1.0. [Section 15] In the above formula (1), M 2 is Zn, t satisfies t=1.0, and the oxide phosphor has an emission spectrum with an emission peak wavelength in the range of 700 nm to 860 nm. [Section 16] Item 16. A light emitting device comprising: the oxide phosphor according to any one of items 1 to 15; and a light emitting element having an emission peak wavelength in the range of 365 nm to 650 nm, which irradiates the oxide phosphor. [Industrial Applicability]

[0147] 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, food products, 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]

[0148] 10: light-emitting element, 11: semiconductor element, 12: substrate, 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): (Li １－ｓ M １ ｓ )(Mg １－ｔ M ２ ｔ ) ｕ (Ga １－ｖ M ３ ｖ ) ｗ O ｘ :Cr ｙ ,M ４ ｚ (1) (In the above formula (1), M １ is at least one element selected from the group consisting of Na, K, Rb, and Cs, and M ２ is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, and M ３ is at least one element selected from the group consisting of Al and Sc, and M ４ represents at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb; s, t, u, v, w, and x are, respectively, 0≦s≦0.5, 0≦t≦1.0, 0.03≦u≦10, 0≦v≦1.0, 5.1≦w≦25, 0.005≦u / w≦0.4, and 8.2≦x≦48; y and z are, respectively, when Li is taken as 1 or when Li and M are taken as １ When the sum of the above is 1, the Li or the Li and the M １ The sum of the above satisfies 0.02≦y≦0.5, 0≦z≦0.3, and y>z.)

2. In the formula (1), y is when Li is 1 or when Li and M are 1. １ When the sum of the above is 1, the Li or the Li and the M １ 2. The oxide phosphor according to claim 1, wherein y satisfies 0.03≦y≦0.48 for the total of

3. In the formula (1), y is when Li is 1 or when Li and M are 1. １ When the sum of the above is 1, the Li or the Li and the M １ 2. The oxide phosphor according to claim 1, wherein y satisfies 0.1≦y≦0.46 for the total of

4. 2. The oxide phosphor according to claim 1, wherein in the formula (1), t and u satisfy t=0 and 0.03≦u≦5, respectively.

5. 2. The oxide phosphor according to claim 1, wherein in the formula (1), t, u, and w satisfy t=0, 0.05≦u≦4, and 5.4≦w≦13, respectively.

6. 2. The oxide phosphor according to claim 1, wherein in the formula (1), s, t, u, and w satisfy s=0, t=0, 0.2≦u≦4, and 5.4≦w≦13, respectively.

7. In the formula (1), M ２ 2. The oxide phosphor according to claim 1, wherein is at least one element selected from the group consisting of Ca, Sr, and Ba, and t satisfies 0.01≦t≦0.

3.

8. 2. The oxide phosphor according to claim 1, wherein the oxide phosphor emits light having an emission peak wavelength in the range of 700 nm to 1500 nm in an emission spectrum when irradiated with excitation light.

9. 2. The oxide phosphor according to claim 1, wherein the oxide phosphor emits light having an emission peak wavelength and a full width at half maximum of an emission spectrum in the range of 150 nm to 280 nm when irradiated with excitation light.

10. In the formula (1), M ４ 2. The oxide phosphor according to claim 1, wherein is Ni and z satisfies 0.001≦z≦0.2 when Li is taken as 1.

11. 2. The oxide phosphor according to claim 1, wherein in the formula (1), t and u satisfy 0.4≦t≦0.6 and 0.2≦u≦5, respectively.

12. 12. The oxide phosphor according to claim 11, wherein the oxide phosphor emits light having an emission peak wavelength in the range of 820 nm to 860 nm in an emission spectrum when irradiated with excitation light.

13. 12. The oxide phosphor according to claim 11, wherein the oxide phosphor emits light having an emission peak wavelength and a full width at half maximum of an emission spectrum in the range of 200 nm to 280 nm when irradiated with excitation light.

14. In the formula (1), M ２ The oxide phosphor according to claim 1 , wherein contains Zn and t satisfies t=1.

0.

15. In the formula (1), M ２ is Zn, t satisfies t=1.0, and the oxide phosphor has an emission spectrum with an emission peak wavelength in the range of 700 nm to 860 nm.

16. A light emitting device comprising: the oxide phosphor according to claim 1; and 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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