JP6288343B2 - Phosphor and light emitting device using the same - Google Patents

Description

  The present invention relates to a phosphor and a light emitting device using the same, and more particularly to a nitride phosphor made of a nitrogen-containing compound and capable of emitting light from green to yellow, and a light emitting device using the same.

  By combining a light source and a wavelength conversion member that can be excited by light from this light source and emit light of a hue different from the hue of the light source, light of various hues can be emitted according to the principle of light color mixing Light emitting devices have been developed. For example, primary light from a short wavelength region corresponding to visible light is emitted from the light emitting element from ultraviolet light, and the phosphor is excited by the emitted light. As a result, at least a part of the primary light is wavelength-converted, and desired light such as red, blue, and green can be obtained. Further, white light can be realized by additively mixing these component lights.

  Using this principle, an LED lamp using a light emitting diode (hereinafter referred to as “LED”) as a light source is used as a signal light, a mobile phone, various types of lighting, an in-vehicle display, or various types of display devices. It is used in many fields. In particular, white LED light-emitting devices formed by combining LEDs and phosphors are actively applied to backlights of liquid crystal displays, small-sized strobes, and the like, and are spreading. In addition, recently, use in lighting devices has been attempted, and it is expected as a light source that can replace fluorescent lamps with reduced environmental load by taking advantage of long life and mercury-free.

  As a configuration of a light emitting device using a white LED, a configuration in which a blue LED and a yellow phosphor are combined can be given (for example, see Patent Document 1). This light emitting device can obtain a white color by mixing blue light from an LED and yellow light obtained by converting a part of the blue light emitted from the LED with a yellow phosphor. Is. Therefore, the phosphor used in this light emitting device is required to have a characteristic of being efficiently excited by blue light having a wavelength of 420 nm to 470 nm emitted from the LED and emitting yellow light.

  On the other hand, research to improve the light emission characteristics of LED light emitting devices is also actively conducted. For example, in order to increase the brightness of white light, it is important to improve the brightness of each color component light. For this reason, the fluorescent substance which can convert the primary light from LED into energy efficiently is preferable. Further, in order to improve the color rendering properties and color purity of white light, it is important that each component light emits light with a predetermined color. For this reason, a phosphor having a peak wavelength in a predetermined wavelength region is desirable.

  As such a yellow phosphor, a cerium activated yttrium / aluminum / garnet phosphor is known. Further, a phosphor is known in which a part of Y of this yellow phosphor is substituted with Lu, Tb, Gd or the like, or a part of Al is substituted with Ga or the like. The cerium-activated yttrium / aluminum / garnet phosphor can be widely adjusted in emission wavelength by adjusting the composition.

On the other hand, nitride phosphors different from such oxide phosphors are also known to have characteristics not found in other inorganic compounds, although they are not easily manufactured compared to oxide phosphors. In particular, Si ₃ N ₄ , AlN, BN, GaN, and the like are used for various applications such as substrate materials, semiconductors, and light-emitting diodes, and are industrially produced. In recent years, nitrides composed of ternary or higher elements have been extensively studied, and it has been reported that there are compounds that emit blue to red light when excited by blue LEDs or near-ultraviolet LEDs. .

By the way, since the emission spectrum differs depending on each compound and phosphor, it has been promoted to further improve the characteristics of the white LED using these phosphors. For example, by adding a (Sr, Ca) AlSiN ₃ : Eu phosphor, which is a nitride-based phosphor, to the white LED described in Patent Document 1, color rendering properties and a color reproduction range can be improved (patent) Reference 2).

Furthermore, by replacing the cerium-activated yttrium / aluminum / garnet phosphor, which is a yellow component, with another phosphor, the color rendering properties and the color reproduction range can be improved. As such a phosphor, La ₃ Si ₆ N ₁₁ : Ce has been reported (Patent Documents 3 and 4).

Japanese Patent No. 3503139 JP 2006-8721 A JP 2008-88362 A JP 2008-285659 A

The present invention has been made in view of such a background. The main object of the present invention is to focus on, for example, La ₃ Si ₆ N ₁₁ : Ce, and to provide a phosphor capable of improving its emission characteristics and a light emitting device using the phosphor.

According to the phosphor according to an aspect of the present invention, a phosphor whose general formula is expressed as _{M x Ce y Si 6-z} B z N 8 + w, M is, La, Y, Tb, Lu At least one element selected from the group consisting of

W, x, y and z in the general formula are each
2.0 <w <4.0,
2.33 <x <3.0,
0.06 <y <0.5,
0 <z <0.3
Can be met.

  In addition, according to the light emitting device according to another aspect, an excitation light source that emits light in a short wavelength region from ultraviolet to visible light, and the above-described fluorescence capable of emitting fluorescence by absorbing a part of the light from the excitation light source The 1st fluorescent substance which is a body, and the wavelength conversion member containing said 1st fluorescent substance can be provided.

  According to the present invention, a phosphor with improved luminance can be realized.

FIG. 1 is a cross-sectional view showing a light emitting device according to this embodiment. FIG. 2 is a graph showing emission spectra of the phosphors according to Examples 1 to 3 and Comparative Example 1. FIG. 3 is a graph showing excitation spectra of the phosphors according to Examples 1 to 3 and Comparative Example 1. FIG. 4 is a 1000 times SEM photograph of the phosphor according to Example 3. FIG. 5 is a graph showing emission spectra of the phosphors according to Example 2, Reference Example 4, and Comparative Examples 2 and 3. FIG. 6 is a graph showing excitation spectra of the phosphors according to Example 2, Reference Example 4 and Comparative Examples 2 and 3. FIG. 7 is a graph showing emission spectra of the phosphors according to Example 2, Reference Example 5, Reference Example 7, and Comparative Example 4. FIG. 8 is a graph showing excitation spectra of the phosphors according to Example 2, Reference Example 5, Reference Example 7, and Comparative Example 4. FIG. 9 is a graph showing emission spectra of light emitting devices using the phosphors according to Examples 1 to 3 and Comparative Example 1. FIG. 10 is an enlarged graph of the region of the emission intensity 1 to 1500 in FIG.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the embodiment described below exemplifies a phosphor for embodying the technical idea of the present invention, a method for manufacturing the phosphor, and a light emitting device using the phosphor. The manufacturing method and the light emitting device using this phosphor are not limited to the following.

According to the phosphor according to the embodiment, the general formula is represented by _{M x Ce y Si 6-z} B z N 8 + w, M is at least one kind of La, Y, Tb, selected from the group consisting of Lu The above-mentioned elements, wherein w, x, y, and z are 2.0 <w <4.0, 2.0 <x <3.5, 0 <y <1.0, and 0 <z <2, respectively. .0.

  In addition, according to the phosphor according to another embodiment, the x, y, and z can be set to 2.0 <x <3.0, 0 <y <0.5, and 0 <z <1.2, respectively. .

  Furthermore, according to the phosphor according to another embodiment, the phosphor can further contain 10 to 10,000 ppm of fluorine.

  Furthermore, according to the phosphor according to another embodiment, the phosphor may further contain 100 to 10,000 ppm of oxygen.

  Furthermore, according to the phosphor according to another embodiment, 50% by weight or more of the phosphor can have a crystal phase.

Furthermore, according to the phosphor according to another embodiment, the particle diameter can be set to 2 μm to 30 μm.
Furthermore, according to the phosphor according to another embodiment, the phosphor is represented by the general formula La ₃ Si ₆ N ₁₁ : Ce and can contain at least boron.

  Furthermore, according to the light emitting device according to another embodiment, at least a part of the light from the excitation light source is further absorbed, and one or more types of second light emitting fluorescence having a peak wavelength different from that of the first phosphor. A phosphor can be provided.

  Furthermore, according to the method for manufacturing a phosphor according to another embodiment, the content of the impurity phase contained in the product can be reduced by treating the fired product in an acidic solution.

  Furthermore, according to the method for manufacturing a phosphor according to another embodiment, hydrochloric acid can be included in the acidic solution.

  Furthermore, according to the method for manufacturing a phosphor according to another embodiment, a fluoride can be contained in the raw material.

  The relationship between the color name and chromaticity coordinates, the relationship between the wavelength range of light and the color name of monochromatic light, and the like comply with JIS Z8110. Specifically, 380 nm to 455 nm is blue purple, 455 nm to 485 nm is blue, 485 nm to 495 nm is blue green, 495 nm to 548 nm is green, 548 nm to 573 nm is yellow green, 573 nm to 584 nm is yellow, 584 nm to 610 nm is yellow red , 610 nm to 780 nm is red.

Phosphor according to Embodiment 1, silicon, nitrogen include, ultraviolet or a light-emitting fluorescent substance absorbs blue light, represented by _{M x Ce y Si 6-z} B z N 8 + w , M is at least one element selected from the group consisting of La, Y, Tb, and Lu, and w, x, y, and z are 2.0 <w <4.0 and 2.0 <, respectively. x <3.5, 0 <y <1.0, and 0 <z <2.0 are satisfied.

Here, the composition x of La is preferably 2.0 <x <3.3, more preferably 2.0 <x <3.0. The reason why the lower limit is set in the range of x is to obtain a phosphor having the desired composition efficiently. For example, in order to obtain a phosphor La ₃ Si ₆ N ₁₁ having a target composition, another impurity LaSi ₃ N ₅ may be obtained. In this case, a separate process of separating the phosphor having the target composition and the phosphor having the other composition by a classification process or other methods is required. On the other hand, in the present invention, a phosphor having the desired composition can be easily obtained by adjusting the composition of the phosphor without taking the time of production by making the above range x. Probability can be increased. Further, the reason why the upper limit is set in the range of x is that even if La greater than that value is added, it is almost unrelated to the generation of the target phosphor, so that the added La is wasted. .

  The Ce composition y is preferably 0 <y <0.8, more preferably 0 <y <0.5. The reason why the range of y is defined in this way is that a certain amount of Ce is necessary to obtain light emission of the target wavelength, but on the other hand, if the amount of Ce is excessively large, it is an activator. This is because the Ce element interferes with each other, which may reduce the luminance of the phosphor.

  The composition z of B is preferably 0 <z <1.5, more preferably 0 <z <1.2. The reason for defining the range of z in this way is that a certain amount of B is necessary to improve the luminance, but on the other hand, even if the amount of B is excessively increased, the luminance of the phosphor is improved to some extent. This is because no further improvement in luminance can be expected.

  This makes it possible to realize a phosphor that is efficiently excited by blue light from near ultraviolet and has light emission including a wide range of components mainly from green to yellow. Furthermore, by using this phosphor in combination with a light emitting element that emits blue light from near-ultraviolet light, a light emitting device with improved luminous efficiency and excellent color rendering and color reproduction range can be configured. Further, if necessary, the emission composition can be further improved by combining another phosphor.

  This phosphor is characterized in that a flux compound that generates a liquid phase at a firing temperature is added to a part of the raw material, and the product contained in the product by treating the fired product in an acidic solution. The content of the phase is reduced.

Moreover, it is preferable that at least a part of the phosphor has a crystal. For example, since the glass body (amorphous) has a loose structure, there is a possibility that the component ratio in the phosphor is not constant and chromaticity unevenness occurs. Therefore, in order to avoid this, it is necessary to control the reaction conditions in the production process to be strictly uniform. On the other hand, since the phosphor according to the first embodiment can be made of powder or particles having crystallinity instead of a glass body, it is easy to manufacture and process. Further, this phosphor can be uniformly dissolved in an organic medium, and adjustment of a light emitting plastic or a polymer thin film material can be easily achieved. Specifically, in the phosphor according to Embodiment 1, at least 50 wt% or more, more preferably 80 wt% or more has crystals. This indicates the proportion of the crystalline phase having luminescent properties, and if it has a crystalline phase of 50% by weight or more, light emission that can withstand practical use can be obtained. Therefore, the more crystal phases, the better. Thereby, the light emission luminance can be increased and the workability is improved.
(Particle size)

Considering mounting in a light emitting device, the particle size of the phosphor is preferably in the range of 1 μm to 50 μm, more preferably 2 μm to 30 μm. Moreover, it is preferable that the phosphor having this average particle diameter value is contained frequently. Furthermore, the particle size distribution is preferably distributed in a narrow range. By using a phosphor having a large particle size and having small particle size and particle size distribution variations and optically excellent characteristics, color unevenness is further suppressed and a light emitting device having a good color tone can be obtained. Therefore, a phosphor having a particle size in the above range has high light absorption and conversion efficiency. On the other hand, a phosphor having a particle size smaller than 2 μm tends to form an aggregate.
(Production method)

  Below, the manufacturing method of the fluorescent substance which concerns on embodiment is demonstrated. The phosphor of the first embodiment is prepared by using, as raw materials, elemental elements, oxides, carbonates, nitrides, or the like contained in the composition thereof so that each raw material has a predetermined composition ratio. An additive material such as a flux can be appropriately added to these raw materials.

Regarding a specific phosphor material, Si of the phosphor composition is preferably a nitride compound or an oxide compound, but an imide compound or an amide compound can be used. For example _{Si 3 N 4, SiO 2,} Si (NH) 2 and the like. On the other hand, it is possible to synthesize a phosphor that is inexpensive and has good crystallinity even if only Si is used. The purity of the raw material is preferably 2N or higher, but may contain different elements such as Li, Na, K and B. Furthermore, a part of Si can be replaced with Al, Ga, In, Tl, Ge, Sn, Ti, Zr, and Hf.

In addition, it is preferable to use a nitride compound, an oxide compound or the like for La of the phosphor composition, but other compounds or simple substances can also be used. For example _{LaN, La 2 O 3, LaSi} , LaSi 2 , and the like. The purity of the raw material is preferably 2N or higher, but other rare earth elements may be contained.

  Furthermore, it is preferable to use a nitride compound, an oxide compound, or the like as Ce as the activator, but the compound or a simple substance can be used. Halides, carbonates, phosphates, silicates and the like can be mentioned.

  Each raw material can be mixed dry or wet using a mixer. In addition to ball mills commonly used in industry, the mixer is a method of increasing specific surface area by pulverizing using a mill such as a vibration mill, roll mill, jet mill, mortar-pestle, ribbon blender, V-type blender It can be mixed by combining with a mixer such as a Henschel mixer. In addition, in order to keep the specific surface area of the powder within a certain range, classification is performed using a settling tank, a hydrocyclone, a wet separator such as a centrifugal separator, and a dry classifier such as a cyclone and an air separator, which are usually used in industry. You can also For materials that are unstable in the air, mixing is performed in a glove box such as in an argon atmosphere or a nitrogen atmosphere.

The mixed raw materials are packed in a crucible made of SiC, quartz, alumina, BN or the like and fired in a reducing atmosphere of N ₂ and H ₂ . As the firing atmosphere, an argon atmosphere, an ammonia atmosphere, a carbon monoxide atmosphere, a hydrocarbon atmosphere, or the like can also be used. Firing is performed at a temperature of 1000 to 2000 ° C. for 1 to 30 hours. The firing pressure is from atmospheric pressure to 10 atmospheres or less. For firing, a tubular furnace, a high-frequency furnace, a metal furnace, an atmosphere furnace, a gas pressurizing furnace, or the like can be used.

The fired product is pulverized, dispersed, filtered, etc. to obtain the desired phosphor powder. Solid-liquid separation can be performed by industrially used methods such as filtration, suction filtration, pressure filtration, centrifugation, and decantation. Drying can be performed by industrially used apparatuses such as a vacuum dryer, a hot-air heating dryer, a conical dryer, and a rotary evaporator. Further, the luminous efficiency can be further improved by treating with an acid solution in order to remove portions other than the target crystal phase.
(Light emitting device)

  Hereinafter, an example of a light-emitting device equipped with the phosphor according to the present embodiment is shown. Examples of the light emitting device include a lighting device such as a fluorescent lamp, a display device such as a display and a radar, and a liquid crystal backlight. The excitation light source is preferably a light-emitting element that emits light in the short wavelength region from near ultraviolet to visible light. In particular, the semiconductor light emitting element emits light of a bright color with a small size and high power efficiency. As another excitation light source, a mercury lamp used for an existing fluorescent lamp can be appropriately used.

  There are various types of light-emitting devices equipped with light-emitting elements, such as a so-called bullet type and surface mount type. In this embodiment, a surface-mounted light-emitting device will be described as an example with reference to FIG.

  FIG. 1 is a schematic diagram of a light emitting device 100 according to the present embodiment. The light emitting device 100 according to this embodiment includes a package 110 having a recess, a light emitting element 101, and a sealing member 103 that covers the light emitting element 101. The light emitting element 101 is disposed on a bottom surface 112 of a recess formed in the package 110 and is electrically connected to a pair of positive and negative lead electrodes 111 disposed on the package 110 by a conductive wire 104. The sealing member 103 is filled in the recess and is formed of a resin containing the phosphor 102. Further, the pair of positive and negative lead electrodes 111 has one end protruding on the outer surface of the package 110 and bent so as to follow the outer shape of the package 110. The light emitting device 100 emits light when externally supplied with electric power through these lead electrodes 111. Below, the member which comprises the light-emitting device which concerns on this Embodiment is demonstrated.

Below, the member which comprises the light-emitting device which concerns on this Embodiment is demonstrated.
(Light emitting element)

The light emitting element 101 can emit light from the ultraviolet region to the visible light region. The peak wavelength of light emitted from the light-emitting element 101 is preferably 240 nm to 520 nm, and more preferably 420 nm to 470 nm. For example, a nitride semiconductor element (In _X Al _Y Ga _1-XY N, 0 ≦ X, 0 ≦ Y, X + Y ≦ 1) can be used as the light emitting element 101. By using a nitride semiconductor element, a stable light-emitting device that is resistant to mechanical shock can be obtained.
(Phosphor)

  The phosphor 102 according to the present embodiment is blended so as to be partially unevenly distributed in the sealing member 103. At this time, the sealing member functions not only as a member for protecting the light emitting element and the phosphor from the external environment but also as a wavelength conversion member. By placing the light emitting element 101 close to the light emitting element 101 in this manner, the light from the light emitting element 101 can be efficiently converted in wavelength, and a light emitting device having excellent light emission efficiency can be obtained. In addition, arrangement | positioning with the member containing fluorescent substance and a light emitting element is not limited to the form which arranges them closely, The wavelength containing a light emitting element and fluorescent substance is considered in consideration of the influence of the heat | fever to fluorescent substance. It can also arrange | position with the space | interval with a conversion member. Further, by mixing the phosphors 102 in the sealing member 103 at a substantially uniform ratio, it is possible to obtain light without color unevenness.

Two or more kinds of phosphors may be used as the phosphor 102. For example, in the light emitting device 100 according to the present embodiment, color rendering properties can be achieved by using the light emitting element 101 that emits blue light, the phosphor of the present invention excited by the light emitting element 101, and the phosphor that emits red light in combination. Excellent white light can be obtained. The phosphor emitting red _{light, (Ca 1-x Sr x} ) AlSiN 3: Eu (0 ≦ x ≦ 1.0) or _{(Ca 1-xy Sr x Ba} y) 2 Si 5 N 8: Eu (0 ≦ x ≦ 1.0, 0 ≦ y ≦ 1.0) and the like, K ₂ (Si _1-xy Ge _x Ti _y ) F ₆ : Mn (0 ≦ x ≦ 1.0, 0 ≦ _y ) ≦ 1.0) or the like can be used in combination with the phosphor according to the present embodiment. By using these phosphors that emit red light in combination, the full width at half maximum of the component light corresponding to the three primary colors can be widened, so that white light richer in warm colors can be obtained.

Other examples of phosphors that can be used in combination include phosphors emitting red light such as (La, Y) ₂ O ₂ S: Eu and other Eu-activated oxysulfide phosphors, (Ca, Sr) S: Eu. Eu-activated sulfide phosphors such as (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn-activated halophosphate phosphors such as Eu and Mn, Lu ₂ CaMg ₂ (Si , Ge) ₃ O ₁₂ : Ce-activated oxide phosphor such as Ce, and Eu-activated oxynitride phosphor such as α-sialon.

  A green phosphor or a blue phosphor can also be combined. The color reproducibility and color rendering can be further improved by further adding a phosphor emitting green light or a phosphor emitting blue light slightly different in emission peak wavelength from the phosphor of the present application. In addition, by adding a phosphor that absorbs ultraviolet light and emits blue light, it is possible to improve color reproducibility and color rendering by combining light emitting elements that emit ultraviolet light instead of light emitting elements that emit blue light. it can.

Examples of phosphors emitting green light include silicate phosphors such as (Ca, Sr, Ba) ₂ SiO ₄ : Eu, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, and Ca ₈ MgSi ₄ O ₁₆ Cl _{2. -δ} : _{Chlorosilicate} phosphor such as Eu, Mn, (Ca, Sr, Ba) ₃ Si ₆ O ₉ N ₄ : Eu, (Ca, Sr, Ba) ₃ Si ₆ O ₁₂ N ₂ : Eu, (Ca, Sr, Ba) Si ₂ O ₂ N ₂ : oxynitride phosphor such as Eu, Si _6-z Al _z O _z N _8-z : oxynitride phosphor such as β-sialon of Eu, (Y, Lu ) ₃ (Al, Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, SrGa ₂ S ₄ : Eu-activated sulfide phosphor such as Eu, and oxide fluorescence such as CaSc ₂ O ₄ : Ce The body can be used.

Examples of the phosphor emitting blue light include (Sr, Ca, Ba) Al ₂ O ₄ : Eu, (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₄ O ₂₅ : Eu-activated aluminate phosphor such as Eu, Tb, Sm, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn-activated aluminin such as Eu, Mn Acid activated phosphors, Ce activated thiogallate phosphors such as SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, Eu activated silicate phosphors such as (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu ( Eu-activated halophosphate phosphors such as Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu can be used.
(Sealing member)

  The sealing member 103 is formed by being filled with a translucent resin or glass resin so as to cover the light emitting element 101 placed in the recess of the light emitting device 100. In view of ease of manufacture, the material of the sealing member is preferably a translucent resin. As the translucent resin, a silicone resin composition is preferably used, but an insulating resin composition such as an epoxy resin composition or an acrylic resin composition can also be used. Moreover, although the phosphor 102 is contained in the sealing member 103, an additive member can be further contained as appropriate. For example, by including a light diffusing material, the directivity from the light emitting element can be relaxed and the viewing angle can be increased.

Examples 1 to 3 of the phosphor according to the present invention are shown below. In Examples 1 to 3, lanthanum nitride (LaN), silicon nitride (Si ₃ N ₄ ), cerium fluoride (CeF ₃ ), and boron nitride (BN) are commonly used as raw materials. The phosphors were obtained by weighing so as to obtain the respective charged composition ratios. However, these examples illustrate phosphors for embodying the technical idea of the present invention and methods for producing the same, and the phosphors according to the present invention and methods for producing the same are not specified as follows.
[Example 1]

In Example 1, each raw material is weighed so that the charged composition ratio is La: Si: B: Ce = 3: 5.85: 0.15: 0.15. Specifically, the following powders were weighed as the phosphor material of Example 1. However, the purity of each phosphor material is assumed to be 100%.
Lanthanum nitride (LaN) ... 5.99 g
Silicon nitride (Si ₃ N ₄ ) ... 3.57 g
Boron nitride (BN) ... 0.05g
Cerium fluoride (CeF ₃ ) ... 0.39 g

The weighed raw materials are thoroughly mixed in a dry manner, further packed in a crucible, and baked at 1500 ° C. for 10 hours in a reducing atmosphere. The fired product was pulverized and treated with a hydrochloric acid solution to obtain a phosphor powder.
[Examples 2 to 3, Comparative Example 1]

  With respect to the phosphor synthesized by adjusting the raw materials so as to have the blending ratio shown in Table 1 by the same method as in Example 1, the particle size, powder characteristics, strength, and the like were measured. In Table 1, Dm is an index indicating an average particle diameter (μm). The particle diameter was measured by a particle measurement method using electrical resistance using the Coulter principle and the pore electrical resistance method (electric detection zone method). Specifically, the particle size was determined based on the electrical resistance generated when the phosphor was dispersed in the solution and passed through the pores of the aperture tube. The emission spectra of the phosphors according to Examples 1 to 3 and Comparative Example 1 obtained above are shown in FIG. 2, and the excitation spectrum is shown in FIG. Moreover, the 1000 time SEM photograph of the fluorescent substance concerning Example 3 is shown in FIG. Furthermore, Table 2 shows the composition ratio calculated from the analysis value as Si + B = 6. In Table 2, since the analysis value of B was below the detection limit of the analyzer, it is indicated by “−” in the table. As shown in Table 1 and FIG. 2, the phosphor according to the example has a higher relative luminance than the phosphor of Comparative Example 1, and the luminance of the phosphor can be improved by replacing part of silicon with boron. Was confirmed. Moreover, as shown in FIG. 3, it has confirmed that it was excited efficiently by the blue light of the wavelength of 420 nm -470 nm. Furthermore, as shown in Table 1 and FIG. 4, it was confirmed that a phosphor having a particle size of 2 μm to 30 μm was contained.

[Reference Example 4, Comparative Examples 2 and 3]

  Next, changes in relative luminance and the like were confirmed when the La composition ratio in the phosphor composition was increased or decreased based on Example 2. The results are shown in Tables 3 to 4 and FIGS. 5 to 6 as Reference Example 4 and Comparative Examples 2 and 3. Also in this case, the particle size, powder characteristics, strength, and the like were measured for the phosphor synthesized by adjusting the raw materials so as to have the blending ratio shown in Table 3 by the same method as in Example 1. In Table 3, as in Table 1, Dm is an index indicating the average particle diameter. FIG. 5 shows an emission spectrum of the phosphor according to Reference Example 4 and Comparative Examples 2 and 3 obtained, and FIG. 6 shows an excitation spectrum. Table 4 shows the composition ratio calculated from the analysis value as Si + B = 6. As shown in Table 3 and FIG. 5, it was confirmed that the phosphor according to Reference Example 4 has a higher relative luminance than the phosphors of Comparative Examples 2 and 3, and can improve the luminance of the phosphor. In other words, if the blending ratio of La is 2 or less or 3.5 or more, the relative luminance is remarkably lowered. Therefore, the blending ratio of La is preferably greater than 2 and less than 3.5. Moreover, as shown in FIG. 6, it was confirmed that the phosphor was efficiently excited by blue light having a wavelength of 420 nm to 470 nm.

[Reference Example 5, Example 6, Reference Example 7, Comparative Example 4]

  Furthermore, changes in relative luminance and the like when the composition ratio of Ce in the phosphor composition was increased or decreased with reference to Example 2 were measured, and the results were obtained as Reference Example 5, Example 6, Reference Example 7, and Comparative Example 4. Are shown in Tables 5 to 6 and FIGS. Also in this case, the particle size, powder characteristics, strength, and the like were measured for the phosphor synthesized by adjusting the raw materials so as to have the blending ratio shown in Table 5 by the same method as in Example 1 and the like. The emission spectra of the phosphors obtained in Reference Example 5, Example 6, Reference Example 7, and Comparative Example 4 are shown in FIG. 7, and the excitation spectrum is shown in FIG. Table 6 shows the composition ratio calculated from the analysis value as Si + B = 6. As shown in Table 5 and FIG. 7, it is confirmed that the phosphors according to Reference Example 5, Example 6, and Reference Example 7 have higher relative luminance than the phosphor of Comparative Example 4, and can improve the luminance of the phosphor. It was done. In other words, if the Ce blending ratio is 1 or more, the relative luminance is remarkably lowered. Therefore, the Ce blending ratio is preferably less than 1. Further, as shown in FIG. 8, it was confirmed that the phosphor was efficiently excited by blue light having a wavelength of 420 nm to 470 nm.

[Light-Emitting Device Using Examples 1 to 3 and Comparative Example 1]

  Further, Table 7 and FIGS. 9 to 10 show the results of actually producing light emitting devices using the phosphors of Examples 1 to 3 and Comparative Example 1. Each Example and Comparative Example shown in these charts are a combination of the phosphors according to Examples 1 to 3 and Comparative Example 1 described above and LED elements as light emitting elements. The LED element emits blue light having a size of 500 μm × 290 μm and a peak wavelength of 450 nm. A light emitting device was constructed using this LED element, and sealed with a silicone resin containing a phosphor. FIG. 9 shows an emission spectrum of the obtained light emitting device, and FIG. 10 shows a graph in which the region of emission intensity 1 to 1500 in FIG. 9 is enlarged. As shown in these charts, the improvement in the luminous flux was confirmed in any of the Examples as compared with Comparative Example 1.

  The phosphor of the present invention and the light-emitting device using the same are a white illumination light source, an LED display, a backlight light source, a traffic light, and an illumination switch, which have particularly excellent light emission characteristics using a blue light emitting diode or an ultraviolet light emitting diode as a light source It can be suitably used for various sensors and various indicators.

DESCRIPTION OF SYMBOLS 101 ... Light emitting element 102 ... Phosphor 103 ... Sealing member 104 ... Conductive wire 110 ... Package 111 ... Lead electrode 112 ... Bottom face 100 of recessed part ... Light emitting device

Claims (11)

Formula is a phosphor represented by _{M x Ce y Si 6-z} B z N 8 + w, M is, La, Y, Tb, at least one or more elements selected from the group consisting of Lu, W, x, y and z in the general formula are each
2.0 <w <4.0,
2.33 <x <3.0,
0.06 <y <0.5,
0 <z <0.3
A phosphor characterized by satisfying The phosphor according to claim 1,
The phosphor, wherein M is at least one element selected from La and Y. The phosphor according to claim 1 or 2,
The phosphor further comprising 10 to 10000 ppm of fluorine. The phosphor according to any one of claims 1 to 3,
A phosphor having 50% by weight or more of the phosphor having a crystal phase. The phosphor according to any one of claims 1 to 4,
A phosphor having a particle size of 2 μm to 30 μm. An excitation light source that emits light in the short wavelength region from ultraviolet to visible light;
A first phosphor that is a phosphor according to any one of claims 1 to 5 capable of absorbing a part of light from the excitation light source and emitting fluorescence.
A wavelength conversion member containing the first phosphor;
A light emitting device comprising: The light-emitting device according to claim 6,
A light emitting device, wherein the excitation light source is a light emitting element having an emission peak wavelength in a range of 420 nm or more and 470 nm or less. The light emitting device according to claim 6 or 7, further comprising at least one type of first light that absorbs at least part of light from the excitation light source and emits fluorescence having an emission peak wavelength different from that of the first phosphor. A light-emitting device comprising two phosphors. The light-emitting device according to claim 8,
The second _{phosphor, (Ca 1-x Sr x} ) AlSiN 3: Eu (0 ≦ x ≦ 1.0), (Ca 1-xy Sr x Ba y) 2 Si 5 N 8: Eu (0 ≦ x ≦ 1.0, 0 ≦ y ≦ 1.0), K ₂ (Si _1-xy Ge _x Ti _y ) F ₆ : Mn (0 ≦ x ≦ 1.0, 0 ≦ y ≦ 1.0) A light emitting device comprising a phosphor having at least one composition. The light-emitting device according to claim 8 or 9,
The second phosphor is (Ca, Sr, Ba) ₂ SiO ₄ : Eu, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, chlorosilicate phosphor, (Ca, Sr, Ba) ₃ Si ₆ O ₉ N ₄ : Eu, (Ca, Sr, Ba) ₃ Si ₆ O ₁₂ N ₂ : Eu, (Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu, β-type sialon phosphor, (Y, Lu) ₃ (Al , Ga) ₅ O ₁₂ : Ce, SrGa ₂ S ₄ : Eu, CaSc ₂ O ₄ : Ce, a light emitting device including a phosphor having at least one composition selected from Ce. The light-emitting device according to any one of claims 8 to 10,
The second phosphor is (Sr, Ca, Ba) Al ₂ O ₄ : Eu, (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₄ O ₂₅ : Eu, Tb, Sm, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn, SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, (Ba, Sr, Ca, Mg) A light emitting device including a phosphor having at least one composition selected from ₂ SiO ₄ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu.