Phosphor, its manufacturing method, light-emitting element, and light-emitting device

Abstract

The present invention provides: a phosphor which emits light having a wavelength of 600 nm or more in the red to near-infrared range when irradiated with visible light or ultraviolet light; a method for producing this phosphor; a light emitting element using this phosphor; and a light emitting device using this phosphor. This phosphor contains an inorganic compound which contains an element A, an element M, an element D and an element E (A is at least one element selected from the group consisting of Mg, Ca, Sr and Ba; M is at least one element selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm and Yb; D is Si and / or Al; and E is O and / or N), while additionally containing, if necessary, an element G (G is elemental Li), and which has a composition represented by (A, M)aDdEeGg, wherein the atomic fraction parameters a, d, e and g are values respectively satisfying 2.4 ≤ a ≤ 4.8, 17.4 ≤ d ≤ 22.2, 26.2 ≤ e ≤ 28.6 and 0 ≤ g ≤ 3.

Description

[Technical field]

[0001] In the present invention, the present disclosure provides Sr 6x (Si,Al) 27-12x (O,N) 31-6x Li 3y , where 0.4≦x≦0.8, 0≦y≦0.35 (hereinafter referred to as this crystal) and Sr3Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 The present invention relates to a phosphor containing an inorganic compound having a crystal having the same crystal structure as that of the above-mentioned compound (hereinafter referred to as the present same crystal) as a host crystal, a method for producing the phosphor, and uses thereof. [Background technology]

[0002] Phosphors are used in vacuum fluorescent displays (VFDs), field emission displays (FEDs or SEDs), plasma display panels (PDPs), cathode ray tubes (CRTs), liquid crystal display backlights, and white light-emitting diodes (LEDs). In any of these applications, in order to make the phosphors emit light, it is necessary to supply the phosphors with energy for exciting the phosphors, and the phosphors are excited by excitation sources having high energy such as vacuum ultraviolet rays, ultraviolet rays, electron beams, and blue light to emit visible light such as blue light, green light, yellow light, orange light, and red light. However, as a result of exposure of phosphors to such excitation sources, the luminance of the phosphors is easily reduced, and a phosphor that does not reduce in luminance is required. Therefore, as an alternative to conventional phosphors such as silicate phosphors, phosphate phosphors, aluminate phosphors, and sulfide phosphors, phosphors based on inorganic crystals that contain nitrogen in their crystal structure, such as sialon phosphors, oxynitride phosphors, and nitride phosphors, have been proposed as phosphors that exhibit little loss in luminance even under high-energy excitation.

[0003] An example of this sialon phosphor is manufactured by the manufacturing process outlined below. First, silicon nitride (Si3N4), aluminum nitride (AlN), calcium oxide (CaO), and europium oxide (Eu2O3) are mixed in a specific molar ratio, and then the mixture is heated to 1700°C for 1 hour in nitrogen at 1 atmosphere (0.1 MPa) and sintered by a hot press method (see, for example, Patent Document 1). The Eu2O3 obtained by this process is 2+It has been reported that ion-activated α-sialon becomes a phosphor that emits yellow light of 550 to 600 nm when excited with blue light of 450 to 500 nm. It is also known that the emission wavelength can be changed by changing the ratio of Si to Al or the ratio of oxygen to nitrogen while maintaining the crystal structure of α-sialon (see, for example, Patent Document 2 and Patent Document 3).

[0004] Another example of a sialon phosphor is a β-type sialon with Eu 2+ A green phosphor activated with Ce is known (see Patent Document 4). It is known that the emission wavelength of this phosphor can be shifted to a shorter wavelength by changing the oxygen content while maintaining the crystal structure (see, for example, Patent Document 5). 3+ It is known that when activated, it becomes a blue phosphor (see, for example, Patent Document 6).

[0005] An example of an oxynitride phosphor is the JEM phase (LaAl(Si 6-z Al z )N 10-z O z A blue phosphor (see Patent Document 7) is known in which Ce is activated by using La as a host crystal. It is known that in this phosphor, by substituting a portion of La with Ca while maintaining the crystal structure, the excitation wavelength and the emission wavelength are shifted to longer wavelengths.

[0006] Another example of an oxynitride phosphor is the La-N crystal, La3Si8N 11 A blue phosphor in which O4 is used as a host crystal and Ce is activated is known (see Patent Document 8).

[0007] An example of a nitride phosphor is Eu with CaAlSiN3 as the host crystal. 2+ A red phosphor activated with Ce (see Patent Document 9) is known. The use of this phosphor has the effect of improving the color rendering of white LEDs. A phosphor doped with Ce as an optically active element has been reported to be an orange phosphor.

[0008] In this way, the color of light emitted by a phosphor is determined by the combination of the host crystal and the metal ions (activator ions) that are dissolved in it. Furthermore, the combination of the host crystal and the activator ions determines the luminescence characteristics such as the emission spectrum and excitation spectrum, as well as the chemical stability and thermal stability, so if the host crystal or activator ions are different, they are considered to be different phosphors. Furthermore, materials with the same chemical composition but different crystal structures are considered to be different phosphors because the luminescence characteristics and stability differ due to the different host crystals.

[0009] Furthermore, in many phosphors, it is possible to replace the types of constituent elements while maintaining the crystal structure of the host crystal, and this has been used to change the color of the emitted light. For example, a phosphor in which Ce is added to YAG emits green light, but a phosphor in which part of the Y in the YAG crystal is replaced with Gd and part of the Al with Ga emits yellow light. Furthermore, in a phosphor in which Eu is added to CaAlSiN3, it is known that by replacing part of Ca with Sr, the composition changes while maintaining the crystal structure, and the emission wavelength becomes shorter. In this way, phosphors that have undergone element replacement while maintaining the crystal structure are considered to be materials in the same group.

[0010] For these reasons, in developing new phosphors, it is important to find a host crystal with a new crystal structure, and by activating such a host crystal with metal ions responsible for luminescence to express fluorescent properties, a phosphor with new luminescence properties can be produced. Furthermore, by changing the constituent elements of the new crystal, it is possible to produce a crystal with a different composition while maintaining the crystal structure, which also allows the production of a phosphor with new luminescence properties. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Patent No. 3668770 specification [Patent Document 2] Patent No. 3837551 Specification [Patent Document 3] Patent No. 4524368 specification [Patent Document 4] Patent No. 3921545 specification [Patent Document 5] International Publication No. 2007 / 066733 [Patent Document 6] International Publication No. 2006 / 101096 [Patent Document 7] International Publication No. 2005 / 019376 [Patent Document 8] JP 2005-112922 A [Patent Document 9] Patent No. 3837588 specification Summary of the Invention [Problem to be solved by the invention]

[0012] In an embodiment of the present invention, a novel phosphor having certain luminescence characteristics is provided. The novel phosphor is expected to have different luminescence characteristics (luminescence color, excitation characteristics, and emission spectrum). In particular, it may emit light in the red and near-infrared regions of 600 nm or more when irradiated with visible light or ultraviolet light. In addition, when combined with an LED of 600 nm or less, an inorganic phosphor with high luminescence intensity may be provided. It is possible to provide a light-emitting element and a light-emitting device having excellent durability using such a phosphor. [Means for solving the problem]

[0013] Under these circumstances, the present inventors conducted detailed research on phosphors based on new nitrogen-containing crystals and crystals in which metal elements or N in the crystal structure are replaced with other elements, and found that the present crystals and inorganic materials that contain the present crystals as their host or host crystals emit high-intensity fluorescence. They also found that certain compositions emit red or near-infrared light.

[0014] The inventors also found that by using this phosphor, it is possible to obtain a light-emitting element containing a light component in the red or near-infrared region, and a light-emitting device using the same, such as a white light-emitting diode or a lighting fixture.

[0015] As a result of intensive research conducted in light of the above-mentioned circumstances, the present inventors have succeeded in providing a phosphor capable of exhibiting a high-luminance light emission phenomenon in a specific wavelength region by adopting the configuration described below. In addition, the inventors have succeeded in producing a phosphor capable of exhibiting excellent light emission characteristics by the following method. Furthermore, the inventors have succeeded in providing a light-emitting element and a light-emitting device having excellent characteristics by using this phosphor and adopting the configuration described below. The details are described below.

[0016] In an embodiment of the present invention, the phosphor contains at least an A element, an M element, a D element, and an E element (wherein A contains at least one or more elements selected from the group consisting of Mg, Ca, Sr, and Ba, M is one or more elements selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm, and Yb, D is one or more elements selected from the group consisting of Si and Al, and E is one or more elements selected from the group consisting of O and N), and optionally a G element (wherein G is Li); (A,M) a D d E e G g The atomic fraction parameters a, d, e, and g are expressed as follows: 2.4 ≦ a ≦ 4.8 17.4≦d≦22.2 26.2≦e≦28.6 0≦g≦3 The inorganic compound may contain an inorganic compound represented by the numerical value of: The parameter g is 0.21 ≦ g ≦ 1.05 It may be expressed as a numerical value in the range of The inorganic compound is (A, M) 6x D 27-12x E31-6x G 3y (wherein x and y satisfy 0.4≦x≦0.8 and 0≦y≦0.35, respectively). Here, "(A,M) 6x " may mean that both A atoms and M atoms are present (i.e., the subscripts of each atom are greater than 0), and the total number of A atoms and M atoms is "6x." For example, if the parameters p and q are set to p+q=6x, the above formula can be rewritten as "(A p M q )D 27-12x E 31-6x G 3y (where p+q=6x, p>0, q>0)" The x may satisfy the relationship 0.45≦x≦0.55. The inorganic compound is (A, M) 6x D 27-12x E 31-6x G 3y (wherein 0.4≦x≦0.8, 0≦y≦0.35) (hereinafter referred to as the present crystal). In addition, it may be a crystal having the same crystal structure as the present crystal (hereinafter referred to as the present identical crystal). The inorganic compound is (Sr,Eu)3(Si,Al) 21 (O,N) 28 Li 0.96 The crystal may include a crystal represented by: The inorganic compound is Sr3Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 It may include crystals having the same crystal structure as The present crystal and the present identical crystal are of a hexagonal system, and the lattice constants a, b, and c are 1.6 < a < 1.8 nm b = a 0.44 < c < 0.52 nm may be also possible. The present crystal and the present identical crystal may be crystals belonging to the P63 space group (space group No. 173 in the International Tables for Crystallography). The inorganic compound is Sr 6x (Si,Al) 27-12x (O,N) 31-6x Li 3y (wherein 0.4≦x≦0.8, 0≦y≦0.35) or a crystal having the same crystal structure as that, and may further contain an M element. The A element may be Sr, the M element may be Eu, and the E element may be one or more elements selected from the group consisting of O and N. The D element includes Si and Al, The relationship 0.4≦Al / (Al+Si)≦0.6 may be satisfied. The E elements include O and N, The condition 0.01≦O / (O+N)≦0.1 may be satisfied. Any of the above phosphors may emit light having a maximum emission peak in a wavelength range of 600 nm or more and 850 nm or less when irradiated with light having a wavelength in the range of 300 nm or more and 600 nm or less. In an embodiment of the present invention, a method for producing any of the phosphors described above may include a step of mixing raw materials selected from one or more of the group consisting of nitrides, oxynitrides, oxides, carbonates, and fluorides of an A element (wherein A is one or more elements selected from the group consisting of Mg, Ca, Sr, and Ba), an M element (wherein M is one or more elements selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm, and Yb), a D element (wherein M is one or more elements selected from the group consisting of Si and Al), and, if necessary, a G element (wherein G is Li), and firing the mixture at a temperature of 1400° C. or higher and 2200° C. or lower. The above problem is solved. There may be provided a light emitting device including an excitation source that emits light having a wavelength in the range of 300 nm to 600 nm, and any one of the phosphors described above. The excitation source may be a light emitting diode (LED) or a laser diode (LD). Any of the light-emitting elements described above may include one or more phosphors that emit fluorescence having a maximum emission peak in a wavelength range of 400 nm or more and 760 nm or less when irradiated with light having a wavelength in the range of 300 nm or more and 600 nm or less. Any of the above-mentioned light-emitting devices may be used. 10 O 17 :Eu, SrSi9Al 19 ON 31 :Eu, LaSi9Al 19 N 32 :Eu, α-sialon:Ce, JEM:Ce, β-sialon:Eu, (Ba,Sr,Ca,Mg)2SiO4:Eu, (Ca,Sr,Ba)Si2O2N2:Eu, YAG:Ce, α-sialon:Eu, CaAlSiN3:Ce, La3Si6N 11 The phosphor may contain one or more phosphors selected from the group consisting of CaAlSiN3:Eu, (Ca,Sr)AlSiN3:Eu, Ca2Si5N8:Eu, and Sr2Si5N8:Eu. In an embodiment of the present invention, the light emitting device includes any one of the light emitting elements described above, and may be any one of a lighting fixture, a backlight for a liquid crystal panel, a lamp for a projector, an infrared light source, and an infrared measurement light source. Effect of the Invention

[0017] In an embodiment of the present invention, the phosphor is Sr 6x (Si,Al) 27-12x (O,N) 31-6x Li 3y Crystal or Sr3Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96The phosphor may contain, as a main component, a crystal having the same crystal structure as that of the phosphor of the present invention. The phosphor may exhibit a higher luminance than conventional oxide phosphors or oxynitride phosphors. In a particular composition, the phosphor may be excellent as a red or near-infrared phosphor. Even when exposed to an excitation source, the luminance of such a phosphor is unlikely to decrease. It is possible to provide a useful phosphor that is suitably used in light-emitting devices such as light-emitting elements such as white light-emitting diodes, lighting fixtures using the same, backlight sources for liquid crystal displays, infrared emitting lighting, and infrared light sources for inspection. [Brief description of the drawings]

[0018] [Figure 1] A diagram showing the crystal structure of Sr3Si12.432Al8.568O1.608N26.392Li0.96 crystal. [Diagram 2] A diagram showing powder X-ray diffraction using CuKα radiation calculated from the crystal structure of Sr3Si12.432Al8.568O1.608N26.392Li0.96 crystal. [Diagram 3] FIG. 1 shows the emission spectrum of the phosphor synthesized in Experiment 1. [Figure 4] FIG. 1 shows the emission spectrum of the phosphor synthesized in Experiment 2. [Diagram 5] 1 is a schematic diagram showing a lighting fixture (bullet-shaped LED lighting fixture) according to the present invention. [Figure 6] 1 is a schematic diagram showing a lighting fixture (board-mounted LED lighting fixture) according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The phosphor of the present invention will now be described in detail. In an embodiment of the present invention, the phosphor includes at least an A element, an M element, a D element, and an E element (wherein A includes at least one or more elements selected from the group consisting of Mg (magnesium), Ca (calcium), Sr (strontium), and Ba (barium), M includes one or more elements selected from the group consisting of Mn (manganese), Eu (europium), Ce (cerium), Nd (neodymium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), and Yb (ytterbium), D includes one or more elements selected from the group consisting of Si (silicon) and Al (aluminum), and E includes one or more elements selected from the group consisting of O (oxygen) and N (nitrogen)), and optionally includes a G element (wherein G is Li (lithium)), and (A,M) a D d E e G g The atomic fraction parameters a, d, e, and g are expressed as follows: 2.4 ≦ a ≦ 4.8 17.4≦d≦22.2 26.2≦e≦28.6 0≦g≦3 The inorganic compound may contain an inorganic compound represented by the numerical value of 600 nm or less. When irradiated with light having a wavelength of 600 nm or less, it may emit light in the red and near infrared regions of 600 nm or more and function as a phosphor. If the numerical values ​​of the parameters are out of this range, there is a risk that the luminescence intensity will be low. The A element may further contain an element selected from the group consisting of Y (yttrium), Lu (lutetium), and La (lanthanum).

[0020] It further includes a G element (G is a Li element), and the parameter values ​​are 0.21 ≦ g ≦ 1.05 This is particularly preferable since it increases the emission intensity.

[0021] In an embodiment of the present invention, the phosphor is (A,M) 6x D 27-12x E31-6x G 3y It may contain an inorganic compound having a composition of 0.4≦x≦0.8, 0≦y≦0.35. This may facilitate crystallization and increase the emission intensity. It may also have a composition range of 0.45≦x≦0.55. This may facilitate crystallization and is preferable. When x=5, the most stable crystal may be obtained.

[0022] Inorganic compounds are (A,M) 6x D 27-12x E 31-6x G 3y (wherein 0.4≦x≦0.8, 0≦y≦0.35) (hereinafter referred to as the present crystal) may be included. In addition, (A,M) 6x D 27-12x E 31-6x G 3y The phosphor has a high luminescence intensity. The same crystal as the SrSi 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 The crystal may have the same crystal structure as the crystal.

[0023] A crystal having the same crystal structure may mean a crystal in which the coordinates of the positions of corresponding atoms in the crystal lattice are the same or close to each other, but the types of the corresponding atoms are partially or entirely different, compared to the original crystal. For example, (A,M) 6x D 27-12x E 31-6x G 3y Represented by Sr3Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 Examples of crystals that have the same crystal structure as a crystal (the original crystal) include crystals in which some of the Sr (corresponding atoms) of this crystal have been replaced with Ba or Eu, some of the Si (corresponding atoms) have been replaced with Al, and some of the N (corresponding atoms) have been replaced with O.

[0024] In addition, SrSi 12.432 Al 8.568 O1.608 N 26.392 Li 0.96 As a crystal with the same crystal structure as the crystal, (A,M) 6x D 27-12x E 31-6x G 3y crystal, A 6x D 27-12x E 31-6x G 3y crystal, (Sr,Eu)3(Si,Al) 21 (O,N) 28 Li 0.96 crystal, Sr3Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 crystal, These crystals were newly synthesized by the present inventors and confirmed to be novel crystals by crystal structure analysis. To the best of the present inventors' knowledge, these crystals have not been reported prior to the present application.

[0025] Sr3Si synthesized by the inventors 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 As a result of single crystal structure analysis, it was found that this crystal belongs to the hexagonal crystal system, the P63 space group (space group number 173 in the International Tables for Crystallography), and has the crystal parameters and atomic coordinate positions shown in Table 1. In Table 1, the lattice constants a, b, and c indicate the lengths of the axes of the unit cell, and α, β, and γ indicate the angles between the axes of the unit cell. The atomic coordinates indicate the position of each atom in the unit cell, with values ​​between 0 and 1 based on the unit cell. The crystal contains Sr, Si, Al, Li, O, and N atoms, and the analysis results showed that Sr exists in two types of sites, A1 and A2. In addition, the analysis results showed that Si and Al exist in nine types of sites, B1 to B9, without distinguishing between sites. In addition, the analysis results showed that N and O exist in 11 types of sites, X1 to X11, without distinguishing between sites.

[0026] [Table 1]

[0027] Figure 1 shows the Sr3Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 FIG. 2 is a diagram showing the crystal structure of a crystal.

[0028] As a result of analysis using the data in Table 1, it was found that this crystal has the structure shown in Figure 1, with Sr and Li elements contained in a framework of linked tetrahedra consisting of bonds between (Si or Al) and (O or N). Figure 1 shows that Sr and (O,N) coexist, but in reality only one of them is present.

[0029] Analysis of the synthesized crystals of various compositions revealed that Sr3Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 It was confirmed that crystals having the same crystal structure as the crystals can have the same crystal structure over a wide range of compositions, and the general formula is (A,M) 6x D 27-12x E 31-6x G 3y It was found that this can be shown by Where: A contains at least one or more elements selected from the group consisting of Mg, Ca, Sr and Ba, M is one or more elements selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm and Yb; D is one or more elements selected from the group consisting of Si and Al; E is one or more elements selected from the group consisting of O and N, G is Li element It is possible to form crystals.

[0030] By changing the parameters x and y, the composition changes while maintaining the crystal structure. x is a parameter that determines the amount of (A, M) and takes a value in the range of 0.4≦x≦0.8. However, it is desirable that the cations A, D, and G and the anion E satisfy the condition that maintains electrical neutrality in the crystal. y is a parameter that determines the amount of G and takes a value in the range of 0≦y≦0.35. In particular, the crystal is likely to stabilize when the range is 0.023≦y≦0.35.

[0031] General formula (A,M) 6x D 27-12x E 31-6x G 3y The crystal structure of SrSi 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 It has the same crystal structure as the (A,M) crystal, and in Table 1, the A01 and A02 sites are occupied by the A and M elements, the B01 to B09 sites are occupied by the D element, the C01 site is occupied by the G element, and the X01 to X11 sites are occupied by the E element. Although the site occupancy rate and lattice constant change when the type and composition of the elements change, the crystal structure and atomic coordinates do not change significantly. For this reason, (A,M) 6x D 27-12x E 31-6x G 3y Crystal formation can be determined using the information in Table 1.

[0032] This crystal or this identical crystal is a hexagonal crystal, and the lattice constants a, b, and c are 1.6 < a < 1.8 nm b = a 0.44 < c < 0.52 nm Phosphors in which luminescent ions are activated in inorganic substances have high luminescence intensity. Phosphors whose host crystals are crystals that belong to the P63 space group (space group number 173 in the International Tables for Crystallography) have high luminescence intensity.

[0033] In one embodiment of the present invention, Sr 6x (Si,Al) 27-12x (O,N) 31-6xLi 3y (where 0.4≦x≦0.8, 0≦y≦0.35) and crystals having the same crystal structure as the crystals may further contain a phosphor containing an M element.

[0034] The crystals containing D elements Si and Al, where 0.4 ≦ Al / (Al+Si) ≦ 0.6, may have particularly stable crystal structures. The emission intensity is high.

[0035] The crystals containing the E elements O and N and having 0.01 ≦ O / (O+N) ≦ 0.1 may have particularly stable crystal structures. The emission intensity is high.

[0036] The crystals containing the G element and having 0.15 ≦ y ≦ 0.3 may have particularly stable crystal structures and high emission intensity.

[0037] In one embodiment of the invention, M is Eu, and (A,M) 6x D 27-12x E 31-6x G 3y The phosphor may have a composition in which the content m of Eu is 0.001≦m≦0.1. 6x-m M m D 27-12x E 31-6x G 3y In this case, these phosphors emit light having a maximum emission peak in the wavelength range of 600 nm or more and 850 nm or less when irradiated with light having a wavelength in the range of 300 nm or more and 600 nm or less, and are therefore suitable as phosphors for this purpose.

[0038] Phosphors in which the inorganic compound is a single crystal particle or an aggregate of single crystals with an average particle size of 0.1 μm to 20 μm may have high luminous efficiency. They may also have good operability when mounted on an LED. It is best to control the particle size to within this range.

[0039] The impurity elements Fe, Co, and Ni contained in inorganic compounds may reduce the emission intensity. The total amount of these elements in the phosphor may be 500 ppm or less. This may reduce the effect of the reduction in emission intensity.

[0040] As one embodiment of the present invention, a phosphor may be included that is composed of a mixture of a phosphor having the present crystal or the present crystal as a host and another crystal phase or an amorphous phase, and the content of the phosphor having the present crystal or the present crystal as a host may be 20% by mass or more. This embodiment can be used when a phosphor containing an inorganic compound having the present crystal or the present crystal as a host or host crystal alone does not have a predetermined characteristic, or when a function such as electrical conductivity is added. The content of the phosphor containing an inorganic compound having the present crystal or the present crystal as a host or host crystal may be adjusted so that a predetermined characteristic is obtained. If it is 20% by mass or less, there is a risk that the emission intensity will be low.

[0041] In such an embodiment of the present invention, the method of manufacturing the phosphor may not be particularly specified. For example, a raw material mixture that is a mixture of metal compounds and that can be fired to form a phosphor based on the present crystal or the present identical crystal may be fired in a nitrogen-containing inert atmosphere at a temperature range of 1400°C to 2200°C. In the embodiment of the present invention, the crystal of the inorganic compound contained in the phosphor may be a hexagonal crystal system belonging to the space group P63. Depending on the synthesis conditions such as the firing temperature, crystals having a different crystal system or space group may be mixed in. Since the change in the light-emitting characteristics is small, it can be used as a high-brightness phosphor.

[0042] The starting materials may be one or more selected from the group consisting of nitrides, oxynitrides, oxides, carbonates and fluorides of an A element (wherein A contains at least one or more elements selected from the group consisting of Mg, Ca, Sr and Ba), an M element (wherein M is one or more elements selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm and Yb), a D element (wherein M is one or more elements selected from the group consisting of Si and Al), and, if necessary, a G element (wherein G is Li).

[0043] The furnace used for sintering is an electric furnace using a metal resistance heating method or a graphite resistance heating method, and using carbon as the material for the high-temperature part of the furnace, since the sintering temperature is high and the sintering atmosphere is an inert atmosphere containing nitrogen.

[0044] The firing temperature should be between 1400°C and 2200°C. If the temperature is lower than 1400°C, the reaction may not proceed sufficiently. If the temperature is higher than 2200°C, the raw material powder and the compound may decompose. The firing time varies depending on the firing temperature, but is usually around 1 to 48 hours.

[0045] The nitrogen-containing inert atmosphere is preferably in the pressure range of 0.1 MPa to 100 MPa, since this suppresses the thermal decomposition of the starting materials and the products, i.e., nitrides and oxynitrides. The oxygen partial pressure in the firing atmosphere is preferably 0.0001% or less, since this suppresses the oxidation reaction of the starting materials and the products, i.e., nitrides and oxynitrides.

[0046] To manufacture phosphor in powder or aggregate form, the raw material may be packed into a container while maintaining a bulk density of 40% or less, and then fired. By keeping the bulk density at 40% or less, strong adhesion between particles can be avoided. Here, the relative bulk density is the ratio of the mass of the powder packed into a container divided by the volume of the container (bulk density) to the true density of the powder material.

[0047] In firing the raw material mixture, various heat-resistant materials can be used as a container for holding the raw material mixture, but in the examples of the present invention, a container coated with boron nitride, as shown in the graphite crucible coated with boron nitride used in the synthesis of α-sialon described in the academic journal Journal of the American Ceramic Society, Vol. 85, No. 5, pp. 1229-1234, 2002, or a boron nitride sintered body is suitable because of the low adverse effect of material deterioration on the metal nitride used. If firing is performed under such conditions, boron or boron nitride components may be mixed into the product from the container, but if the amount is small, the luminescence characteristics will not decrease and the effect is small. Furthermore, the addition of a small amount of boron nitride may improve the durability of the product, which may be preferable in some cases.

[0048] To produce a phosphor in powder or aggregate form, it is preferable that the average particle size of the raw material powder particles or aggregates is 500 μm or less, as this provides excellent reactivity and operability.

[0049] As a method for reducing the particle size of the particles or aggregates to 500 μm or less, it is preferable to use a spray dryer, sieving, or air classification, which has excellent work efficiency and operability.

[0050] The sintering method does not involve hot pressing, and is preferably a sintering method that does not involve external mechanical pressure, such as atmospheric pressure sintering or gas pressure sintering, as a method for obtaining a powder or aggregate product.

[0051] The average particle size of the phosphor powder is preferably 50 nm to 200 μm in volume median diameter (d50) because it has high luminescence intensity. The volume average particle size can be measured, for example, by a microtrack or laser scattering method. The average particle size of the phosphor powder synthesized by firing may be adjusted to 50 nm to 200 μm by using one or more methods selected from pulverization, classification, and acid treatment.

[0052] By heat treating the fired phosphor powder, the crushed phosphor powder, or the particle size adjusted phosphor powder at a temperature of 1000°C or higher but lower than the firing temperature, defects in the powder or damage caused by crushing may be repaired. Defects and damage may be the cause of a decrease in luminescence intensity, and in this case, the luminescence intensity may be restored by heat treatment.

[0053] During firing to synthesize a phosphor, adding an inorganic substance that forms a liquid phase at temperatures below the firing temperature can act as a flux, promoting reaction and grain growth and resulting in stable crystals, which can improve the luminescence intensity.

[0054] Examples of inorganic substances that form a liquid phase at temperatures below the firing temperature include one or a mixture of two or more of fluorides, chlorides, iodides, bromides, or phosphates of one or more elements selected from Li, Na, K, Mg, Ca, Sr, and Ba. These inorganic substances have different melting points, so it is best to use them according to the synthesis temperature.

[0055] Furthermore, by washing with a solvent after firing, the content of inorganic substances that form a liquid phase at temperatures equal to or lower than the firing temperature can be reduced, which can increase the luminescence intensity of the phosphor.

[0056] In the embodiment of the present invention, when the phosphor is used for applications such as a light emitting device, it is preferable to use such a phosphor in a form dispersed in a liquid medium. Also, in the embodiment of the present invention, it can be used as a phosphor mixture containing the phosphor. In the embodiment of the present invention, the phosphor dispersed in the medium is called a phosphor-containing composition.

[0057] In the embodiment of the present invention, the medium usable in the phosphor-containing composition may be one that can suitably disperse the phosphor in the embodiment of the present invention. Any medium that does not cause undesirable reactions can be selected according to the purpose. Examples of the medium include glass, silicone resin, epoxy resin, polyvinyl resin, polyethylene resin, polypropylene resin, polyester resin, etc. These media may be used alone or in any combination and ratio of two or more.

[0058] The amount of medium used may be adjusted as appropriate depending on the application, etc., but generally, in the embodiments of the present invention, the weight ratio of medium to phosphor may be in the range of usually 3 wt % or more, preferably 5 wt % or more, and usually 30 wt % or less, preferably 15 wt % or less.

[0059] In the embodiment of the present invention, the light-emitting element may be constructed using at least an excitation source (light-emitting light source) and the phosphor in the embodiment of the present invention. Examples of light-emitting light sources include light-emitting diodes (LEDs), laser diodes (LDs), organic EL light-emitting elements, fluorescent lamps, and the like. LEDs can be manufactured using the phosphor in the embodiment of the present invention by known methods such as those described in JP-A-5-152609, JP-A-7-99345, and Japanese Patent Publication No. 2927279. In this case, the light-emitting body or light-emitting light source is preferably one that emits light having a wavelength in the range of 300 nm to 600 nm, and examples of usable light-emitting bodies include ultraviolet (or violet) LED light-emitting elements that emit light having a wavelength in the range of 300 nm to 420 nm, blue LED light-emitting elements that emit light having a wavelength in the range of 420 nm to 500 nm, and green, yellow, and red LED light-emitting elements that emit light having a wavelength in the range of 500 nm to 600 nm. Some of these LEDs are made of semiconductors such as GaN, InGaN, and AlGaAs, and by adjusting the composition, they can become light-emitting light sources that emit light of a predetermined wavelength.

[0060] In the embodiment of the present invention, as one form of the light-emitting device, in addition to the phosphor in the embodiment of the present invention, a phosphor that emits fluorescence having a maximum emission peak in a wavelength range of 400 nm to 760 nm when irradiated with light having a wavelength in the range of 300 nm to 600 nm may be included. Such phosphors may be included alone or in combination. This can result in a light-emitting device containing 400 nm purple, blue, green, yellow, red, and infrared color components.

[0061] In the embodiment of the present invention, as one form of the light-emitting device, in addition to the phosphor in the embodiment of the present invention, a blue phosphor that emits light with a peak wavelength of 400 nm or more and 500 nm or less by a light emitting body or a light emission light source can be included. Such phosphors include AlN:(Eu,Si), BaMgAl 10 O 17 :Eu, SrSi9Al 19 ON 31 :Eu, LaSi9Al 19 N 32 :Eu, α-sialon:Ce, JEM:Ce, etc.

[0062] In the embodiment of the present invention, as one form of the light-emitting element, in addition to the phosphor in the embodiment of the present invention, a green phosphor that emits light with a peak wavelength of 500 nm or more and 550 nm or less by a light emitter or a light source can be included. Examples of such green phosphors include β-sialon:Eu, (Ba,Sr,Ca,Mg)2SiO4:Eu, (Ca,Sr,Ba)SiO2N2:Eu, etc.

[0063] In the embodiment of the present invention, as one form of the light-emitting device, in addition to the phosphor in the embodiment of the present invention, a yellow phosphor that emits light with a peak wavelength of 550 nm or more and 600 nm or less by a light emitter or a light source can be included. Such yellow phosphors include YAG:Ce, α-sialon:Eu, CaAlSiN3:Ce, La3Si6N 11 :Ce, etc.

[0064] In the embodiment of the present invention, as one form of the light-emitting element, in addition to the phosphor in the embodiment of the present invention, a red phosphor that emits light with a peak wavelength of 600 nm or more and 700 nm or less by a light emitter or a light source can be included. Such red phosphors include CaAlSiN3:Eu, (Ca,Sr)AlSiN3:Eu, Ca2Si5N8:Eu, Sr2Si5N8:Eu, etc.

[0065] In an embodiment of the present invention, when an LED that emits light with a wavelength in the range of 320 nm or more and 500 nm or less is used as a light-emitting element as a light-emitting body or light source, the light-emitting efficiency is high, and therefore a highly efficient light-emitting device can be constructed.

[0066] In the embodiments of the present invention, the light-emitting device includes the light-emitting element described above, and examples of such light-emitting devices include lighting equipment, backlights for liquid crystal panels, projector lamps, infrared lighting, light sources for infrared measurement, etc. It has been confirmed that the phosphor in the embodiments of the present invention emits light when excited by electron beams, vacuum ultraviolet light of 100 to 190 nm, ultraviolet light of 190 to 380 nm, visible light of 380 to 600 nm, etc., and the above-mentioned light-emitting device can be configured by combining these excitation sources with the phosphor of the present invention.

[0067] The phosphor in the embodiment of the present invention, which is made of an inorganic crystal phase having a specific chemical composition, has a red object color and can be used as a pigment or fluorescent pigment. That is, in the embodiment of the present invention, when the phosphor is irradiated with sunlight or lighting such as a fluorescent lamp, a red object color is observed, and since the color is good and does not deteriorate over a long period of time, the phosphor in the embodiment of the present invention is suitable as an inorganic pigment. Therefore, when used as a colorant added to paints, inks, paints, glazes, and plastic products, it is possible to maintain a good color development for a long period of time.

[0068] In the embodiment of the present invention, the phosphor absorbs ultraviolet rays, so it is also suitable as an ultraviolet absorbing agent. Therefore, when it is used as a paint or applied to the surface of a plastic product or kneaded into the inside of the product, it has a high ultraviolet blocking effect and can effectively protect the product from ultraviolet degradation.

[0069] In an embodiment of the present invention, another light-emitting device includes a white light-emitting diode, an infrared light-emitting diode, a diode that emits white and infrared light, or a lighting fixture or a backlight for a liquid crystal panel that includes a plurality of such light-emitting diodes, each of which includes a phosphor in an embodiment of the present invention. EXAMPLES

[0070] The present invention will be described in more detail by the following examples. However, these examples are merely disclosed as an aid to easily understand the present invention, and the present invention is not limited to these examples.

[0071] <<Raw material powder>> The raw powder used for the synthesis had a specific surface area of ​​11.2 m 2 Silicon nitride powder (SN-E10 grade manufactured by Ube Industries, Ltd.) with a particle size of 1.29 wt. % and α-type content of 95%, and a specific surface area of ​​3.3 m 2 Aluminum nitride powder (E grade, manufactured by Tokuyama Corporation) with a particle size of 1.0 / g and an oxygen content of 0.82% by weight and a specific surface area of ​​13.2 m 2 The materials used were aluminum oxide powder (Taimicron, manufactured by Taimei Chemical Industry Co., Ltd.) with a particle size of 1000 nm / g, lithium nitride (Li3N; manufactured by High Purity Chemical Laboratory) powder, magnesium nitride (Mg3N2; manufactured by High Purity Chemical Laboratory), calcium nitride (Ca3N2; manufactured by High Purity Chemical Laboratory), strontium nitride (Sr3N2; manufactured by Materion) with a purity of 99.5%, barium nitride (Ba3N2; manufactured by Materion) with a purity of 99.7%, europium nitride (EuN; manufactured by Materion), rare earth nitrides (manufactured by Materion), and rare earth oxides (purity 99.9%, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0072] <<Structural analysis of this crystal>> Sr3Si12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 Crystals were synthesized and the crystal structure was analyzed.

[0073] Silicon nitride (Si3N4), aluminum nitride (AlN), aluminum oxide (Al2O3), lithium nitride (Li3N), and strontium nitride (Sr3N2) are classified into Sr3Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 To obtain the composition, the molar ratios of Si3N4 4.144, AlN 7.496, Al2O3 0.536, Li3N 0.32, and Sr3N2 1 were weighed out and mixed for 5 minutes using a pestle and mortar made of sintered silicon nitride in a glove box with a nitrogen atmosphere containing 1 ppm oxygen. The resulting mixed powder was then placed in a crucible made of sintered boron nitride. The bulk density of the mixed powder (powder) was approximately 30%.

[0074] The crucible containing the mixed powder was placed in a graphite resistance heating electric furnace. The firing process was carried out by first changing the firing atmosphere to 1×10 -1 The furnace was evacuated to a pressure of less than 1 Pa and heated from room temperature to 800°C at a rate of 500°C per hour. At 800°C, nitrogen with a purity of 99.999% by volume was introduced to make the pressure inside the furnace 1 MPa. The temperature was then increased at a rate of 500°C per hour to 1900°C and held at that temperature for 2 hours.

[0075] The composite was observed under an optical microscope, and crystal particles of 40 μm in size were extracted from the composite. The elements contained in these crystal particles were analyzed using a scanning electron microscope (SEM; Hitachi High-Technologies SU1510) equipped with an energy dispersive elemental analyzer (EDS; Bruker AXS QUANTAX). As a result, the presence of Sr, Si, and Al elements was confirmed, and it was confirmed that the composition was as designed.

[0076] Next, the crystal was fixed to the tip of a glass fiber with an organic adhesive. X-ray diffraction measurements were performed using a single crystal X-ray diffractometer (SMART APEXII Ultra manufactured by Bruker AXS) equipped with a rotating anticathode and MoKα radiation, with the X-ray source output at 50 kV and 50 mA. As a result, it was confirmed that the crystal particle was a single crystal.

[0077] Next, the crystal structure was determined from the results of the X-ray diffraction measurement using single crystal structure analysis software (APEX2 manufactured by Bruker AXS). The obtained crystal structure data is shown in Table 1, and a diagram of the crystal structure is shown in Figure 1. Table 1 describes the crystal system, space group, lattice constant, type of atoms, and atomic positions, and this data can be used to determine the shape and size of the unit cell and the arrangement of atoms within it.

[0078] This crystal belongs to the hexagonal crystal system, the space group P63 (space group number 173 in the International Tables for Crystallography), and the lattice constant is a=b= 1.7416 nm, c = 0.48775 nm, Angle α = β = 90° Angle γ=120° The atomic positions are as shown in Table 1. Si and Al exist in the same atomic position B at a certain ratio, and this ratio was determined from the atomic ratio of EDS. O and N exist in the same atomic position X at a certain ratio, and this ratio was determined from the condition of electroneutrality of the crystal. The composition of this crystal determined from single crystal X-ray structure analysis is Sr3Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 It was.

[0079] The crystal structure data confirmed that this crystal is a novel substance that has not been reported before.

[0080] Figure 2 shows the Sr3Si 12.432 Al 8.568 O 1.608 N26.392 Li 0.96 FIG. 2 shows powder X-ray diffraction using CuKα radiation calculated from the crystal structure of the crystal.

[0081] Therefore, a powder X-ray diffraction measurement of the compound is performed. If the measured powder pattern is substantially the same as that shown in Figure 2, it is determined that the compound is the crystalline Sr3Si of Figure 1. 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 Furthermore, for those in which the lattice constants have been changed while maintaining the crystal structure by changing the composition, etc., the powder X-ray pattern can be calculated from the lattice constants obtained by powder X-ray diffraction measurement and the crystal structure data in Table 1, so by comparing the calculated pattern, it can be determined that the same crystal has been formed.

[0082] Sr3Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 From the crystal structure analysis, (1) Si and Al occupy the same site and can be substituted (2) O and N occupy the same seat and can be substituted (3) The Sr site in the crystal can be substituted for the (Si,Al)(O,N)4 site. (4) The amount of Li can be varied. Therefore, this crystal can be expressed as follows, using parameters x and y: Sr 6x (Si,Al) 27-12x (O,N) 31-6x Li 3y x=0.5 y=0.32 Al / (Al+Si)=8.568 / 21 O / (O+N)=1.608 / 28 We synthesized crystals with various compositions, and all of the crystals obtained were Sr 6x (Si,Al) 27-12x (O,N) 31-6xLi 3y The parameters x and y are written as follows: 0.4≦x≦0.8 0≦y≦0.35 It was found that this crystal structure is observed in the range of

[0083] As the values ​​of x and y change, the occupancy rates of A01, A02, B06, B07, B08, B09, C01, X10, and X11 in Table 1 change.

[0084] Furthermore, when various element compositions were synthesized, it was found that the Sr site could be replaced by the A element and the M element. Here, the A element is an element selected from the group consisting of Mg, Ca, Sr, and Ba, and the M element is an element selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm, and Yb. From these results, it was found that this crystal and this identical crystal have the general formula (A, M) 6x D 27-12x E 31-6x G 3y where the E elements are O and / or N, and the G element is Li.

[0085] <<Synthesis of phosphors>> [Experiment 1] Next, Sr 6x (Si,Al) 27-12x (O,N) 31-6x Li 3y ; Phosphor (Sr, Eu) with host crystal of x=0.5, y=0.28 6x (Si,Al) 27-12x (O,N) 31-6x Li 3y was synthesized.

[0086] Silicon nitride (Si3N4), aluminum nitride (AlN), aluminum oxide (Al2O3), lithium nitride (Li3N), strontium nitride (Sr3N2), and europium nitride (EuN) are 2.9 ,EU 0.1 )(Si 12.6 ,Al 8.4 )(O1.56 ,N 26.44 )Li 0.84 The mixture composition was designed so that the composition would be as follows: Eu in the raw material EuN is trivalent, but changes to divalent during firing, and the composition was designed assuming that excess nitrogen is released outside the sample.

[0087] The raw powders were weighed out to have a molar ratio of Si3N4:31.281, AlN:55.0075, Al2O3:3.8864, Li3N:2.09268, Sr3N2:7.1996, and EuN:0.74479, and mixed for 5 minutes using a pestle and mortar made of sintered silicon nitride in a glove box with a nitrogen atmosphere containing 1 ppm oxygen. The mixed powder was then placed in a crucible made of sintered boron nitride. The bulk density of the mixed powder (powder) was about 30%.

[0088] The crucible containing the mixed powder was placed in a graphite resistance heating electric furnace. The firing process was carried out by first changing the firing atmosphere to 1×10 -1 The furnace was evacuated to a pressure of less than 1 Pa and heated from room temperature to 800°C at a rate of 500°C per hour. At 800°C, nitrogen with a purity of 99.999% by volume was introduced to make the pressure inside the furnace 1 MPa. The temperature was then increased at a rate of 500°C per hour to 1900°C and held at that temperature for two hours.

[0089] The composite was observed under an optical microscope, and crystal particles of 40 μm in size were extracted from the composite. The elements contained in the crystal particles were analyzed using a scanning electron microscope (SEM; Hitachi High-Technologies SU1510) equipped with an energy dispersive elemental analyzer (EDS; Bruker AXS QUANTAX). As a result, the presence of Sr, Eu, Si, and Al elements was confirmed, and it was confirmed that the composition was as designed.

[0090] Next, this crystal was fixed to the tip of a glass fiber with an organic adhesive. X-ray diffraction measurements were performed on this using a single crystal X-ray diffractometer (SMART APEXII Ultra manufactured by Bruker AXS) equipped with a rotating anticathode and MoKα radiation, with the X-ray source output at 50 kV and 50 mA. As a result, it was confirmed that this crystal particle was a single crystal.

[0091] The crystal structure was determined from the results of the X-ray diffraction measurement using single crystal structure analysis software (APEX2 manufactured by Bruker AXS). The obtained structure was the same as the crystal structure of this crystal. Sr and Eu are present at the same atomic positions, and oxygen and nitrogen are present at the same atomic positions, and when averaged as a whole, this is the composition ratio of the crystal.

[0092] Next, the excitation and emission spectra of the collected crystal particles were measured using a JASCO FP8600 fluorescence spectrophotometer. The results are shown in Figure 3. FIG. 3 is a diagram showing the emission spectrum of the phosphor synthesized in Experiment 1.

[0093] According to FIG. 3, the sample of Experiment 1 was found to be a red-emitting phosphor having a maximum emission peak at a wavelength of 667 nm when excited with light having a wavelength of 410 nm.

[0094] [Experiment 2 to Experiment 37] Mix the compositions shown in Table 2 and prepare them in the same manner as in Experiment 1 (A, M). 6x D 27-12x E 31-6x G 3y The phosphor was synthesized. Crystal particles were collected from the synthesized product and the crystal phase was identified using a single crystal X-ray diffraction device. The results were as follows: Sr3Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 The crystal structure of these powders was confirmed to be the same as that of the powders shown in Table 3 and Figure 4.

[0095] [Table 2]

[0096] [Table 3]

[0097] As shown in Table 3, all of the samples obtained in Experiments 2 to 37 were phosphors that had a maximum emission peak at a wavelength of 600 nm or more and emitted red or near infrared light. FIG. 4 is a diagram showing the emission spectrum of the phosphor synthesized in Experiment 2.

[0098] The sample synthesized in experiment 2 was (Sr2,Eu1)(Si 12.6 , Al 8.4 )(O 1.56 , N 26.44 )Li 0.84 It was found to be an infrared-emitting phosphor having a maximum emission peak at a wavelength of 741 nm when excited by light having a wavelength of 424 nm.

[0099] [Experiment 38~Experiment 101] Mix the compositions shown in Tables 4 and 5 and prepare them in the same manner as in Experiment 1 (A, M). 6x D 27-12x E 31-6x G 3y The phosphors were synthesized. Crystal particles were collected from the synthesized products, and the crystal phases were identified using a single crystal X-ray diffraction device. As a result, the crystal phases were identified as Sr3Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 It was confirmed that the crystal structure was the same as that of the above. Here, Experiment 59 and Experiment 69 are reference experimental examples.

[0100] [Table 4]

[0101] [Table 5]

[0102] When the samples (particles) synthesized in Experiments 38 to 101 were observed by microspectroscopy while irradiating them with light of 360 nm, red to near-infrared emission was confirmed, except for the samples synthesized in Experiments 59 and 69. Note that the compositions in Tables 4 and 5 are (A, M) 6x D 27-12x E 31-6x G 3y In some cases, the phase may deviate from the above range, in which case the crystal is a mixture of the same crystal and other phases.

[0103] [Experiment 102~Experiment 113] Mix the compositions shown in Table 6 and prepare them in the same manner as in Experiment 1 (A, M). 6x D 27-12x E 31-6x G 3y The phosphor was synthesized. Crystal particles were collected from the synthesized product and the crystal phase was identified using a single crystal X-ray diffraction device. The results were as follows: Sr3Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 It was confirmed that the crystal structure is the same as that of the crystalline structure.

[0104] [Table 6]

[0105] When the samples (particles) synthesized in Experiments 102 to 113 were irradiated with 360 nm ultraviolet light, visible to infrared light was observed.

[0106] As described above, in the embodiment of the present invention, at least the A element, the M element, the D element, and the E element (wherein A includes at least one or more elements selected from the group consisting of Mg, Ca, Sr, and Ba, M is one or more elements selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm, and Yb, D is one or more elements selected from the group consisting of Si and Al, and E is one or more elements selected from the group consisting of O and N), and optionally the G element (wherein G is the Li element), (A,M) a D d E e G g The atomic fraction parameters a, d, e, and g are expressed as follows: 2.4 ≦ a ≦ 4.8 17.4≦d≦22.2 26.2≦e≦28.6 0≦g≦3 However, the specific composition in which M is Eu as shown below is particularly important. (Mg,Eu) a S d O e Li g , (Mg,Eu) a S d O e , (Mg,Eu) a S d (O,N) e Li g , (Mg,Eu) a S d (O,N) e , (Mg,Eu) a S d N e Li g , (Mg,Eu) a S d N e , (Mg,Eu) a (Si,Al) d O e Li g , (Mg,Eu) a (Si,Al) d O e , (Mg,Eu) a (Si,Al) d (O,N) e Li g , (Mg,Eu) a (Si,Al) d (O,N) e , (Mg,Eu) a (Si,Al) d N e Li g , (Mg,Eu) a (Si,Al) d Ne 、(Mg,Iu) a the d A e them g 、(Mg,Iu) a the d A e 、(Mg,Iu) a the d (Y,N) e them g 、(Mg,Iu) a the d (Y,N) e 、(Mg,Iu) a the d N e them g 、(Mg,Iu) a the d N e 、(Like,I) a And d A e them g 、(Like,I) a And d A e 、(Like,I) a And d (Y,N) e them g 、(Like,I) a And d (Y,N) e 、(Like,I) a And d N e them g 、(Like,I) a And d N e 、(Like,I) a (Si,Al) d A e them g 、(Like,I) a (Si,Al) d A e 、(Like,I) a (Si,Al) d (Y,N) e them g 、(Like,I) a (Si,Al) d (Y,N) e 、(Like,I) a(Si,Al) d N e them g 、(Like,I) a (Si,Al) d N e 、(Like,I) a the d A e them g 、(Like,I) a the d A e 、(Like,I) a the d (Y,N) e them g 、(Like,I) a the d (Y,N) e 、(Like,I) a the d N e them g 、(Like,I) a the d N e 、(Sr,I) a And d A e them g 、(Sr,I) a And d A e 、(Sr,I) a And d (Y,N) e them g 、(Sr,I) a And d (Y,N) e 、(Sr,I) a And d N e them g 、(Sr,I) a And d N e 、(Sr,I) a (Si,Al) d A e them g 、(Sr,I) a (Si,Al) d A e 、(Sr,I) a (Si,Al) d (Y,N) e themg 、(Sir, I) a (Si,Al) d (O,N) e 、(Sir, I) a (Si,Al) d N e I read g 、(Sir, I) a (Si,Al) d N e 、(Sir, I) a Al d THE e I read g 、(Sir, I) a Al d THE e 、(Sir, I) a Al d (O,N) e I read g 、(Sir, I) a Al d (O,N) e 、(Sir, I) a Al d N e I read g 、(Sir, I) a Al d N e 、(Ba,I) a Yes d THE e I read g 、(Ba,I) a Yes d THE e 、(Ba,I) a Yes d (O,N) e I read g 、(Ba,I) a Yes d (O,N) e 、(Ba,I) a Yes d N e I read g 、(Ba,I) a Yes d N e 、(Ba,I) a (Si,Al) d THE e I read g 、(Ba,I) a (Si,Al)d THE e 、(Ba,I) a (Si,Al) d (O,N) e I read g 、(Ba,I) a (Si,Al) d (O,N) e 、(Ba,I) a (Si,Al) d N e I read g 、(Ba,I) a (Si,Al) d N e 、(Ba,I) a Al d THE e I read g 、(Ba,I) a Al d THE e 、(Ba,I) a Al d (O,N) e I read g 、(Ba,I) a Al d (O,N) e 、(Ba,I) a Al d N e I read g 、(Ba,I) a Al d N e 、(Mg,Ca,Eu) a Yes d THE e I read g 、(Mg,Ca,Eu) a Yes d THE e 、(Mg,Ca,Eu) a Yes d (O,N) e I read g 、(Mg,Ca,Eu) a Yes d (O,N) e 、(Mg,Ca,Eu) a Yes d N e I read g 、(Mg,Ca,Eu) a Yes d Ne 、(Mg,Ca,Iu) a (Si,Al) d A e them g 、(Mg,Ca,Iu) a (Si,Al) d A e 、(Mg,Ca,Iu) a (Si,Al) d (Y,N) e them g 、(Mg,Ca,Iu) a (Si,Al) d (Y,N) e 、(Mg,Ca,Iu) a (Si,Al) d N e them g 、(Mg,Ca,Iu) a (And,Al,I) d N e 、(Mg,Ca,Iu) a the d A e them g 、(Mg,Ca,Iu) a the d A e 、(Mg,Ca,Iu) a the d (Y,N) e them g 、(Mg,Ca,Iu) a the d (Y,N) e 、(Mg,Ca,Iu) a the d N e them g 、(Mg,Ca,Iu) a the d N e 、(Mg,Sr,Iu) a And d A e them g 、(Mg,Sr,Iu) a And d A e 、(Mg,Sr,Iu) a And d (Y,N) e them g 、(Mg,Sr,Iu) aYes d (O,N) e 、(Mg,Sr,I) a Yes d N e I read g 、(Mg,Sr,I) a Yes d N e 、(Mg,Sr,I) a (Si,Al) d THE e I read g 、(Mg,Sr,I) a (Si,Al) d THE e 、(Mg,Sr,I) a (Si,Al) d (O,N) e I read g 、(Mg,Sr,I) a (Si,Al) d (O,N) e 、(Mg,Sr,I) a (Si,Al) d N e I read g 、(Mg,Sr,I) a (Si,Al、I) d N e 、(Mg,Sr,I) a Al d THE e I read g 、(Mg,Sr,I) a Al d THE e 、(Mg,Sr,I) a Al d (O,N) e I read g 、(Mg,Sr,I) a Al d (O,N) e 、(Mg,Sr,I) a Al d N e I read g 、(Mg,Sr,I) a Al d N e 、(Mg,Ba,Eu) a Yes d THE e I read g、(Mg,Ba,Eu) a Yes d THE e 、(Mg,Ba,Eu) a Yes d (O,N) e I read g 、(Mg,Ba,Eu) a Yes d (O,N) e 、(Mg,Ba,Eu) a Yes d N e I read g 、(Mg,Ba,Eu) a Yes d N e 、(Mg,Ba,Eu) a (Si,Al) d THE e I read g 、(Mg,Ba,Eu) a (Si,Al) d THE e 、(Mg,Ba,Eu) a (Si,Al) d (O,N) e I read g 、(Mg,Ba,Eu) a (Si,Al) d (O,N) e 、(Mg,Ba,Eu) a (Si,Al) d N e I read g 、(Mg,Ba,Eu) a (Si,Al、I) d N e 、(Mg,Ba,Eu) a Al d THE e I read g 、(Mg,Ba,Eu) a Al d THE e 、(Mg,Ba,Eu) a Al d (O,N) e I read g 、(Mg,Ba,Eu) a Al d (O,N) e 、(Mg,Ba,Eu) a Al d Ne them g 、(Mg,Ba,Iu) a the d N e 、(As,Sr,I) a And d A e them g 、(As,Sr,I) a And d A e 、(As,Sr,I) a And d (Y,N) e them g 、(As,Sr,I) a And d (Y,N) e 、(As,Sr,I) a And d N e them g 、(As,Sr,I) a And d N e 、(As,Sr,I) a (Si,Al) d A e them g 、(As,Sr,I) a (Si,Al) d A e 、(As,Sr,I) a (Si,Al) d (Y,N) e them g 、(As,Sr,I) a (Si,Al) d (Y,N) e 、(As,Sr,I) a (Si,Al) d N e them g 、(As,Sr,I) a (And,Al,I) d N e 、(As,Sr,I) a the d A e them g 、(As,Sr,I) a the d A e 、(As,Sr,I)a the d (Y,N) e them g 、(As,Sr,I) a the d (Y,N) e 、(As,Sr,I) a the d N e them g 、(As,Sr,I) a the d N e 、(As,So,I) a And d A e them g 、(As,So,I) a And d A e 、(As,So,I) a And d (Y,N) e them g 、(As,So,I) a And d (Y,N) e 、(As,So,I) a And d N e them g 、(As,So,I) a And d N e 、(As,So,I) a (Si,Al) d A e them g 、(As,So,I) a (Si,Al) d A e 、(As,So,I) a (Si,Al) d (Y,N) e them g 、(As,So,I) a (Si,Al) d (Y,N) e 、(As,So,I) a (Si,Al) d N e them g 、(As,So,I) a (And,Al,I) d Ne 、(Ca,Ba,Eu) a Al d THE e I read g 、(Ca,Ba,Eu) a Al d THE e 、(Ca,Ba,Eu) a Al d (O,N) e I read g 、(Ca,Ba,Eu) a Al d (O,N) e 、(Ca,Ba,Eu) a Al d N e I read g 、(Ca,Ba,Eu) a Al d N e 、(Mr,Ba,I) a Yes d THE e I read g 、(Mr,Ba,I) a Yes d THE e 、(Mr,Ba,I) a Yes d (O,N) e I read g 、(Mr,Ba,I) a Yes d (O,N) e 、(Mr,Ba,I) a Yes d N e I read g 、(Mr,Ba,I) a Yes d N e 、(Mr,Ba,I) a (Si,Al) d THE e I read g 、(Mr,Ba,I) a (Si,Al) d THE e 、(Mr,Ba,I) a (Si,Al) d (O,N) e I read g 、(Mr,Ba,I) a (Si,Al)d (O,N) e 、(Mr,Ba,I) a (Si,Al) d N e I read g 、(Mr,Ba,I) a (Si,Al、I) d N e 、(Mr,Ba,I) a Al d THE e I read g 、(Mr,Ba,I) a Al d THE e 、(Mr,Ba,I) a Al d (O,N) e I read g 、(Mr,Ba,I) a Al d (O,N) e 、(Mr,Ba,I) a Al d N e I read g 、(Mr,Ba,I) a Al d N e 、(Mg,Ca,Sr,Eu) a Yes d THE e I read g 、(Mg,Ca,Sr,Eu) a Yes d THE e 、(Mg,Ca,Sr,Eu) a Yes d (O,N) e I read g 、(Mg,Ca,Sr,Eu) a Yes d (O,N) e 、(Mg,Ca,Sr,Eu) a Yes d N e I read g 、(Mg,Ca,Sr,Eu) a Yes d N e 、(Mg,Ca,Sr,Eu) a (Si,Al) d THE e I read g、(Mg,Ca,Sr,Iu) a (Si,Al) d A e 、(Mg,Ca,Sr,Iu) a (Si,Al) d (Y,N) e them g 、(Mg,Ca,Sr,Iu) a (Si,Al) d (Y,N) e 、(Mg,Ca,Sr,Iu) a (Si,Al) d N e them g 、(Mg,Ca,Sr,Iu) a (And,Al,I) d N e 、(Mg,Ca,Sr,Iu) a the d A e them g 、(Mg,Ca,Sr,Iu) a the d A e 、(Mg,Ca,Sr,Iu) a the d (Y,N) e them g 、(Mg,Ca,Sr,Iu) a the d (Y,N) e 、(Mg,Ca,Sr,Iu) a the d N e them g 、(Mg,Ca,Sr,Iu) a the d N e 、(Mg,Ca,Ba,Iu) a And d A e them g 、(Mg,Ca,Ba,Iu) a And d A e 、(Mg,Ca,Ba,Iu) a And d (Y,N) e them g 、(Mg,Ca,Ba,Iu) a And d (Y,N) e、(Mg,Ca,Ba,Iu) a And d N e them g 、(Mg,Ca,Ba,Iu) a And d N e 、(Mg,Ca,Ba,Iu) a (Si,Al) d A e them g 、(Mg,Ca,Ba,Iu) a (Si,Al) d A e 、(Mg,Ca,Ba,Iu) a (Si,Al) d (Y,N) e them g 、(Mg,Ca,Ba,Iu) a (Si,Al) d (Y,N) e 、(Mg,Ca,Ba,Iu) a (Si,Al) d N e them g 、(Mg,Ca,Ba,Iu) a (And,Al,I) d N e 、(Mg,Ca,Ba,Iu) a the d A e them g 、(Mg,Ca,Ba,Iu) a the d A e 、(Mg,Ca,Ba,Iu) a the d (Y,N) e them g 、(Mg,Ca,Ba,Iu) a the d (Y,N) e 、(Mg,Ca,Ba,Iu) a the d N e them g 、(Mg,Ca,Ba,Iu) a the d N e 、(Mg,Sr,Ba,Iu) a And d A e themg 、(Mg,Sr,Ba,Eu) a Yes d THE e 、(Mg,Sr,Ba,Eu) a Yes d (O,N) e I read g 、(Mg,Sr,Ba,Eu) a Yes d (O,N) e 、(Mg,Sr,Ba,Eu) a Yes d N e I read g 、(Mg,Sr,Ba,Eu) a Yes d N e 、(Mg,Sr,Ba,Eu) a (Si,Al) d THE e I read g 、(Mg,Sr,Ba,Eu) a (Si,Al) d THE e 、(Mg,Sr,Ba,Eu) a (Si,Al) d (O,N) e I read g 、(Mg,Sr,Ba,Eu) a (Si,Al) d (O,N) e 、(Mg,Sr,Ba,Eu) a (Si,Al) d N e I read g 、(Mg,Sr,Ba,Eu) a (Si,Al、I) d N e 、(Mg,Sr,Ba,Eu) a Al d THE e I read g 、(Mg,Sr,Ba,Eu) a Al d THE e 、(Mg,Sr,Ba,Eu) a Al d (O,N) e I read g 、(Mg,Sr,Ba,Eu) a Al d (O,N)e 、(Mg,Sr,Ba,Eu) a Al d N e I read g 、(Mg,Sr,Ba,Eu) a Al d N e 、(Ca,Sr,Ba,I) a Yes d THE e I read g 、(Ca,Sr,Ba,I) a Yes d THE e 、(Ca,Sr,Ba,I) a Yes d (O,N) e I read g 、(Ca,Sr,Ba,I) a Yes d (O,N) e 、(Ca,Sr,Ba,I) a Yes d N e I read g 、(Ca,Sr,Ba,I) a Yes d N e 、(Ca,Sr,Ba,I) a (Si,Al) d THE e I read g 、(Ca,Sr,Ba,I) a (Si,Al) d THE e 、(Ca,Sr,Ba,I) a (Si,Al) d (O,N) e I read g 、(Ca,Sr,Ba,I) a (Si,Al) d (O,N) e 、(Ca,Sr,Ba,I) a (Si,Al) d N e I read g 、(Ca,Sr,Ba,I) a (Si,Al、I) d N e 、(Ca,Sr,Ba,I) a Al d THEe I read g 、(Ca,Sr,Ba,I) a Al d THE e 、(Ca,Sr,Ba,I) a Al d (O,N) e I read g 、(Ca,Sr,Ba,I) a Al d (O,N) e 、 (Ca,Sr,Ba,Me) a Al d N e I read g 、(Ca,Sr,Ba,I) a Al d N e 、(Mg,Ca,Sr,Ba,Eu) a Yes d THE e I read g 、(Mg,Ca,Sr,Ba,Eu) a Yes d THE e 、(Mg,Ca,Sr,Ba,Eu) a Yes d (O,N) e I read g 、(Mg,Ca,Sr,Ba,Eu) a Yes d (O,N) e 、(Mg,Ca,Sr,Ba,Eu) a Yes d N e I read g 、(Mg,Ca,Sr,Ba,Eu) a Yes d N e 、(Mg,Ca,Sr,Ba,Eu) a (Si,Al) d THE e I read g 、(Mg,Ca,Sr,Ba,Eu) a (Si,Al) d THE e 、(Mg,Ca,Sr,Ba,Eu) a (Si,Al) d (O,N) e I read g、(Mg,Ca,Sr,Ba,Eu) a (Si,Al) d (O,N) e 、(Mg,Ca,Sr,Ba,Eu) a (Si,Al) d N e I read g 、(Mg,Ca,Sr,Ba,Eu) a (Si,Al、I) d N e 、(Mg,Ca,Sr,Ba,Eu) a Al d THE e I read g 、(Mg,Ca,Sr,Ba,Eu) a Al d THE e 、(Mg,Ca,Sr,Ba,Eu) a Al d (O,N) e I read g 、(Mg,Ca,Sr,Ba,Eu) a Al d (O,N) e 、(Mg,Ca,Sr,Ba,Eu) a Al d N e I read g 、(Mg,Ca,Sr,Ba,Eu) a Al d N e 、(Mg,Ca,Sr,Ba,Eu) a Yes d THE e I read g 、(Mg,Ca,Sr,Ba,Eu) a Yes d THE e 、(Mg,Ca,Sr,Ba,Eu) a Yes d (O,N) e I read g 、(Mg,Ca,Sr,Ba,Eu) a Yes d (O,N) e 、(Mg,Ca,Sr,Ba,Eu) a Yes d N e I read g 、(Mg,Ca,Sr,Ba,Eu) a Yesd N e , (Mg, Ca, Sr, Ba, Eu) a (Si,Al) d O e Li g , (Mg, Ca, Sr, Ba, Eu) a (Si,Al) d O e , (Mg, Ca, Sr, Ba, Eu) a (Si,Al) d (O,N) e Li g , (Mg, Ca, Sr, Ba, Eu) a (Si,Al) d (O,N) e , (Mg, Ca, Sr, Ba, Eu) a (Si,Al) d N e Li g , (Mg, Ca, Sr, Eu) a (Si, Al, Eu) d N e , (Mg, Ca, Sr, Eu) a Al d O e Li g , (Mg, Ca, Sr, Ba, Eu) a Al d O e , (Mg, Ca, Sr, Ba, Eu) a Al d (O,N) e Li g , (Mg, Ca, Sr, Ba, Eu) a Al d (O,N) e , (Mg, Ca, Sr, Ba, Eu) a Al d N e Li g , (Mg, Ca, Sr, Ba, Eu) a Al d N e . Also included in the present invention are examples that contain Mn, Ce, Nd, Tb, Dy, Ho, Er, Tm, and / or Yb together with or instead of Eu, as shown in Experiments 105 to 113 (Table 6).

[0107] <<Light emitting device>> [Example 114] FIG. 5 is a schematic diagram showing a lighting fixture (bullet-type LED lighting fixture) according to the present invention.

[0108] As a light-emitting device, a bullet-shaped white light-emitting diode lamp (1) as shown in FIG. 5 was produced. There are two lead wires (2, 3), one of which (2) has a recess, on which an ultraviolet light-emitting diode element (4) with an emission peak at 365 nm is placed. The lower electrode of the ultraviolet light-emitting diode element (4) and the bottom surface of the recess are electrically connected by conductive paste, and the upper electrode and the other lead wire (3) are electrically connected by a gold thin wire (5). Phosphor (7) is dispersed in resin and mounted near the light-emitting diode element (4). This first resin (6) in which the phosphor is dispersed is transparent and covers the entire ultraviolet light-emitting diode element (4). The tip of the lead wire including the recess, the blue light-emitting diode element, and the first resin in which the phosphor is dispersed are sealed with a transparent second resin (8). The transparent second resin (8) is generally cylindrical in shape, and its tip is curved in a lens shape, and is commonly called a bullet type.

[0109] In Example 114, the phosphor powder prepared in Experiment 1, JEM:Ce blue phosphor, β-sialon:Eu, and CaAlSiN3:Eu were mixed in a mass ratio of 4:4:1:1, and mixed with epoxy resin at a concentration of 35% by weight, and an appropriate amount of this was dropped using a dispenser to form a first resin (6) with the phosphor mixture (7) dispersed therein. The color of the obtained light-emitting device was white, containing luminescent components ranging from blue to infrared.

[0110] [Example 115] FIG. 6 is a schematic diagram showing a lighting fixture (board-mounted LED lighting fixture) according to the present invention.

[0111] We produced a chip-type light-emitting diode lamp (11) for mounting on a board, as shown in Figure 6. Two lead wires (12, 13) are fixed to a white alumina ceramics substrate (19) with high visible light reflectance, with one end of each wire located almost in the center of the substrate and the other end protruding from the substrate to serve as an electrode to be soldered when mounted on an electric substrate. A blue light-emitting diode element (14) with an emission peak wavelength of 450 nm is placed and fixed on one end of one of the lead wires (12) so that it is in the center of the substrate. The lower electrode of the blue light-emitting diode element (14) and the lower lead wire are electrically connected by conductive paste, and the upper electrode and the other lead wire (13) are electrically connected by a thin gold wire (15).

[0112] A mixture of the first resin (16) and a phosphor (17) obtained by mixing the phosphor prepared in Experiment 1 and a CaAlSiN3:Eu red phosphor in a mass ratio of 1:1 is mounted near the light-emitting diode element. The first resin in which the phosphor is dispersed is transparent and covers the entire blue light-emitting diode element (14). A wall member (20) having a hole in the center is fixed on the ceramic substrate. The center of the wall member (20) is a hole for the blue light-emitting diode element (14) and the resin (16) in which the phosphor (17) is dispersed, and the portion facing the center is a slope. This slope is a reflective surface for extracting light forward, and the curved shape of the slope is determined in consideration of the direction of light reflection. At least the surface constituting the reflective surface is a surface having a high visible light reflectance with a white or metallic luster. In this example, the wall member (20) is made of a white silicone resin. The hole in the center of the wall member forms a recess in the final shape of the chip-type light-emitting diode lamp, and this is filled with a transparent second resin (18) so as to seal all of the first resin (16) in which the blue light-emitting diode element (14) and the phosphor (17) are dispersed. In this example, the same epoxy resin is used for the first resin (16) and the second resin (18). Red and infrared emitting LEDs were obtained. [Industrial Applicability]

[0113] The nitride / oxynitride phosphor of the present invention has emission characteristics (emission color, excitation characteristics, emission spectrum) different from conventional phosphors, and has high emission intensity even when combined with an LED excitation source, is chemically and thermally stable, and furthermore, the decrease in brightness of the phosphor when exposed to the excitation source is small, so it is a nitride phosphor suitable for use in white LEDs, etc. It is expected that in the future, it will be widely used in material design for various display devices and contribute to industrial development. [Explanation of symbols]

[0114] 1. Bullet-type white light-emitting diode lamp 2, 3 Lead Wires 4. Ultraviolet light-emitting diode element 5 Gold thin wire 6, 8 Resin 7 Phosphors 11. Chip-type light-emitting diode lamp for substrate mounting 12, 13 Lead wire 14 Blue light emitting diode element 15 Gold thin wire 16, 18 Resin 17 Phosphor 19 Alumina ceramic substrate 20 Wall components

Claims

1. at least an A element, an M element, a D element, and an E element (wherein A includes at least one or more elements selected from the group consisting of Mg, Ca, Sr, and Ba, M includes one or more elements selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm, and Yb, D includes Si and Al or an element consisting of Al, and E includes O and N or an element consisting of N), and optionally includes a G element (wherein G is a Li element); (A, M) ａ D ｄ E ｅ G ｇ The atomic fraction parameters a, d, e, and g are expressed as follows: 2.4 ≦ a ≦ 4.8 17.4 ≦ d ≦ 22.2 26.2 ≦ e ≦ 28.6 0≦g≦3 A 6x-m M m D 27-12x E 31-6x G 3y (wherein x and y are each 0.4≦x≦0.8, 0≦3y≦1.05, or 3y is either 1.5 or 3, and the M content m is 0.001≦m≦0.1, or m is either 0.12, 0.3, 1, 1.2, 1.5, or 2), and the inorganic compound is (Sr, Eu) ３ (Si, Al) ２１ (O, N) ２８ Li ０．９６ A phosphor is a crystal represented by the formula:

2. at least an A element, an M element, a D element, and an E element (wherein A includes at least one or more elements selected from the group consisting of Mg, Ca, Sr, and Ba, M includes one or more elements selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm, and Yb, D includes Si and Al or an element consisting of Al, and E includes O and N or an element consisting of N), and optionally includes a G element (wherein G is a Li element); (A, M) ａ D ｄ E ｅ G ｇ The atomic fraction parameters a, d, e, and g are expressed as follows: 2.4 ≦ a ≦ 4.8 17.4 ≦ d ≦ 22.2 26.2 ≦ e ≦ 28.6 0≦g≦3 and a composition of A 6x-m M m D 27-12x E 31-6x G 3y (wherein x and y are each 0.4≦x≦0.8, 0≦3y≦1.05, or 3y is either 1.5 or 3, and the content m of M is 0.001≦m≦0.1, or m is either 0.12, 0.3, 1, 1.2, 1.5, or 2), and the inorganic compound is It is a hexagonal crystal with lattice constants a, b, and c. 1.6 < a < 1.8 nm b = a 0.44<c<0.52nm That is, phosphor.

3. The parameter g is 0.21 ≦ g ≦ 1.05 The phosphor according to claim 1 or 2, which is represented by a numerical value in the range of:

4. The phosphor according to claim 1 , wherein the x satisfies 0.45≦x≦0.

55.

5. The phosphor according to claim 1, wherein y satisfies 0≦y≦0.

35.

6. The inorganic compound is Sr ３ S １２．４３２ A ８．５６８ O １．６０８ N ２６．３９２ Li ０．９６ The phosphor according to claim 1 or 2, which is a crystal having the same crystal structure as

7. The crystal is P6 ３ 3. The phosphor according to claim 1, which is a crystal belonging to space group 173 of the International Tables for Crystallography.

8. The phosphor according to claim 1 , wherein the A element is Sr.

9. The D element is The phosphor according to claim 1 or 2, which satisfies 0.4≦Al / (Al+Si)≦0.

6.

10. The E element is The phosphor according to claim 1 or 2, which satisfies 0.01≦O / (O+N)≦0.

1.

11. 3. The phosphor according to claim 1, which emits light having a maximum emission peak in the wavelength range of 600 nm to 850 nm when irradiated with light having a wavelength in the range of 300 nm to 600 nm.

12. 12. The method for producing a phosphor according to claim 1, comprising mixing raw materials selected from the group consisting of nitrides, oxynitrides, oxides, carbonates, and fluorides of an A element (wherein A is one or more elements selected from the group consisting of Mg, Ca, Sr, and Ba), an M element (wherein M is one or more elements selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm, and Yb), a D element (an element consisting of Si and Al or consisting of Al), and, if necessary, a G element (wherein G is Li), and firing the mixture at a temperature of 1400° C. or higher and 2200° C. or lower.

13. A light-emitting device comprising an excitation source that emits light having a wavelength in the range of 300 nm to 600 nm, and the phosphor according to any one of claims 1 to 11.

14. The light-emitting device according to claim 13, wherein the excitation source is a light-emitting diode (LED) or a laser diode (LD).

15. The light-emitting device according to claim 13, further comprising one or more phosphors that emit fluorescence having a maximum emission peak in a wavelength range of 400 nm to 760 nm when irradiated with light having a wavelength in the range of 300 nm to 600 nm.

16. Furthermore, AlN:(Eu,Si), BaMgAl １０ O １７ : Eu, SrSi ９ A １９ ON ３１ : Eu, LaSi ９ A １９ N ３２ : Eu, α-sialon: Ce, JEM: Ce, β-sialon: Eu, (Ba, Sr, Ca, Mg) ２ SiO ４ :Eu, (Ca, Sr, Ba)Si ２ O ２ N ２ : Eu, YAG: Ce, α-sialon: Eu, CaAlSiN ３ : Ce, La ３ S ６ N １１ :Ce, CaAlSiN ３ :Eu, (Ca,Sr)AlSiN ３ : Eu, Ca ２ S ５ N ８ : Eu and Sr ２ S ５ N ８ 16. The light-emitting device according to claim 13, comprising one or more phosphors selected from the group consisting of: Eu.

17. A light-emitting device comprising the light-emitting element according to claim 13, which is any one of a lighting fixture, a backlight for a liquid crystal panel, a lamp for a projector, an infrared light source, and an infrared measurement light source.

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