Oxide phosphors and light-emitting devices

Abstract

Provided are an oxide phosphor and a light-emitting device. 【Solution means】An oxide phosphor having a composition represented by formula (1). (Li 1-q M 1 q )2(Zn 1-r M 2 r ) s (Ga 1-t M 3 t ) u (Ge 1-v M 4 v ) w O x :Cr y ,M 5 z (1) (In formula (1), M 1 is one or more selected from Na, K, Rb, and Cs, M 2 is one or more selected from Mg, Ca, Sr, and Ba, M 3 is one or more selected from Al, Sc, and In, M 4 is one or more selected from Si, Ti, Zr, Sn, and Hf, M 5 is one or more selected from Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, 0 ≦ q ≦ 0.5, 0 ≦ r ≦ 1.0, 0 ≦ s ≦ 4.0, 0 ≦ t ≦ 1.0, 5 ≦ u ≦ 10, 0 ≦ v ≦ 1.0, 0.5 ≦ w ≦ 5.0, 10 ≦ x ≦ 30, y and z satisfy 0.02 ≦ y ≦ 0.5, 0 ≦ z ≦ 0.3, and y > z when the total of Li and M 1 is 2 or when the total of Li and M is 2.)

Description

[Technical Field]

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

[0002] Light-emitting devices that emit light intensity in the wavelength range from red light to near-infrared light are desired for use as light sources for plant cultivation and growth, for example. In addition to the above uses, light-emitting devices that emit light intensity in the wavelength range from red light to near-infrared light are desired for use in infrared cameras, infrared communications, vein authentication (a type of biometric authentication), and food component analysis equipment for non-destructively measuring the sugar content of fruits and vegetables. Light-emitting devices that emit light in the visible light wavelength range as well as the red light to near-infrared wavelength range are also desired. One example of such a light-emitting device is one that combines a light-emitting diode (LED) and a phosphor.

[0003] Patent Document 1 describes a phosphor that can also be used in the aforementioned light-emitting device, having an emission peak wavelength in the wavelength range of 680 nm to 760 nm, and having a composition of CaYAlO4:Mn 4+ A phosphor represented by [the given formula] is disclosed. As a phosphor suitable for each of the above-mentioned applications, for example, there may be a need for a phosphor that emits red light to near-infrared light and emits light with higher emission intensity. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 2020-528486 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present disclosure aims 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 upon irradiation 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-q M 1 q )2(Zn 1-r M 2 r ) s (Ga 1-t M 3 t ) u (Ge 1-v M 4 v ) w O x :Cr y ,M 5 z (1) (In the formula (1), M 1 is at least one element selected from the group consisting of Na, K, Rb, and Cs, M 2 is at least one element selected from the group consisting of Mg, Ca, Sr, and Ba, M 3 is at least one element selected from the group consisting of Al, Sc, and In, M 4 is at least one element selected from the group consisting of Si, Ti, Zr, Sn, and Hf, M 5 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, q, r, s, t, u, v, w, and x are respectively 0 ≦ q ≦ 0.5, 0 ≦ r ≦ 1.0, 0 ≦ s ≦ 4.0, 0 ≦ t ≦ 1.0, 5 ≦ u ≦ 10, 0 ≦ v ≦ 1.0, 0.5 ≦ w ≦ 5.0, 10 ≦ x ≦ 30, y and z satisfy 0.02 ≦ y ≦ 0.5, 0 ≦ z ≦ 0.3, and y > z when the total of Li is 2 or when the total of Li and M 1 is 2.) 1

[0007] The second aspect is a light-emitting device including the oxide phosphor and a light-emitting element that emits light having an emission peak wavelength within the range of 365 nm or more and 650 nm or less and irradiates the oxide phosphor.​ [Effects of the Invention]

[0008] According to one aspect of this disclosure, an oxide phosphor and a light-emitting device can be provided that emit light having an emission peak wavelength in the wavelength range of red light to near-infrared light, from 680 nm to 1500 nm, upon irradiation with excitation light. [Brief explanation of the drawing]

[0009] [Figure 1] Figure 1 is a schematic cross-sectional view showing a first example configuration of a light-emitting device. [Figure 2] Figure 2 is a schematic cross-sectional view showing another example of the first configuration of the light-emitting device. [Figure 3] Figure 3 is a schematic plan view showing a second configuration example of the light-emitting device. [Figure 4] Figure 4 is a schematic cross-sectional view showing a second example configuration of the light-emitting device. [Figure 5] Figure 5 shows the emission spectra of the oxide phosphors according to Examples 1 and 2, and the emission spectrum of the oxide phosphor according to Comparative Example 1. [Figure 6] Figure 6 shows the emission spectra of oxide phosphors according to Examples 3 and 4. [Figure 7] Figure 7 shows the emission spectra of oxide phosphors related to Examples 5 and 6. [Figure 8] Figure 8 shows the emission spectra of oxide phosphors related to Examples 7 and 8. [Figure 9] Figure 9 shows the emission spectra of oxide phosphors related to Examples 9 and 10. [Figure 10] Figure 10 shows the emission spectra of oxide phosphors related to Examples 11 and 12. [Figure 11] Figure 11 shows the emission spectra of oxide phosphors related to Examples 13, 14, and 15. [Figure 12] Figure 12 shows the emission spectra of oxide phosphors related to Examples 16, 17, and 18. [Figure 13]Figure 13 shows the emission spectra of oxide phosphors related to Examples 19 and 20. [Modes for carrying out the invention]

[0010] The oxide phosphor and light-emitting device relating to this disclosure will be described below. However, the embodiments shown below are illustrative examples for realizing 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. Regarding visible light, the relationship between color names and chromaticity coordinates, the relationship between the wavelength range of light and the color names of monochromatic light, etc., will be in accordance with JIS Z8110.

[0011] Light-emitting devices using phosphors are required to emit light within an optimal wavelength range depending on the object being viewed and the usage situation. For example, in medical settings, it is sometimes necessary to easily obtain information about the inside of a living organism. The inside of a living organism contains light absorbers such as water, hemoglobin, and melanin. For example, hemoglobin has a high absorption rate of light in the visible light wavelength range with a wavelength of less than 650 nm. Therefore, with light-emitting devices that emit light in the visible light wavelength range, it is difficult for light in the visible light wavelength range to penetrate into the living organism, making it difficult to obtain information about the inside of a living organism. If it is possible to irradiate with light in a wavelength range in which light absorption and scattering in living tissue are small, it becomes easier to obtain information about the deeper parts of the living organism. For this reason, there is a need for light-emitting devices that can emit light in a wavelength range called the "living window" in which light easily penetrates into the living organism. The wavelength range from approximately 650 nm to 950 nm is sometimes called the "first biological window," the wavelength range from approximately 1000 nm to 1350 nm is called the "second biological window," and the wavelength range from approximately 1500 nm to 1800 nm is sometimes called the "third biological window." If it is possible to irradiate with light in a wavelength range in which light absorption and scattering in biological tissues are small, it becomes easier to obtain information about the deeper parts of the body. For example, if it is possible to measure the increase or decrease in oxygen concentration in the blood of a body by measuring the increase or decrease in light absorption of hemoglobin, which binds to oxygen, then it becomes possible to easily obtain information about the inside of the body by irradiating with light from a light-emitting device. Furthermore, if information about the deep parts of the body can be obtained by irradiating with light from phosphors and light-emitting elements, rather than by irradiation with X-rays, then it is possible to obtain information about the inside of the body more safely. For this reason, phosphors used in light-emitting devices are sometimes required to have emission peak wavelengths in the wavelength range from red light to near-infrared light. The phosphors used in light-emitting devices may require phosphors that emit light with a peak emission wavelength in the range of 680 nm to 1500 nm, preferably 700 nm to 1500 nm, or phosphors that emit light with 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 with 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 can visualize deeper parts of the body more clearly and is highly safe.Furthermore, in a light-emitting device including a light-emitting element and a phosphor, if a phosphor with high emission intensity that can emit high-power light is provided, the detection capability can be further enhanced, making it easier to obtain information from within the body.

[0012] In the fields of agriculture and food, there is a demand for non-destructive refractometers that can measure the sugar content of agricultural products and fruits and vegetables non-destructively, and measuring instruments that can perform non-destructive taste tests on products such as rice (e.g., a taste meter (registered trademark)). Near-infrared spectroscopy is sometimes used as a non-destructive method to measure internal quality such as sugar content, acidity, ripeness, and internal damage of fruits and vegetables, as well as surface quality that appears on the surface of the peel or the surface layer of the peel near the surface, such as abnormal drying. Near-infrared spectroscopy involves irradiating fruits and vegetables with light in the near-infrared wavelength range, and measuring the quality of the fruits and vegetables by receiving the transmitted light that passes through the fruits and vegetables and the reflected light that is reflected by the fruits and vegetables, and observing the decrease in light intensity (light absorption). Light sources such as tungsten lamps and xenon lamps are used in the analytical instruments for near-infrared spectroscopy used in the food field. The general rules for near-infrared spectroscopy in JIS K0134 state that near-infrared refers to the wavelength range of 700 nm to 2500 nm.

[0013] Furthermore, amidst environmental changes such as climate change, there is a need to ensure a stable supply of vegetables and other plants and to improve the efficiency of plant production. Plant factories, which allow for artificial control, can stably supply safe vegetables to the market and are expected to be a next-generation industry. Such plant factories require light-emitting devices that emit light that can promote plant growth. The plant's response to light can be divided into photosynthesis and photomorphogenesis. Photosynthesis is a reaction that uses light energy to break down water, generate oxygen, and fix carbon dioxide into organic matter, and is a reaction necessary for plant growth. Photomorphogenesis is a morphological reaction that uses light as a signal to perform seed germination, differentiation (germination formation, leaf formation, etc.), movement (stomatal opening and closing, chloroplast movement), and light refraction. It has been found that light in the wavelength range of 690 nm to 800 nm affects the photoreceptors of plants for photomorphogenesis. Therefore, light-emitting devices used in plant factories and similar facilities are sometimes required to be able to emit light within a wavelength range that affects plant photoreceptors (chlorophyll a, chlorophyll b, carotenoids, phytochrome, cryptochrome, and phototropin) and promote plant growth.

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

[0015] Furthermore, there are cases where a light-emitting device is required that emits light in the wavelength range from red light to near-infrared light, as well as light in the wavelength range of 365 nm to less than 700 nm. For example, in addition to obtaining internal information of living organisms or fruits and vegetables, it may be necessary to emit light in the visible light wavelength range to improve the visibility of the target object.

[0016] The oxide phosphor has a composition represented by the following formula (1). (Li 1-q M 1 q )2(Zn 1-r M 2r ) s (Ga 1-t M 3 t ) u (Ge 1-v M 4 v ) w O x :Cr y M 5 z (1) (In the above formula (1), M 1 is at least one element selected from the group consisting of Na, K, Rb, and Cs, and M 2 is at least one element selected from the group consisting of Mg, Ca, Sr, and Ba, and M 3 is at least one element selected from the group consisting of Al, Sc, and In, and M 4 is at least one element selected from the group consisting of Si, Ti, Zr, Sn, and Hf, and M 5 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, where q, r, s, t, u, v, w, and x are 0≦q≦0.5, 0≦r≦1.0, 0≦s≦4.0, 0≦t≦1.0, 5≦u≦10, 0≦v≦1.0, 0.5≦w≦5.0, 10≦x≦30, and y and z are when Li is set to 2 or Li and M 1 When the sum of is 2, the Li or the Li and the M 1 For the sum of the terms, the following conditions are met: 0.02 ≤ y ≤ 0.5, 0 ≤ z ≤ 0.3, and y > z.

[0017] In this specification, "molar ratio" refers to the ratio of each element in 1 mole of the chemical composition of the phosphor, unless otherwise specified. In this specification, multiple elements separated by commas (,) in a composition formula mean that at least one of these multiple elements is contained in the composition. In this specification, in a composition formula representing the composition of a phosphor, the elements before the colon (:) represent the elements constituting the matrix crystal and their molar ratios, and the elements after the colon (:) represent the activating elements. In this specification, in the composition represented by formula (1) above, "M 1 "M2 ", "M 3 ", "M 4 " and "M 5 " may each be represented as "element M 1 ", "element M 2 ", "element M 3 ", "element M 4 ", "element M 5 ".

[0018] The oxide phosphor having the composition represented by the formula (1) contains Cr, which is an activating element, in the formula (1). In the formula (1) of the oxide phosphor, the variable y representing the molar ratio of Cr, which is an activating element, satisfies the range of 0.02 or more and 0.5 or less (0.02 ≤ t ≤ 0.5) with respect to Li when Li is 2 or the total of Li and M 1 when the total of is 2, and preferably satisfies the range of 0.02 or more and 0.4 or less (0.02 ≤ y ≤ 0.4), more preferably satisfies the range of more than 0.02 and 0.3 or less (0.02 < y ≤ 0.3), still more preferably satisfies the range of more than 0.02 and 0.2 or less (0.02 < y ≤ 0.2), and particularly preferably satisfies the range of 0.025 or more and 0.18 or less (0.025 ≤ y ≤ 0.18). In the formula (1) of the oxide phosphor, when the total of Li or Li and M 1 is 2, if the variable y representing the molar ratio of Cr, which is an activating element, satisfies the range of 0.02 or more and 0.5 or less (0.02 ≤ y ≤ 0.5) with respect to the total of Li or Li and M 1 then the oxide phosphor can emit light with higher emission intensity in the wavelength range from red light to near-infrared light upon irradiation with excitation light. 1

[0019] ​The oxide phosphor having the composition represented by formula (1) preferably emits light having an emission peak wavelength in the emission spectrum of 680 nm to 1500 nm when irradiated with excitation light, more preferably emits light having an emission peak wavelength in the emission spectrum of 680 nm to 1400 nm, even more preferably emits light having an emission peak wavelength in the emission spectrum of 680 nm to 1200 nm, even more preferably has an emission peak wavelength in the emission spectrum of 680 nm to 1000 nm, and particularly preferably has an emission peak wavelength in the emission spectrum of 680 nm to 900 nm. The excitation light may also be light having an emission peak wavelength in the emission spectrum of 365 nm to 650 nm. When the emission spectrum of the oxide phosphor emits light having an emission peak wavelength in the emission spectrum of 680 nm to 1500 nm when irradiated with excitation light, it can be used in light-emitting devices for obtaining information from living organisms, light-emitting devices for obtaining information from agricultural products and fruits and vegetables non-destructively, and light-emitting devices for promoting the growth of plants such as vegetables.

[0020] The oxide phosphor has a composition represented by formula (1), and preferably the full width at half maximum of the emission spectrum having an emission peak wavelength is in the range of 5 nm to 250 nm, more preferably in the range of 7 nm to 250 nm, even more preferably in the range of 15 nm to 250 nm, even more preferably in the range of 40 nm to 250 nm, and particularly preferably in the range of 40 nm to 245 nm. In this specification, full width at half maximum (FMAX) refers to the wavelength range in the emission spectrum where the emission intensity is 50% of the emission intensity at the emission peak wavelength that shows the maximum emission intensity. In living organisms, light absorption and scattering occur, and in order to measure subtle changes in the propagation behavior of light in the blood within the body, it is preferable to irradiate with light that has a broad FMAX of emission spectrum with an emission peak wavelength. Also, when non-destructively measuring information about agricultural products and fruits and vegetables, it is preferable to irradiate with light that has a broad FMAX of emission spectrum with an emission peak wavelength in order to obtain information about the inside of agricultural products and fruits and vegetables. Furthermore, the way in which the color of an object appears when irradiated with light (hereinafter also referred to as "color rendering") is desirable if the emission spectrum has a wide wavelength range, and a broad FMAX allows for the emission of light with superior color rendering. For example, when used in places where work is performed, such as factories, it may be necessary to emit light that does not disrupt the spectral balance of light so that workers can work easily.

[0021] The oxide phosphor, in the composition represented by formula (1), preferably has an emission peak wavelength in the range of 700 nm to 900 nm, and more preferably has an emission peak wavelength in the range of 710 nm to 890 nm. When an oxide phosphor having the composition represented by formula (1) is irradiated with excitation light, if it emits light with an emission peak wavelength in the range of 700 nm to 900 nm, or if it emits light with an emission peak wavelength in the range of 700 nm to 1500 nm, it can be used in light-emitting devices for obtaining information from living organisms, light-emitting devices for obtaining information from agricultural products and fruits and vegetables non-destructively, or light-emitting devices for promoting the growth of plants such as vegetables.

[0022] The oxide phosphor having the composition represented by formula (1) is an oxide phosphor having the composition represented by the following formula (a), wherein part or all of the Ga in the composition is Zn, element M 2 , element M 3 , Ge and element M 4By being substituted with one or more elements selected from the group consisting of the following, Ga in the composition represented by formula (a) below can emit light with a higher emission intensity in the wavelength range from red light to near-infrared light when irradiated with excitation light than oxide phosphors having the composition represented by formula (a) below which Ga is not substituted with other elements. In the oxide phosphor having the composition represented by formula (1), a portion of Ga in the composition represented by formula (a) below is replaced with Zn, element M 2 , element M 3 , Ge and element M 4 It is unclear why substituting with one or more elements selected from the group consisting of the above results in a higher emission intensity than oxide phosphors having the composition represented by formula (a) below. It is presumed that in oxide phosphors having the composition represented by formula (1), some or all of the Ga in the composition represented by formula (a) below is replaced with Zn and / or Ge, which are highly reactive and therefore react easily at relatively low temperatures (for example, 1200°C to 1600°C, preferably 1200°C to 1500°C), thereby improving crystallinity and enabling the emission of light with higher emission intensity upon irradiation with excitation light. Furthermore, in oxide phosphors having the composition represented by formula (1), some or all of the Ga in the composition represented by formula (a) below is replaced with Zn, element M 2 , element M 3 , Ge and element M 4 It is hypothesized that the crystal's symmetry changes when it is substituted with one or more elements selected from the group consisting of the elements M. This change in crystal symmetry allows for a more appropriate arrangement of the activating element Cr in the crystal structure and reduces the likelihood of concentration quenching, thereby enabling the emission of light with higher emission intensity upon irradiation with excitation light. 2 is at least one element selected from the group consisting of Mg, Ca, Sr, and Ba. 4 is at least one element selected from the group consisting of Si, Ti, Zr, Sn, and Hf. (Li 1-aq M a1 aq )Ga5O8:Cr ay ,Ma a5 az (a) In the formula (a), M a1 is at least one element selected from the group consisting of Na, K, Rb, and Cs, and M a5 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb. aq satisfies 0 ≦ aq ≦ 0.5, and ay and az are Li or Li and M a1 such that when the total of Li or Li and M a1 is 1, 0.02 ≦ ay ≦ 0.5, 0 ≦ az ≦ 0.3, and ay > az are satisfied.

[0023] The oxide phosphor having the composition represented by the formula (1) has a composition in which a part of Ga in the composition is replaced with one or more elements selected from the group consisting of Zn, element M 2 element M 3 element M 4 Ge, and element M

[0024]

[0025]

[0026]

[0027] 2 In the composition represented by the formula (1), the oxide phosphor may not contain Mg in element M 2 In the composition represented by the formula (1), element M 2 may be at least one selected from the group consisting of Ca, Sr, and Ba. When the oxide phosphor does not contain Mg in element M 2 in the composition represented by the formula (1), it is preferable that the variable r representing the molar ratio of element M 2However, r may be at least one selected from the group consisting of Ca, Sr, and Ba, and r may satisfy 0 ≤ r ≤ 0.5.

[0026] The oxide phosphor has a composition represented by formula (1) above, in which element M 2 It does not have to include element M 2 The variable r, which represents the molar ratio, may be 0 (r=0). The oxide phosphor has a composition represented by formula (1) above, in which element M 2 It does not contain element M 2 If the variable r, which represents the molar ratio of Ge or Ge and M, is 0, then Ge or Ge and M 4 The sum of the values ​​of the molecules is defined by a variable w representing the molar ratio, which is in the range of 0.5 to 5.0 (0.5 ≤ w ≤ 5.0), and may also be in the range of 0.6 to 4.0 (0.6 ≤ w ≤ 4.0), or in the range of 0.8 to 3.0 (0.8 ≤ w ≤ 3.0).

[0027] The oxide phosphor, in the composition represented by formula (1), contains Zn and element M 2 It does not contain Mg, or the element M 2 If it does not contain Ge or element M 4 Or Ge and element M 4 The sum of the molars can be in the range of 1.3 to 3.2 (1.3 ≤ w ≤ 3.2) or in the range of 1.5 to 3.0 (1.5 ≤ w ≤ 3.0).

[0028] The oxide phosphor may have a composition represented by the following formula (1a), which is included in the composition represented by formula (1). (Li 1-q M 1 q )2Zn s (Ga 1-t M 3 t ) u (Ge 1-v M 4 v ) w O x :Cr y M 5 z (1a) In the above formula (1a), M1 is at least one element selected from the group consisting of Na, K, Rb, and Cs, and M 3 is at least one element selected from the group consisting of Al, Sc, and In, and M 4 is at least one element selected from the group consisting of Si, Ti, Zr, Sn, and Hf, and M 5 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and q, s, t, u, v, w, and x may be 0≦q≦0.5, 1.0≦s≦4.0, preferably 1.0≦s≦3.5, 0≦t≦1.0, 5≦u≦10, 0≦v≦1.0, 0.5≦w≦5.0, preferably 0.8≦w≦3.2, 0, 10≦x≦30, and y and z are when Li is set to 2 or Li and M 1 When the sum of these is 2, Li or Li and M 1 For the sum of the terms, the following conditions are met: 0.02 ≤ y ≤ 0.5, 0 ≤ z ≤ 0.3, and y > z.

[0029] The oxide phosphor, in the composition represented by formula (1), contains Zn and element M 2 It does not contain Mg, or the element M 2 If it does not contain, the full width at half maximum of the emission spectrum having the emission peak wavelength is preferably in the range of 40 nm to 250 nm, more preferably in the range of 50 nm to 245 nm, even more preferably in the range of 60 nm to 245 nm, and particularly preferably in the range of 70 nm to 245 nm. Oxide phosphors can be used in light-emitting devices for obtaining information from living organisms, light-emitting devices for obtaining information from agricultural products and fruits and vegetables non-destructively, and light-emitting devices for promoting the growth of plants such as vegetables, as the full width at half maximum of the emission spectrum having the emission peak wavelength is in the range of 40 nm to 250 nm.

[0030] The oxide phosphor, in the composition represented by formula (1), contains Zn and element M 2 It does not contain Mg, or the element M 2 Does not contain Ge or element M 4Or Ge and element M 4 When the variable w, which represents the molar ratio in the sum of the elements, is within the range of 1.3 to 3.2 (1.3 ≤ w ≤ 3.2), it is preferable that the total width at half maximum of the emission spectrum having the emission peak wavelength is within the range of 190 nm to 250 nm, more preferably within the range of 200 nm to 245 nm, and even more preferably within the range of 205 nm to 245 nm. Oxide phosphors, by having a wider total width at half maximum of 190 nm to 250 nm in the emission spectrum having the emission peak wavelength, can be used in light-emitting devices that can obtain information from living organisms, agricultural products and fruits and vegetables non-destructively, and light-emitting devices that emit light to promote the growth of plants such as vegetables.

[0031] The oxide phosphor, in the composition represented by formula (1), contains Zn and element M 2 It does not contain Mg, or the element M 2 If it does not contain [the specified element], it is preferable that the emission spectrum has an emission peak wavelength in the range of 700 nm to 900 nm, and preferably in the range of 710 nm to 890 nm. When an oxide phosphor emits light with an emission peak wavelength in the range of 700 nm to 900 nm in its emission spectrum upon irradiation with excitation light, it can be used in light-emitting devices for obtaining information from living organisms, light-emitting devices for obtaining information from agricultural products and fruits and vegetables non-destructively, and light-emitting devices for promoting the growth of plants such as vegetables.

[0032] The oxide phosphor, in the composition represented by formula (1), contains Zn and element M 2 It does not contain Mg, or the element M 2 Does not contain Ge or element M 4 Or Ge and element M 4When the variable w, which represents the molar ratio in the total, is within the range of 1.3 to 3.2 (1.3 ≤ w ≤ 3.2), it is preferable that the emission peak wavelength in the emission spectrum is in the range of 750 nm to 900 nm, preferably in the range of 770 nm to 890 nm, and even more preferably in the range of 780 nm to 885 nm. Oxide phosphors, upon irradiation with excitation light, emit light in the emission spectrum having an emission peak wavelength in the range of 750 nm to 900 nm and within the wavelength range of near-infrared light, making it easier to obtain information from living organisms, agricultural products and fruits and vegetables non-destructively. They can be used in light-emitting devices that can obtain this information, or light-emitting devices that emit light to promote the growth of plants such as vegetables.

[0033] In the oxide phosphor, in the composition represented by formula (1), s and v may satisfy s=0 and v=0, respectively. In the oxide phosphor, in the composition represented by formula (1), if s is 0 (s=0), then Zn and element M may be present in the composition represented by formula (1). 2 It does not contain. In the composition represented by formula (1), if v=0, the oxide phosphor contains element M. 4 It does not include.

[0034] The oxide phosphor may have a composition represented by the following formula (1b), which is included in the composition represented by formula (1). (Li 1-q M 1 q )2(Ga 1-t M 3 t ) u Ge w O x :Cr y M 5 z (1b) In the above formula (1b), M 1 is at least one element selected from the group consisting of Na, K, Rb, and Cs, and M 3is at least one element selected from the group consisting of Al, Sc, and In, and M 5 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, where q, t, u, w, and x are 0≦q≦0.5, 0≦t≦1.0, 5≦u≦10, 0.5≦w≦5.0, preferably 0.8≦w≦3.2, 1.0≦w≦3.0, 10≦x≦30, preferably 12≦x≦20, and y and z are when Li is set to 2 or Li and M 1 When the sum of these is 2, Li or Li and M 1 For the sum of the terms, the following conditions are met: 0.02 ≤ y ≤ 0.5, 0 ≤ z ≤ 0.3, and y > z.

[0035] The oxide phosphor has a composition represented by formula (1) above, where s and v satisfy s=0 and v=0, respectively, and contains Zn and element M 2 It does not contain element M 4 If it does not contain [the specified element], the full width at half maximum (FMAX) of the emission spectrum having the emission peak wavelength is preferably in the range of 190 nm to 240 nm, more preferably in the range of 200 nm to 235 nm, and even more preferably in the range of 210 nm to 230 nm. Oxide phosphors have a wider FMAX value, such as the emission spectrum having the emission peak wavelength being in the range of 190 nm to 240 nm, which makes it easier to obtain information from living organisms, agricultural products and fruits and vegetables non-destructively, and can be used in light-emitting devices that can obtain this information, or light-emitting devices that emit light to promote the growth of plants such as vegetables.

[0036] The oxide phosphor has a composition represented by formula (1) above, where s and v satisfy s=0 and v=0, respectively, and contains Zn and element M 2 It does not contain element M 4If it does not contain [the specified element], it is preferable that the emission peak wavelength in the emission spectrum is in the range of 800 nm to 860 nm, more preferably in the range of 810 nm to 850 nm, and even more preferably in the range of 820 nm to 840 nm. Oxide phosphors, upon irradiation with excitation light, emit light having an emission peak wavelength in the emission spectrum within the range of 800 nm to 860 nm and within the wavelength range of near-infrared light, making it easier to obtain information from living organisms, agricultural products and fruits and vegetables non-destructively. They can be used in light-emitting devices that can obtain this information, or light-emitting devices that emit light to promote the growth of plants such as vegetables.

[0037] In the composition represented by formula (1), the oxide phosphor may satisfy s=0 and v=1.0, respectively. In the composition represented by formula (1), if s is 0 (s=0), the oxide phosphor may contain Zn and element M in the composition represented by formula (1). 2 It does not contain. When the oxide phosphor satisfies v=1.0 in the composition represented by formula (1), it does not contain Ge in the composition represented by formula (1). The oxide phosphor, in the composition represented by formula (1), contains element M 4 It is possible that is Si, and s and v satisfy s=0 and v=1.0, respectively.

[0038] The oxide phosphor may have a composition represented by the following formula (1c), which is included in the composition represented by formula (1). (Li 1-q M 1 q )2(Ga 1-t M 3 t ) u M 4 w O x :Cr y M 5 z (1c) In the above formula (1c), M 1is at least one element selected from the group consisting of Na, K, Rb, and Cs, and M 3 is at least one element selected from the group consisting of Al, Sc, and In, and M 4 is at least one element selected from the group consisting of Si, Ti, Zr, Sn, and Hf, and M 4 Si is also acceptable, M 5 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, where q, t, u, w, and x are 0≦q≦0.5, 0≦t≦1.0, 5≦u≦10, 0.5≦w≦5.0, preferably 0.8≦w≦3.2, 1.0≦w≦3.0, 10≦x≦30, preferably 12≦x≦20, and y and z are when Li is set to 2 or Li and M 1 When the sum of these is 2, Li or Li and M 1 For the sum of the terms, the following conditions are met: 0.02 ≤ y ≤ 0.5, 0 ≤ z ≤ 0.3, and y > z.

[0039] The oxide phosphor may have a composition represented by the following formula (1c-1), which is included in the composition represented by formula (1). (Li 1-q M 1 q )2(Ga 1-t M 3 t ) u Si w O x :Cr y M 5 z (1c-1) In the above formula (1c-1), M 1 is at least one element selected from the group consisting of Na, K, Rb, and Cs, and M 3 is at least one element selected from the group consisting of Al, Sc, and In, and M 5is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, where q, t, u, w, and x are 0≦q≦0.5, 0≦t≦1.0, 5≦u≦10, 0.5≦w≦5.0, preferably 0.8≦w≦3.2, 1.0≦w≦3.0, 10≦x≦30, preferably 12≦x≦20, and y and z are when Li is set to 2 or Li and M 1 When the sum of these is 2, Li or Li and M 1 For the sum of the terms, the following conditions are met: 0.02 ≤ y ≤ 0.5, 0 ≤ z ≤ 0.3, and y > z.

[0040] The oxide phosphor has a composition represented by formula (1) above, in which element M 4 The element is Si, and s and v satisfy s=0 and v=1.0, respectively, and Zn and element M 2 If it does not contain [the specified element], the full width at half maximum (FMAX) of the emission spectrum having the emission peak wavelength is preferably 30 nm or less, more preferably 20 nm or less, and may be 5 nm or more. When the oxide phosphor has an emission spectrum having the emission peak wavelength with a FMAX of 30 nm or less, the FMAX is in a relatively narrow range, and even when used in places where work is performed, such as factories, it can emit light that does not disrupt the spectral balance of light, making it easy for workers to perform their tasks.

[0041] The oxide phosphor has a composition represented by formula (1) above, in which element M 4 The element is Si, and s and v satisfy s=0 and v=1.0, respectively, and Zn and element M 2If it does not contain [the specified element], it is preferable that the emission peak wavelength in the emission spectrum is in the range of 690 nm to 720 nm, and more preferably in the range of 700 nm to 720 nm. When irradiated with excitation light, the oxide phosphor emits light having an emission peak wavelength in the emission spectrum in the range of 690 nm to 720 nm, and an emission peak wavelength within the wavelength range of red light to near-infrared light. When used in light-emitting devices to obtain information about agricultural products and fruits and vegetables in vivo or non-destructively, or in light-emitting devices to promote the growth of plants such as vegetables, it can emit light that does not disrupt the spectral balance of light, making it easy for operators to work with.

[0042] The oxide phosphor has a composition represented by formula (1) above, in which element M 2 It contains Mg, 2 In addition to Mg, it may also contain at least one element selected from the group consisting of Ca, Sr, and Ba. The oxide phosphor has a composition represented by formula (1) above, in which element M 2 is Mg, and r may be 1 (r=1.0). In the composition represented by formula (1) above, if r is 1 (r=1.0), Zn is not included. In the composition represented by formula (1) above, if r is 1 (r=1.0), element M 2 It is preferable that it contains Mg, and element M 2 In addition to Mg, it may also contain at least one element selected from the group consisting of Ca, Sr, and Ba.

[0043] The oxide phosphor has a composition represented by formula (1) above, in which element M 2When the material contains Mg and r is 1.0 (r=1.0), it is preferable that the full width at half maximum (FMAX) of the emission spectrum having the emission peak wavelength be in the range of 50 nm to 130 nm, and more preferably in the range of 50 nm to 125 nm. When the oxide phosphor has an emission spectrum having an emission peak wavelength that is in the range of 50 nm to 130 nm, the FMAX is in a relatively narrow range, and even when used in places where work is performed, such as factories, it can emit light that does not disrupt the spectral balance of light, making it easy for workers to work.

[0044] The oxide phosphor has a composition represented by formula (1) above, in which element M 2 When the oxide phosphor contains Mg and r is 1.0 (r=1.0), it is preferable that the emission peak wavelength in the emission spectrum is in the range of 680 nm to 730 nm, and more preferably in the range of 690 nm to 730 nm. When the oxide phosphor is irradiated with excitation light, it emits light in which the emission peak wavelength in the emission spectrum is in the range of 680 nm to 730 nm. When used in a light emission device to obtain information about agricultural products and fruits and vegetables in vivo or non-destructively, or in a light emission device to promote the growth of plants such as vegetables, it can emit light that does not disrupt the spectral balance of light, making it easy for the operator to work with.

[0045] The light-emitting device comprises 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 included in a wavelength conversion member, and the wavelength conversion member may include a light-transmitting material.

[0046] 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. As materials for the semiconductor structure constituting the light-emitting element, In X Al Y Ga 1-X-YA range such as N(0≦X≦1, 0≦Y≦1, X+Y≦1) can be used. As a material for a light-emitting element that emits red light, for example, a gallium-aluminum-arsenide semiconductor or an aluminum-indium-gallium-phosphorus semiconductor can be selected. As a light-emitting element, it is preferable to use, for example, an LED chip or an LD chip.

[0047] The light-emitting element may have an emission peak wavelength in the range of 365 nm to 650 nm, or it may have an emission peak wavelength in the range of 365 nm to 500 nm, or it may have an emission peak wavelength in the range of 370 nm to 490 nm, or it may have an emission peak wavelength in the range of 375 nm to 480 nm. Furthermore, the light-emitting element may have an emission peak wavelength in the range of 500 nm to 650 nm, or it may have an emission peak wavelength in the range of 510 nm to 650 nm, or it 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 an oxide phosphor, it is possible to construct a light-emitting device that emits mixed light in a desired wavelength range of light from the light-emitting element and fluorescence from a phosphor containing an oxide phosphor. 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 made of nitride semiconductor as the excitation light source, it is possible to obtain a stable light-emitting device that is highly efficient, has high linearity of output to input, and is resistant to mechanical shock.

[0048] The light-emitting device requires a first phosphor containing the oxide phosphor described above, and may also contain phosphors having different compositions. Preferably, in addition to the first phosphor, the light-emitting device comprises at least one phosphor selected from the group consisting of a second phosphor having an emission peak wavelength in the range of 455 nm to less than 495 nm in the emission spectrum of the phosphor, a third phosphor having an emission peak wavelength in the range of 495 nm to less than 610 nm, a fourth phosphor having an emission peak wavelength in the range of 610 nm to less than 700 nm, and a fifth phosphor having an emission peak wavelength in the range of 700 nm to 1600 nm. The light-emitting device comprises a light-emitting element and a first phosphor containing the oxide phosphor described above, and at least one phosphor selected from the group consisting of the second phosphor, third phosphor, fourth phosphor, and fifth phosphor, and can be used as a light source that emits light having an emission spectrum in a wavelength range including visible light to a part of near-infrared light. The light-emitting device has an emission spectrum similar to that of conventionally used tungsten and xenon lamps, and can be used as a light source that is smaller than tungsten and xenon lamps. A small light-emitting device can be mounted on small mobile devices such as smartphones and smartwatches, and if biological information can be obtained, it can be used for health management and other purposes. The light-emitting device can be used, for example, in reflection spectroscopy measuring devices, or in lighting devices that require light with excellent color rendering that can non-destructively measure living organisms or fruits and vegetables.

[0049] 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 the composition represented by the following formula (2a), an aluminate phosphor having the composition represented by the following formula (2b), and an aluminate phosphor having the 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)

[0050] The third phosphor preferably includes at least one phosphor selected from the group consisting of a silicate phosphor having a composition represented by formula (3a), an aluminate phosphor or galliumate phosphor having a composition represented by formula (3b), a β-sialon phosphor having a composition represented by formula (3c), a cesium lead halide phosphor having a composition represented by formula (3d), and a nitride phosphor having a composition represented by formula (3e), and may include two or more phosphors. If the third phosphor includes two or more phosphors, it is preferable that each of the two or more third phosphors has an emission peak wavelength in a different range within the range of 495 nm to less than 610 nm. (Ca,Sr,Ba)8MgSi4O 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)

[0051] 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)

[0052] The fifth phosphor is a gallium salt 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 has a different composition from the oxide phosphors above, a phosphor having a composition represented by the following formula (5d) which has a different composition from the oxide phosphors above, a phosphor having a composition represented by the following formula (5e) which has a different composition from the oxide phosphors above, a phosphor having a composition represented by the following formula (5f) which has a different composition from the oxide phosphors above, a phosphor having a composition represented by the following formula (5g) which has a different composition from the oxide phosphors above, a phosphor having a composition represented by the following formula (5h) which has a different composition from the oxide phosphors above, and a phosphor having a composition represented by the following formula (5h) which has a different composition from the oxide phosphors above Preferably, the material contains at least one phosphor selected from the group consisting of a phosphor having a composition represented by the following formula (5i) that is different from the oxide phosphor, a phosphor having a composition represented by the following formula (5j) that is different from the oxide phosphor, a phosphor having a composition represented by the following formula (5k) that is different from the oxide phosphor, a phosphor having a composition represented by the following formula (5l) that is different from the oxide phosphor, a phosphor having a composition represented by the following formula (5m) that is different from the oxide phosphor, a phosphor having a composition represented by the following formula (5n) that is different from the oxide phosphor, and a phosphor having a composition that is different from the oxide phosphor or has a composition represented by the following formula (5o). It may also contain two or more phosphors.

[0053] ZnGa2O4:Cr (5a) (Lu,Y,Gd,Tb)3(Al,Ga)5O 12 :Ce,Cr (5b)

[0054] M 8 g M 9 h M 10 i M 11 50 j :Cr e M 12 f (5c) (In the above formula (5c), M 8is at least one element selected from the group consisting of Li, Na, K, Rb, and Cs, and M 9 is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and M 10 is at least one element selected from the group consisting of 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.)

[0055] (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 ≤ 3.0, 5 ≤ x4 ≤ 9, 0.005 ≤ y4 ≤ 1.0, 0 ≤ z4 ≤ 0.5.)

[0056] (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 above 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 (where 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 conditions, respectively: 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.)

[0057] 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, M 21 is at least one element selected from the group consisting of Group 13 elements excluding Al, and M 22 (where 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 conditions, respectively: 0.004 ≤ v6 ≤ 0.8, 0 ≤ w6 ≤ 0.4, 0.004 ≤ v6 + w6 ≤ 0.8, 1.0 ≤ x6 ≤ 4.0, 0 ≤ y6 ≤ 0.7, and 4.0 ≤ z6 ≤ 1.50.)

[0058] M 23 t7 M 24 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.)

[0059] (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(where 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 the following conditions, respectively: 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.)

[0060] (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 (where 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 conditions, respectively: 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.)

[0061] (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 M38 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 35 is 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 (where p10, q10, r10, s10, t10, u10, v10, w10, x10, y10, and z10 satisfy the following conditions, respectively: 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, and 0.9≦q10+s10+u10≦1.2.)

[0062] (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 41is at least one element selected from the group consisting of P, V, Sb, and Bi, and M 42 (where is 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 conditions, respectively: 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.)

[0063] (Ga 1-v12 M 43 v12 )2O3:Cr x12 (5L) (In the above formula (5l), M 43 (v12 and x12 satisfy 0 ≤ v12 ≤ 1.0 and 0.02 ≤ x12 ≤ 0.3, respectively.)

[0064] (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 satisfy 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, respectively.

[0065] (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, M 48 is at least one element selected from the group consisting of B, Al, In, and Sc, 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, v14, w14, x14, and y14 satisfy, respectively, 0≦t14≦0.8, 0.7≦u14≦1.3, 0≦v14<0.8, 3.7≦w14≦4.3, 0.02<x14≦0.3, 0≦y14≦0.2, x14>y14.

[0066] (Li 1-s15 M 50 s15 )(Mg 1-t15 M 51 t15 ) u15 (Ga 1-v15 M 52 v15 ) w15 O x15 :Cr y15 ,M 53 z15 (5o) It should be noted that there seems to be a small error in the original text where "<° 1-v14-x14-y14 " is likely a misrepresentation. I've translated it as " 1-v14-x14-y14 " as best as possible while maintaining the integrity of the text. If this is a specific format that needs to be corrected in a different way, more context would be helpful.(In the formula (5o), M 50 is at least one element selected from the group consisting of Na, K, Rb, and Cs, and M 51 is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, and M 52 is at least one element selected from the group consisting of Al and Sc, and M 53 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, s15, t15, u15, v15, w15, and x15 are respectively 0 ≦ s15 ≦ 0.5, 0 ≦ t15 ≦ 1.0, 0.03 ≦ u15 ≦ 10, 0 ≦ v15 ≦ 1.0, 5.1 ≦ w15 ≦ 25, 0.005 ≦ u15 / w15 ≦ 0.4, 8.2 ≦ x15 ≦ 48, y15 and z15 are when taking Li as 1 or when taking the total of Li and M 50 as 1, with respect to the total of the said Li or the said Li and the said M 50 satisfy 0.02 ≦ y15 ≦ 0.5, 0 ≦ z15 ≦ 0.3, and y15 > z15.)

[0067] An example of a light-emitting device will be described based on the drawings. FIG. 1 is a schematic cross-sectional view showing an example of a first configuration example of the light-emitting device. FIG. 2 is a schematic cross-sectional view showing another example of the first configuration example of the light-emitting device.

[0068] As shown in Figure 1, the light-emitting device 100 comprises a molded body 40 having a recess, a light-emitting element 10 which serves as an excitation light source, and a wavelength conversion member 50 which covers the light-emitting element 10. The molded body 40 is integrally molded from a first lead 20 and a second lead 30 and a resin part 42 containing a thermoplastic resin or a thermosetting resin. At least the first lead 20 and the second lead 30 of the molded body 40 constitute the bottom surface of the recess, and at least the resin part 42 constitutes 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, and these pairs of positive and negative electrodes are electrically connected to the first lead 20 and the second lead 30, respectively, via wires 60. The light-emitting element 10 is covered by the wavelength conversion member 50. Preferably, the wavelength conversion member 50 contains a phosphor 70 that converts the wavelength of light emitted from the light-emitting element 10 and a light-transmitting material. The phosphor 70 essentially includes a first phosphor 71 containing an oxide phosphor. The oxide phosphor contained in the first phosphor 71 contains an oxide phosphor having the composition represented by formula (1). The phosphor 70 may also contain phosphors with different compositions from the first phosphor 71. As shown in Figure 2, the phosphor 70 preferably contains at least one phosphor selected from the group consisting of the second phosphor 72, third phosphor 73, fourth phosphor 74, and fifth phosphor 75 described above, and may contain two or more. The phosphor 70 essentially includes the first phosphor 71 and may also contain the second phosphor 72, third phosphor 73, fourth phosphor 74, and fifth phosphor 75. The wavelength conversion member 50 also functions as a member for protecting the light-emitting element 10, wire 60, and phosphor 70, etc., from the external environment. The light-emitting device 100 emits light by receiving power from an external source via the first lead 20 and the second lead 30.

[0069] Figures 3 and 4 show a second configuration example of the light-emitting device. Figure 3 is a schematic plan view of the light-emitting device 200. Figure 4 is a schematic cross-sectional view of the light-emitting device 200 shown in Figure 3, taken along line III-III'. The light-emitting device 200 comprises 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 is excited by light from the light-emitting element 10 and emits light, and a light-transmitting body 53 disposed on the emission surface side of the wavelength converter 52. The light-emitting element 10 is flip-chip mounted on a substrate 12 via a bump which is a conductive member 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 are covered on their sides by a coating member 90 that reflects light. The wavelength converter 52 contains a phosphor that is excited by light from the light-emitting element 10. The phosphor included in the wavelength converter 52 must include a first phosphor 71 which contains an oxide phosphor. The oxide phosphor included in the first phosphor 71 contains an oxide phosphor having the composition represented by formula (1). The phosphor may also include phosphors with a different composition from the first phosphor 71. The wavelength converter 52 may include at least one selected from the group consisting of a second phosphor, a third phosphor, a fourth phosphor, and a fifth phosphor. The light-emitting element 10 can emit light from the light-emitting device 200 by receiving power from outside the light-emitting device 200 via wiring and conductive members 61 formed on the substrate 12. The light-emitting device 200 may include semiconductor elements 11 such as protective elements to prevent the light-emitting element 10 from being destroyed by the application of excessive voltage. The semiconductor elements 11 may be mounted on the substrate 12 via the conductive members 61. The covering member 90 is arranged, for example, to cover the semiconductor elements 11. The following describes each component used in the light-emitting device. Further details can be found in, for example, Japanese Patent Publication No. 2014-112635.

[0070] The light-transmitting material that constitutes the wavelength converter together with the phosphor may be at least one selected from the group consisting of resins, glass, and inorganic materials. The resin may be at least one selected from the group consisting of silicone resins, epoxy resins, phenolic resins, polycarbonate resins, acrylic resins, and modified resins thereof. Silicone resins and modified silicone resins are preferred because they have excellent heat resistance and light resistance. In addition to the phosphor and light-transmitting material, the wavelength conversion member may optionally contain fillers, colorants, and light-diffusing materials. Examples of fillers include silicon dioxide, barium titanate, titanium dioxide, and aluminum oxide.

[0071] 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. If the wavelength conversion member includes a substrate, the substrate is preferably made of an insulating material that does not easily transmit light from the light-emitting element or ambient light. Examples of substrate materials include ceramics such as aluminum oxide and aluminum nitride, and resins such as phenolic resin, epoxy resin, polyimide resin, bismaleimidotriazine resin (BT resin), and polyphthalamide (PPA) resin. If 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 placed on the wavelength conversion member.

[0072] Semiconductor elements that may be provided in the light-emitting device as needed include, for example, transistors for controlling light-emitting elements and protective elements for suppressing damage or performance degradation of light-emitting elements due to excessive voltage application. Zener diodes are an example of protective elements. If the light-emitting device is equipped with a covering member, it is preferable to use an insulating material for the covering member. More specifically, examples include phenolic resin, epoxy resin, bismaleimidotriazine 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 also use bumps as conductive members. As materials for the bumps, Au or its alloys, and as other conductive members, eutectic solder (Au-Sn), Pb-Sn, lead-free solder, etc., can be used.

[0073] An example of a method for manufacturing the light-emitting device of the first configuration example will be described. For further details, see, for example, the disclosure in Japanese Patent Application Publication 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. If an aggregate molded body having a plurality of recesses is used as the molded body, a fragmentation step of separating each unit region into resin packages may be included after the resin package formation step.

[0074] In the preparation process for the molded body, multiple leads are integrally molded using a thermosetting resin or thermoplastic resin to prepare a molded body having recesses with side and bottom surfaces. The molded body may be a molded body consisting of an aggregate substrate containing multiple recesses.

[0075] In the process of arranging the light-emitting element, the light-emitting element is placed on the bottom surface of the recess in 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.

[0076] In the process of arranging the composition for forming the wavelength conversion member, the composition for forming the wavelength conversion member is placed in the recess of the molded body.

[0077] In the resin package molding process, a wavelength conversion member forming composition placed in the recesses of the molded body is cured to form a resin package and manufacture a light-emitting device. When a molded body consisting of an aggregate substrate containing multiple recesses is used, after the resin package formation process, in the individualization process, each unit region of the aggregate substrate having multiple recesses is separated into resin packages, and individual light-emitting devices are manufactured. In this way, the light-emitting device shown in Figure 1 or Figure 2 can be manufactured.

[0078] An example of a method for manufacturing the light-emitting device of the second configuration example will be described. For further details, please refer to, for example, the disclosures in Japanese Patent Publication No. 2014-112635 or Japanese Patent Publication No. 2017-117912. The method for manufacturing the light-emitting device preferably includes a step of arranging the light-emitting element, a step of arranging the semiconductor element if necessary, 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 coating member.

[0079] For example, in the process of arranging the light-emitting element, the light-emitting element is arranged on a substrate. The light-emitting element and the semiconductor element are mounted on the substrate, for example, using a flip-chip mounting method. Next, in the process of forming a wavelength conversion member including 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 transparent material by printing, bonding, compression molding, or electrodeposition. For example, in the printing method, a wavelength conversion member including a wavelength converter can be formed by printing a wavelength conversion member composition containing a phosphor and a resin that serves as a binder or solvent onto one surface of a transparent material. Next, in the bonding process of the light-emitting element and the wavelength conversion member, the wavelength conversion member is placed facing the light-emitting surface of the light-emitting element and bonded to the light-emitting element by an adhesive layer. Next, in the process of forming a coating member, the sides of the light-emitting element and the wavelength conversion member are covered with a coating member composition. This coating member is for reflecting the light emitted from the light-emitting element, and if the light-emitting device also includes a semiconductor element, it is preferable to form the coating member so that the semiconductor element is embedded in the coating member. In this way, the light-emitting device shown in Figures 3 and 4 can be manufactured.

[0080] The method for producing oxide phosphors includes a first compound containing Li, a ninth compound containing Cr, a third compound containing Zn, and element M. 2 A fourth compound containing Ga, a fifth compound containing element M 3 A sixth compound containing , a seventh compound containing Ge, and element M 4 It comprises at least one compound selected from the group consisting of eight compounds including, and optionally contains element M 1 A second compound containing the element M may be included if necessary. 5 The method includes preparing a raw material mixture which may contain a tenth compound, 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.

[0081] The raw material mixture preferably contains a ninth compound containing Cr such that, when the molar ratio of Li or the total molar ratio of Li and element M1 in one mole of the resulting oxide phosphor is 2, the molar ratio of Cr to Li or the total of Li and element M1 is 0.02 or more and 0.5 or less.

[0082] The raw material mixture is preferably prepared by mixing each compound containing each element such that the resulting oxide phosphor satisfies the composition represented by formula (1).

[0083] The raw materials are a first compound containing Li, and element M. 1 A second compound containing Zn, a third compound containing element M 2 A fourth compound containing Ga, a fifth compound containing element M 3 A sixth compound containing [element], a seventh compound containing Ge, and element M 4 Compound 8 containing , Compound 9 containing Cr, Element M 5 The tenth compound containing is preferably at least one selected from the group consisting of oxides, carbonates, chlorides, and hydrates thereof. At least one of the first to tenth compounds is preferably an oxide, and the ninth compound containing Cr is preferably an oxide.

[0084] The raw materials are a first compound containing Li, a ninth compound containing Cr, a third compound containing Zn, and element M. 2 A fourth compound containing Ga, a fifth compound containing element M 3 A sixth compound containing , a seventh compound containing Ge, and element M 4 At least one compound selected from the group consisting of eight compounds including and optionally containing element M 1 A second compound containing and, if necessary, element M 5 The tenth compound containing the above may be mixed using a mixer to obtain a raw material mixture. In addition to ball mills commonly used in industry, vibratory mills, roll mills, jet mills, etc., can be used as mixers.

[0085] The raw material mixture may contain a flux. The inclusion of a flux in the raw material mixture promotes the reaction between the raw materials and allows for more uniform solid-phase reactions, resulting in a phosphor with larger particle size and superior luminescence properties. If the heat treatment temperature for obtaining the phosphor is approximately the same as the temperature at which the liquid phase of the compound used as the flux is formed, the flux promotes the reaction between the raw materials. As the flux, 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. Among halides, fluorides can be used as the flux. If 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, or the flux can be added after the raw materials have been mixed to achieve the desired composition.

[0086] The raw material mixture can be placed in a crucible or boat made of materials such as graphite (carbon), boron nitride (BN), alumina (Al2O3), tungsten (W), or molybdenum (Mo), and then heat-treated in a furnace.

[0087] The heat treatment is preferably carried out in an atmosphere containing oxygen. The oxygen content in the atmosphere is not particularly limited. The oxygen content in the atmosphere containing oxygen is preferably 5% by volume or more, more preferably 10% by volume or more, and still more preferably 15% by volume or more. The heat treatment is preferably carried out in an air atmosphere (oxygen content is 20% by volume or more). If the atmosphere contains no oxygen with an oxygen content of less than 1% by volume, an oxide phosphor having a desired composition may not be obtained.

[0088] The heat treatment temperature is in the range of 1200 °C or higher and 1700 °C or lower, preferably in the range of 1250 °C or higher and 1650 °C or lower, and more preferably in the range of 1260 °C or higher and 1600 °C or lower. If the heat treatment temperature is 1200 °C or higher and 1700 °C or lower, thermal decomposition is suppressed, and an oxide phosphor having the desired composition and a stable crystal structure can be obtained.

[0089] In the heat treatment, a holding time may be provided at a predetermined temperature. The holding time may be, for example, 0.5 hours or more and 48 hours or less, may be 1 hour or more and 40 hours or less, or may be 2 hours or more and 30 hours or less. By providing the holding time within the range of 0.5 hours or more and 48 hours or less, crystal growth can be promoted. <http: / / www.wipo.int / standards / XMLSchema / xsd

[0090] The pressure of the heat treatment atmosphere may be standard atmospheric pressure (0.101 MPa), may be 0.101 MPa or more, or may be carried out in a pressurized atmosphere within the range of 0.11 MPa or more and 200 MPa or less. When the heat treatment temperature of the heat-treated product obtained by the heat treatment is high, the crystal structure is likely to be decomposed, but when it is in a pressurized atmosphere, the decomposition of the crystal structure can be suppressed.

[0091] The heat treatment time can be appropriately selected depending on the heat treatment temperature and the atmospheric pressure during heat treatment, and is preferably 0.5 hours to 20 hours. Even when two or more heat treatments are performed, it is preferable that the time for each heat treatment is 0.5 hours to 20 hours. When the heat treatment time is 0.5 hours to 20 hours, the decomposition of the resulting heat-treated product is suppressed, and a phosphor with a stable crystalline structure and desired luminescence 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 hour to 10 hours, and even more preferably 1.5 hours to 9 hours.

[0092] The heat-treated product obtained by heat treatment may undergo post-treatment such as grinding, dispersion, solid-liquid separation, and drying. Solid-liquid separation can be carried out by industrially commonly used methods such as filtration, suction filtration, pressure filtration, centrifugal separation, and decantation. Drying can be carried out by industrially commonly used equipment such as vacuum dryers, hot air heating dryers, conical dryers, and rotary evaporators. [Examples]

[0093] The present invention will be described in detail below with reference to examples. The present invention is not limited to these examples.

[0094] Example 1 The raw materials are 1.1g of Li2CO3, 1.2g of ZnO, 11.3g of Ga2O3, 1.6g of GeO2, and 0.06g of Cr2O3 (the initial composition is Li2ZnGa8GeO 16 :Cr 0.026 The ingredients are weighed to obtain the raw material mixture, and then mixed using an agate mortar and pestle for approximately 10 minutes. In this specification, in the preparation composition or the composition represented by formula (1), the molar ratio of elements for which no molar ratio value is specified is 1. Also, the molar ratio of Cr or element M in the preparation composition or the composition represented by formula (1) is specified. 5 The molar ratio is Li or Li and M 1 When the sum of these is 2, Li or Li and M 1This is the molar ratio to the total. The resulting raw material mixture is placed in an alumina vessel and heat-treated for 6 hours at 1260°C in an atmospheric environment (20% oxygen by volume) at standard pressure (0.101 MPa). After heat treatment, the resulting heat-treated material is pulverized to obtain an oxide phosphor according to Example 1, which has a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 1 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 1, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 1.0 (s=1.0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 16 (x=16), the variable y is 0.026 (y=0.026), and the variable z is 0 (z=0).

[0095] Example 2 The raw materials are 1.1g of Li2CO3, 1.2g of ZnO, 11.3g of Ga2O3, 1.6g of GeO2, and 0.12g of Cr2O3 (the initial composition is Li2ZnGa8GeO 16 :Cr 0.053 Except for weighing the raw materials to obtain the raw material mixture, the process is the same as in Example 1 to obtain an oxide phosphor according to Example 2 having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 2 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 2, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 1.0 (s=1.0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 16 (x=16), the variable y is 0.053 (y=0.053), and the variable z is 0 (z=0).

[0096] Example 3 The raw materials are 1.1g of Li2CO3, 1.2g of ZnO, 11.3g of Ga2O3, 1.6g of GeO2, and 0.18g of Cr2O3 (the initial composition is Li2ZnGa8GeO 16 :Cr 0.079 Except for weighing the raw materials to obtain the raw material mixture, the process is the same as in Example 1 to obtain an oxide phosphor according to Example 3 having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 3 has the composition shown in Table 1 and the composition represented by formula (1) above. In the oxide phosphor according to Example 3, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 1.0 (s=1.0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 16 (x=16), the variable y is 0.053 (y=0.079), and the variable z is 0 (z=0).

[0097] Example 4 The raw materials are 1.1g of Li2CO3, 1.2g of ZnO, 11.3g of Ga2O3, 1.6g of GeO2, and 0.27g of Cr2O3 (the initial composition is Li2ZnGa8GeO 16 :Cr 0.12 Except for weighing the raw materials to obtain the raw material mixture, the oxide phosphor according to Example 4 is obtained in the same manner as in Example 1, having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 4 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 4, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 1.0 (s=1.0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 16 (x=16), the variable y is 0.12 (y=0.12), and the variable z is 0 (z=0).

[0098] Example 5 The raw materials are 1.1g of Li2CO3, 0.6g of MgO, 11.3g of Ga2O3, 1.6g of GeO2, and 0.18g of Cr2O3 (the composition of the preparation is Li2MgGa8GeO 16 :Cr 0.079 Except for weighing the raw materials to obtain the raw material mixture, the process is the same as in Example 1 to obtain an oxide phosphor according to Example 5 having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 5 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 5, the variable q in formula (1) is 0 (q=0), and M 2 θ is Mg, the variable r is 1.0 (r=1.0), the variable s is 1.0 (s=1.0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 16 (x=16), the variable y is 0.079 (y=0.079), and the variable z is 0 (z=0).

[0099] Example 6 The raw materials consist of 1.1g of Li2CO3, 0.6g of MgO, 11.3g of Ga2O3, 0.92g of SiO2, and 0.18g of Cr2O3 (the initial composition is Li2MgGa8SiO2). 16 :Cr 0.079 Except for weighing the raw materials to obtain the raw material mixture, the process is the same as in Example 1 to obtain an oxide phosphor according to Example 6 having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 6 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 6, the variable q in formula (1) is 0 (q=0), and M 2 If Mg is Mg, then the variable r is 1.0 (r=1.0), the variable s is 1.0 (s=1.0), the variable t is 0 (t=0), and the variable u is 8 (u=8), M 4 Let be Si, the variable v be 1.0 (v=1.0), the variable w be 1.0 (w=1.0), the variable x be 16 (x=16), the variable y be 0.079 (y=0.079), and the variable z be 0 (z=0).

[0100] Example 7 The raw materials are 1.1g of Li2CO3, 0.6g of MgO, 5.7g of Ga2O3, 3.1g of Al2O3, 0.92g of SiO2, and 0.12g of Cr2O3 (the composition of the preparation is Li2Mg(Ga 0.5 Al 0.5 )8SiO 16 :Cr 0.053 Except for weighing the raw materials to obtain the raw material mixture, the oxide phosphor according to Example 7 is obtained in the same manner as in Example 1, having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 7 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 7, the variable q in formula (1) is 0 (q=0), and M 2 Here, Mg is Mg, the variable r is 1.0 (r=1.0), the variable s is 1.0 (s=1.0), and M 3 Al is, the variable t is 0.5 (t=0.5), the variable u is 8 (u=8), and M 4 Let be Si, the variable v be 1.0 (v=1.0), the variable w be 1.0 (w=1.0), the variable x be 16 (x=16), the variable y be 0.053 (y=0.053), and the variable z be 0 (z=0).

[0101] Example 8 The raw materials consist of 1.1g of Li2CO3, 0.6g of MgO, 6.2g of Al2O3, 0.92g of SiO2, and 0.12g of Cr2O3 (the initial composition is Li2MgAl8SiO2). 16 :Cr 0.053 Except for weighing the raw materials to obtain the raw material mixture, the process is the same as in Example 1 to obtain an oxide phosphor according to Example 8 having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 8 has the composition shown in Table 1 and has the composition represented by formula (1). In the oxide phosphor according to Example 8, the variable q in formula (1) is 0 (q=0), and M 2 Here, Mg is Mg, the variable r is 1.0 (r=1.0), the variable s is 1.0 (s=1.0), and M 3Al is, the variable t is 1.0 (t=1.0), the variable u is 8 (u=8), M 4 Let be Si, the variable v be 1.0 (v=1.0), the variable w be 1.0 (w=1.0), the variable x be 16 (x=16), the variable y be 0.053 (y=0.053), and the variable z be 0 (z=0).

[0102] Example 9 The raw materials are 1.1g of Li2CO3, 1.2g of ZnO, 11.3g of Ga2O3, 2.4g of GeO2, and 0.18g of Cr2O3 (the initial composition is Li2ZnGa8Ge 1.5 O 17 :Cr 0.079 Except for weighing the raw materials to obtain the raw material mixture, the process is the same as in Example 1 to obtain an oxide phosphor according to Example 9 having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 9 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 9, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 1.0 (s=1.0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 1.5 (w=1.5), the variable x is 17 (x=17), the variable y is 0.079 (y=0.079), and the variable z is 0 (z=0).

[0103] Example 10 The raw materials are 1.1g of Li2CO3, 1.2g of ZnO, 11.3g of Ga2O3, 3.2g of GeO2, and 0.18g of Cr2O3 (the initial composition is Li2ZnGa8Ge2O 18 :Cr 0.079 Except for weighing the raw materials to obtain the raw material mixture, the oxide phosphor according to Example 10 is obtained in the same manner as in Example 1, having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 10 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 10, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 1.0 (s=1.0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 2.0 (w=2.0), the variable x is 18 (x=18), the variable y is 0.079 (y=0.079), and the variable z is 0 (z=0).

[0104] Example 11 The raw materials are 1.1g of Li2CO3, 1.2g of ZnO, 11.3g of Ga2O3, 3.2g of GeO2, and 0.27g of Cr2O3 (the initial composition is Li2ZnGa8Ge2O 18 :Cr 0.12 Except for weighing the raw materials to obtain the raw material mixture, the oxide phosphor according to Example 11 is obtained in the same manner as in Example 1, having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 11 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 11, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 1.0 (s=1.0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 2.0 (w=2.0), the variable x is 18 (x=18), the variable y is 0.12 (y=0.12), and the variable z is 0 (z=0).

[0105] Example 12 The raw materials are 1.1g of Li2CO3, 1.2g of ZnO, 11.3g of Ga2O3, 3.2g of GeO2, and 0.36g of Cr2O3 (the initial composition is Li2ZnGa8Ge2O 18 :Cr 0.16 Except for weighing the raw materials to obtain the raw material mixture, the oxide phosphor according to Example 12 is obtained in the same manner as in Example 1, having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 12 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 12, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 1.0 (s=1.0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 2.0 (w=2.0), the variable x is 18 (x=18), the variable y is 0.16 (y=0.16), and the variable z is 0 (z=0).

[0106] Example 13 The raw materials are 1.1g of Li2CO3, 1.2g of ZnO, 11.3g of Ga2O3, 4.8g of GeO2, and 0.18g of Cr2O3 (the initial composition is Li2ZnGa8Ge3O 20 :Cr 0.079 Except for weighing the raw materials to obtain the raw material mixture, the oxide phosphor according to Example 13 is obtained in the same manner as in Example 1, having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 13 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 13, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 1.0 (s=1.0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 3.0 (w=3.0), the variable x is 20 (x=20), the variable y is 0.079 (y=0.079), and the variable z is 0 (z=0).

[0107] Example 14 The raw materials are 1.1g of Li2CO3, 2.4g of ZnO, 11.3g of Ga2O3, 3.2g of GeO2, and 0.18g of Cr2O3 (the initial composition is Li2Zn2Ga8Ge2O 19 :Cr 0.079 Except for weighing the raw materials to obtain the raw material mixture, the oxide phosphor according to Example 14 is obtained in the same manner as in Example 1, having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 14 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 14, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 2.0 (s=2.0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 2.0 (w=2.0), the variable x is 19 (x=19), the variable y is 0.079 (y=0.079), and the variable z is 0 (z=0).

[0108] Example 15 The raw materials are 1.1g of Li2CO3, 1.2g of ZnO, 5.7g of Ga2O3, 3.2g of GeO2, 3.1g of Al2O3, and 0.30g of Cr2O3 (the composition of the preparation is Li2Zn(Ga 0.5 Al 0.5 )8Ge2O 18 :Cr 0.13 Except for weighing the raw materials to obtain the raw material mixture, the oxide phosphor according to Example 15 is obtained in the same manner as in Example 1, having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 15 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 15, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), and the variable s is 1.0 (s=1.0), and M 3 Al is the variable t is 0.5 (t=0.5), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 2.0 (w=2.0), the variable x is 18 (x=18), the variable y is 0.13 (y=0.13), and the variable z is 0 (z=0).

[0109] Example 16 The raw materials consist of 1.1g of Li2CO3, 11.3g of Ga2O3, 1.6g of GeO2, and 0.18g of Cr2O3 (the initial composition is Li2Ga8GeO 15 :Cr 0.079 Except for weighing the raw materials to obtain the raw material mixture, the oxide phosphor according to Example 16 is obtained in the same manner as in Example 1, having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 16 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 16, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 0 (s=0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 15 (x=15), the variable y is 0.079 (y=0.079), and the variable z is 0 (z=0).

[0110] Example 17 The raw materials consist of 1.1g of Li2CO3, 11.3g of Ga2O3, 1.6g of GeO2, and 0.36g of Cr2O3 (the initial composition is Li2Ga8GeO 15 :Cr 0.16 Except for weighing the raw materials to obtain the raw material mixture, the oxide phosphor according to Example 17 is obtained in the same manner as in Example 1, having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 17 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 17, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 0 (s=0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 1.0 (w=1.0), the variable x is 15 (x=15), the variable y is 0.16 (y=0.16), and the variable z is 0 (z=0).

[0111] Example 18 The raw materials consist of 1.1g of Li2CO3, 11.3g of Ga2O3, 2.4g of GeO2, and 0.18g of Cr2O3 (the initial composition is Li2Ga8Ge 1.5 O 16 :Cr 0.079 Except for weighing the raw materials to obtain the raw material mixture, the oxide phosphor according to Example 18 is obtained in the same manner as in Example 1, having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 18 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 18, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 0 (s=0), the variable t is 0 (t=0), the variable u is 8 (u=8), the variable v is 0 (v=0), the variable w is 1.5 (w=1.5), the variable x is 16 (x=16), the variable y is 0.079 (y=0.079), and the variable z is 0 (z=0).

[0112] Example 19 The raw materials consist of 1.1g of Li2CO3, 11.3g of Ga2O3, 0.92g of SiO2, and 0.18g of Cr2O3 (the initial composition is Li2Ga8SiO2). 15 :Cr 0.079 Except for weighing the raw materials to obtain the raw material mixture, the oxide phosphor according to Example 19 is obtained in the same manner as in Example 1, having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 19 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 19, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 0 (s=0), the variable t is 0 (t=0), and the variable u is 8 (u=8), M 4 Let be Si, the variable v be 1.0 (v=1.0), the variable w be 1.0 (w=1.0), the variable x be 15 (x=15), the variable y be 0.079 (y=0.079), and the variable z be 0 (z=0).

[0113] Example 20 The raw materials are 1.1g of Li2CO3, 11.3g of Ga2O3, 1.8g of SiO2, and 0.18g of Cr2O3 (the initial composition is Li2Ga8Si2O 17 :Cr 0.079 Except for weighing the raw materials to obtain the raw material mixture, the oxide phosphor according to Example 20 is obtained in the same manner as in Example 1, having a molar ratio similar to that of the initial composition. The oxide phosphor according to Example 20 has the composition shown in Table 1 and the composition represented by formula (1). In the oxide phosphor according to Example 20, the variable q in formula (1) is 0 (q=0), the variable r is 0 (r=0), the variable s is 0 (s=0), the variable t is 0 (t=0), the variable u is 8 (u=8), and M 4 Let θ be Si, the variable v be 1.0 (v=1.0), the variable w be 2.0 (w=2.0), the variable x be 17 (x=17), the variable y be 0.079 (y=0.079), and the variable z be 0 (z=0).

[0114] Comparative Example 1 The raw materials consist of 0.74g of Li2CO3, 9.4g of Ga2O3, and 0.26g of Cr2O3 (the initial composition is LiGa5O8:Cr 0.17 Except for weighing the raw materials to obtain the raw material mixture, the same procedure as in Example 1 is followed to obtain an oxide phosphor according to Comparative Example 1 having a molar ratio similar to that of the initial composition. The oxide phosphor according to Comparative Example 1 does not have the composition represented by formula (1), and its composition contains Zn and element M represented by the composition formula. 2 , element M 3 , Ge and element M 4 It does not contain at least one element selected from the group consisting of the following. The oxide phosphor according to Comparative Example 1 has a composition represented by formula (a), which is different from that of formula (1), and in formula (a), the variable aq is 0 (aq=0), the variable ay is 1 (ay=0.17), and the variable az is 0 (az=0).

[0115] Measurement of emission spectrum, emission peak wavelength, full width at half maximum (FWHM), and relative emission intensity. For each oxide phosphor in the Examples and Comparative Examples, the emission spectrum was measured using a quantum efficiency measurement system (QE-2000, manufactured by Otsuka Electronics Co., Ltd.). The emission peak wavelength of the excitation light of the light-emitting element, a semiconductor device used in the quantum efficiency measurement system, was 450 nm. From the emission spectra of each phosphor obtained, the emission characteristics, such as relative emission intensity, emission peak wavelength, and full width at half maximum, were determined. Specifically, the emission peak wavelength (nm) and the full width at half maximum (FWHM) (nm) of the emission spectrum having the emission peak wavelength were determined. For the oxide phosphors in Examples 1 to 20, the relative emission intensity (%) was determined with the emission intensity at the emission peak wavelength of the oxide phosphor in Comparative Example 1 set as 100%. The results are shown in the table. The emission spectra of each oxide phosphor in the Examples and Comparative Examples are shown in the respective figures.

[0116] [Table 1]

[0117] The oxide phosphors according to Examples 1 to 20 have a composition represented by formula (1), and their relative luminescence is higher than that of the phosphor according to Comparative Example 1, which has a different composition from that represented by formula (1).

[0118] The oxide phosphors according to Examples 1 to 20 have a composition represented by formula (1) and, upon irradiation with excitation light, can emit light having an emission peak wavelength in the wavelength range of red light to near-infrared light in the emission spectrum, ranging from 680 nm to 900 nm.

[0119] The oxide phosphors according to Examples 1 to 20 have a composition represented by formula (1) and their emission peak wavelength is within the range of 5 nm to 250 nm in the full width at half maximum of the emission spectrum.

[0120] The oxide phosphors according to Examples 1 to 4 have a composition represented by formula (1) that includes Zn and element M 2 It does not contain Mg, or the element M 2It does not contain, and the full width at half maximum of the emission spectrum having an emission peak wavelength is in the range of 40 nm to 250 nm, and the emission peak wavelength in the emission spectrum is in the range of 700 nm to 900 nm. Figure 5 shows the emission spectra of the oxide phosphors according to Examples 1 and 2 and the oxide phosphor according to Comparative Example 1. Figure 6 shows the emission spectra of the oxide phosphors according to Examples 3 and 4.

[0121] The oxide phosphors of Examples 5 to 8 have a composition represented by formula (1), where M 2 The element is Mg, r is 1 (r=1.0), the full width at half maximum of the emission spectrum having an emission peak wavelength is in the range of 50 nm to 130 nm, and the emission peak wavelength in the emission spectrum is in the range of 680 nm to 730 nm. Figure 7 shows the emission spectra of oxide phosphors according to Examples 5 and 6. Figure 8 shows the emission spectra of oxide phosphors according to Examples 7 and 8.

[0122] The oxide phosphors according to Examples 9 to 15 have a composition represented by formula (1) that includes Zn and element M 2 It does not contain Mg, or the element M 2 It does not contain, the variable w is in the range of 1.3 to 3.2 (1.3 ≤ w ≤ 3.2), the full width at half maximum of the emission spectrum having an emission peak wavelength is in the range of 190 nm to 250 nm, and the emission peak wavelength in the emission spectrum is in the range of 750 nm to 900 nm. Figure 9 shows the emission spectra of oxide phosphors according to Examples 9 and 10. Figure 10 shows the emission spectra of oxide phosphors according to Examples 11 and 12. Figure 11 shows the emission spectra of oxide phosphors according to Examples 13 to 15.

[0123] The oxide phosphors of Examples 16 to 18 have a composition represented by formula (1) in which s and v satisfy s=0 and v=0, respectively, and contain Zn and element M 2 It does not contain element M 4It does not contain, and the total width at half maximum of the emission spectrum having an emission peak wavelength is in the range of 190 nm to 240 nm, and the emission peak wavelength in the emission spectrum is in the range of 800 nm to 860 nm. Figure 12 shows the emission spectra of oxide phosphors according to Examples 16 to 18.

[0124] The oxide phosphors in Examples 19 and 20 have a composition represented by formula (1) above, where M 4 The element is Si, and s and v satisfy s=0 and v=1.0, respectively. The emission spectrum has a full width at half maximum of 5 nm or more and 30 nm or less, and the emission peak wavelength is within the range of 690 nm or more and 720 nm or less. Figure 13 shows the emission spectra of oxide phosphors according to Examples 19 and 20.

[0125] The oxide phosphor of Comparative Example 1 has an oxide composition in which part or all of Ga is replaced by Zn, element M. 2 , element M 3 , Ge and element M 4 It is not substituted with one or more elements selected from the group consisting of the above, and the luminescence intensity is lower compared to the oxide phosphors of Examples 1 to 20. The oxide phosphor of Comparative Example 1 has the composition represented by formula (a) above.

[0126] The embodiments relating to this disclosure include the following oxide phosphors and light-emitting devices.

[0127] [Section 1] An oxide phosphor having a composition represented by the following formula (1). (Li 1-q M 1 q )2(Zn 1-r M 2 r ) s (Ga 1-t M 3 t ) u (Ge 1-v M 4 v ) w O x :Cry , M 5 z (1) (In the 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 Mg, Ca, Sr, and Ba, and M 3 is at least one element selected from the group consisting of Al, Sc, and In, and M 4 is at least one element selected from the group consisting of Si, Ti, Zr, Sn, and Hf, and M 5 is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, and q, r, s, t, u, v, w, and x are 0 ≦ q ≦ 0.5, 0 ≦ r ≦ 1.0, 0 ≦ s ≦ 4.0, 0 ≦ t ≦ 1.0, 5 ≦ u ≦ 10, 0 ≦ v ≦ 1.0, 0.5 ≦ w ≦ 5.0, 10 ≦ x ≦ 30, respectively. y and z satisfy 0.02 ≦ y ≦ 0.5, 0 ≦ z ≦ 0.3, and y > z when Li is 2 or when the total of Li and M 1 is 2.) 1 )(When the total of Li or the total of Li and M [Item 2] In the formula (1), y satisfies 0.02 < y ≦ 0.2 with respect to the total of Li or the total of Li and M 1 when Li is 2 or when the total of Li and M 1 is 2. The oxide phosphor according to Item 1.) [Item 3] In the formula (1), y satisfies 0.025 ≦ y ≦ 0.18 with respect to the total of Li or the total of Li and M 1 when Li is 2 or when the total of Li and M 1 is 2. The oxide phosphor according to Item 1 or 2.) [Item 4] In the formula (1), s satisfies 1.0 ≦ s ≦ 3.5. The oxide phosphor according to any one of Items 1 to 3.) [Item 5] The oxide phosphor according to any one of claims 1 to 4, wherein in formula (1), r and w satisfy r=0 and 0.8≦w≦3.0, respectively. [Section 6] The oxide phosphor according to item 5, wherein the oxide phosphor has an emission spectrum with an emission peak wavelength whose full width at half maximum is in the range of 40 nm to 250 nm. [Section 7] The oxide phosphor according to claim 5 or 6, wherein the emission peak wavelength in the emission spectrum is in the range of 700 nm to 900 nm. [Section 8] In formula (1) above, w is an oxide phosphor according to any one of items 1 to 4, satisfying 1.3 ≤ w ≤ 3.2. [Section 9] The oxide phosphor according to claim 8, wherein the oxide phosphor has an emission spectrum with an emission peak wavelength whose full width at half maximum is in the range of 190 nm to 250 nm. [Section 10] The oxide phosphor according to item 8 or 9, wherein the oxide phosphor has an emission peak wavelength in the range of 750 nm to 900 nm in its emission spectrum. [Section 11] The oxide phosphor according to any one of claims 1 to 3, wherein in formula (1), s and v satisfy s=0 and v=0, respectively. [Section 12] The oxide phosphor according to claim 11, wherein the oxide phosphor has an emission spectrum with an emission peak wavelength whose full width at half maximum is in the range of 190 nm to 240 nm. [Section 13] The oxide phosphor according to item 11 or 12, wherein the oxide phosphor has an emission peak wavelength in the range of 800 nm to 860 nm in its emission spectrum. [Section 14] In the above formula (1), M 4 An oxide phosphor according to any one of items 1 to 3, wherein is Si, and s and v satisfy s=0 and v=1.0, respectively. [Section 15] The oxide phosphor according to item 14, wherein the oxide phosphor has an emission spectrum with an emission peak wavelength and a full width at half maximum of 30 nm or less. [Section 16] The oxide phosphor according to item 14 or 15, wherein the oxide phosphor has an emission peak wavelength in the range of 690 nm to 720 nm in its emission spectrum. [Section 17] In the above formula (1), M 2 is Mg, and r is an oxide phosphor according to any one of items 1 to 3, satisfying r = 1.0. [Section 18] The oxide phosphor according to claim 17, wherein the oxide phosphor has an emission spectrum with an emission peak wavelength whose full width at half maximum is in the range of 50 nm to 130 nm. [Section 19] The oxide phosphor according to item 17 or 18, wherein the oxide phosphor has an emission peak wavelength in the range of 680 nm to 730 nm in its emission spectrum. [Section 20] A light-emitting device comprising an oxide phosphor described in any one of items 1 to 19, and a light-emitting element having an emission peak wavelength in the range of 365 nm to 650 nm, for irradiating the oxide phosphor. [Industrial applicability]

[0128] The oxide phosphors relating to this disclosure can also be used in medical light-emitting devices for obtaining information from within living organisms, light-emitting devices for monitoring health conditions when mounted on small mobile devices such as smartphones and smartwatches, light-emitting devices used in medical devices, light-emitting devices for analytical devices that non-destructively measure internal information of 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 spectrometers used to measure film thickness, etc. [Explanation of symbols]

[0129] 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 converter, 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: Coating member, 100, 200: Light-emitting device.

Claims

1. An oxide phosphor having a composition represented by the following formula (1). (Li １－ｑ M １ ｑ ) ２ (Zn １－ｒ M ２ ｒ ) ｓ (Ga １－ｔ M ３ ｔ ) ｕ (Ge １－ｖ M ４ ｖ ) ｗ O ｘ :Cr ｙ ,M ５ ｚ (1) (In the above formula (1), M １ is at least one element selected from the group consisting of Na, K, Rb, and Cs, and M ２ is at least one element selected from the group consisting of Mg, Ca, Sr, and Ba, and M ３ is at least one element selected from the group consisting of Al, Sc, and In, and M ４ is at least one element selected from the group consisting of Si, Ti, Zr, Sn, and Hf, and M ５ is at least one element selected from the group consisting of Ni, Ce, Eu, Fe, Mn, Nd, Tm, Ho, Er, and Yb, where q, r, s, t, u, v, w, and x are 0 ≤ q ≤ 0.5, 0 ≤ r ≤ 1.0, 0 ≤ s ≤ 4.0, 0 ≤ t ≤ 1.0, 5 ≤ u ≤ 10, 0 ≤ v ≤ 1.0, 0.5 ≤ w ≤ 5.0, 10 ≤ x ≤ 30, and y and z are when Li is 2 or Li and M １ When the sum of these is 2, then Li or Li and M １ For the sum of the terms, the following conditions are met: 0.02 ≤ y ≤ 0.5, 0 ≤ z ≤ 0.3, and y > z.

2. In formula (1) above, y is when Li is 2 or Li and M １ When the sum of these is 2, then Li or Li and M １ The oxide phosphor according to claim 1, wherein the sum satisfies 0.02 < y ≤ 0.

2.

3. In formula (1) above, y is when Li is 2 or Li and M １ When the sum of these is 2, then Li or Li and M １ The oxide phosphor according to claim 1, wherein the sum satisfies 0.025 ≤ y ≤ 0.

18.

4. The oxide phosphor according to claim 1, wherein in formula (1), s satisfies 1.0 ≤ s ≤ 3.

5.

5. The oxide phosphor according to claim 1, wherein in formula (1), r and w satisfy r = 0 and 0.8 ≤ w ≤ 3.0, respectively.

6. The oxide phosphor according to claim 5, wherein the oxide phosphor has an emission spectrum having an emission peak wavelength, and the full width at half maximum of that spectrum is in the range of 40 nm to 250 nm.

7. The oxide phosphor according to claim 5, wherein the oxide phosphor has an emission peak wavelength in the emission spectrum within the range of 700 nm to 900 nm.

8. The oxide phosphor according to claim 1, wherein in formula (1), w satisfies 1.3 ≤ w ≤ 3.

2.

9. The oxide phosphor according to claim 8, wherein the oxide phosphor has an emission spectrum with an emission peak wavelength whose full width at half maximum is in the range of 190 nm to 250 nm.

10. The oxide phosphor according to claim 8, wherein the oxide phosphor has an emission peak wavelength in the emission spectrum within the range of 750 nm to 900 nm.

11. The oxide phosphor according to claim 1, wherein in formula (1), s and v satisfy s = 0 and v = 0, respectively.

12. The oxide phosphor according to claim 11, wherein the oxide phosphor has an emission spectrum having an emission peak wavelength, and the full width at half maximum of that spectrum is in the range of 190 nm to 240 nm.

13. The oxide phosphor according to claim 11, wherein the oxide phosphor has an emission peak wavelength in the emission spectrum within the range of 800 nm to 860 nm.

14. In the formula (1), M ４ The oxide phosphor according to claim 1, wherein is Si, and s and v satisfy s = 0 and v = 1.0, respectively.

15. The oxide phosphor according to claim 14, wherein the oxide phosphor has an emission spectrum with an emission peak wavelength and a full width at half maximum of 30 nm or less.

16. The oxide phosphor according to claim 14, wherein the oxide phosphor has an emission peak wavelength in the emission spectrum within the range of 690 nm to 720 nm.

17. In the formula (1), M ２ The oxide phosphor according to claim 1, wherein is Mg and r satisfies r = 1.

0.

18. The oxide phosphor according to claim 17, wherein the oxide phosphor has an emission spectrum having an emission peak wavelength, and the full width at half maximum of that spectrum is in the range of 50 nm to 130 nm.

19. The oxide phosphor according to claim 17, wherein the oxide phosphor has an emission peak wavelength in the range of 680 nm to 730 nm in its emission spectrum.

20. A light-emitting device comprising an oxide phosphor according to any one of claims 1 to 19, and a light-emitting element having an emission peak wavelength in the range of 365 nm to 650 nm, for irradiating the oxide phosphor.

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