JPWO2014068907A1 - Phosphor, wavelength conversion member and light emitting device - Google Patents

Abstract

The phosphor of the present invention has a composition represented by the general formula: AE14MI6MII10O35: Mn4 +. In the formula, AE represents at least one element selected from the group consisting of Ca, Sr and Ba. MI represents at least one element selected from the group consisting of Zn and Mg. MII represents at least one element selected from the group consisting of Al and Ga. The phosphor is excited by absorbing light in the near ultraviolet to blue region emitted from the light emitting element. Further, when the excited phosphor transitions to the ground state, it emits red fluorescence having a peak at 700 to 750 nm.

Description

  The present invention relates to a phosphor that absorbs light and emits light having a wavelength different from that of the light, a wavelength conversion member, and a light emitting device.

  2. Description of the Related Art In recent years, light emitting devices using LEDs have become widespread along with higher efficiency of light emitting diodes (LEDs). In particular, a light-emitting device including an LED and a phosphor that converts the wavelength of light emitted from the LED can be highly efficient, small and thin, and can save power. Features such as the ability to emit light in color. For this reason, this type of light-emitting device is used for indoor and outdoor lighting fixtures, liquid crystal displays, backlight light sources such as mobile phones and personal digital assistants, display devices used for indoor and outdoor advertising, and in-vehicle light sources. It is expected to be used and is being developed. Attempts have also been made to deploy LEDs to lighting devices for plant growth.

Conventionally, as a plant growing lighting device, one using a fluorescent lamp as a light source is known (see, for example, Patent Document 1). The illumination of Patent Document 1 uses LiAlO ₂ : Fe ³⁺ as a phosphor for a lamp, and emits blue radiation generated by mercury discharge and red light having a peak at 735 nm emitted from the phosphor excited by ultraviolet rays. We are using.

Conventionally, a plant growing lighting device using LEDs has been disclosed (see, for example, Patent Document 2). The illumination device of Patent Document 2 supplies light necessary for plant growth, and includes a first light emitting unit that has a red phosphor and emits red light, and a blue phosphor that emits blue light. A second light emitting unit. And as the red phosphor, CaAlSiN ₃ shows an emission peak around 630 nm: ^{Eu 2+} are illustrated.

Here, when a phosphor is used as the red component of the plant-growing lighting device using the LED, the phosphor can be excited by light in the near ultraviolet to blue region emitted from the LED, and is further excited. To emit red light. Conventionally, as a phosphor that can be excited by light in the near ultraviolet to blue region, the composition formula is 2.5 MgO · 0.5CaO · 1.0 MgF ₂ .0.90GeO ₂ · 0.10 TiO ₂ : 0.02Mn ⁴⁺ The fluorescent substance represented is disclosed (for example, refer patent document 3). Conventionally, a red phosphor having a composition represented by a composition formula: M ₂ Si ₅ N ₈ : Eu ²⁺ (wherein M represents Ca, Sr, Ba) has also been disclosed (for example, Non-Patent Document 1). reference).

Japanese Patent Publication No.51-42436 JP 2010-29098 A JP 2011-6501 A

Yuan Qiang Li, “Structure and Luminescence Properties of Novel Rare-Earth Doped Silicon Nitride Based Materials”, Eindhoven University of Technology, 2005

  However, the phosphor described in Patent Document 1 is excited only by ultraviolet light near 254 nm, and cannot be excited by light in the near ultraviolet to blue region. The red phosphors described in Patent Documents 2 and 3 have an emission peak in the wavelength region of 600 to 700 nm, but do not show an emission peak on the longer wavelength side.

The phosphor described in Non-Patent Document 1 has an emission peak in the near infrared of 700 to 800 nm. However, since CaAlSiN ₃ : Eu ²⁺ in Patent Document 2 and M ₂ Si ₅ N ₈ : Eu ^{2+ in} Non-Patent Document 1 are nitride phosphors, special manufacturing equipment for firing the raw material at a high temperature in a nitrogen atmosphere And the manufacturing process becomes complicated.

  The present invention has been made in view of such problems of the prior art. An object of the present invention is a phosphor that can be excited by light in the near ultraviolet to blue region, has a main emission peak at 700 to 800 nm, and can be manufactured by a simple method, and a wavelength conversion member including the phosphor. And providing a light emitting device.

The gist of the phosphor according to the first aspect of the present invention is that it has a composition represented by the general formula: AE ₁₄ M ^I ₆ M ^II ₁₀ O ₃₅ : Mn ⁴⁺ . In the formula, AE represents at least one element selected from the group consisting of Ca, Sr and Ba. M ^I represents at least one element selected from the group consisting of Zn and Mg. M ^II is representative of at least one element selected from the group consisting of Al and Ga.

  The phosphor according to the second aspect of the present invention is summarized in that, in the phosphor according to the first aspect, AE contains at least Ca.

The phosphor according to the third aspect of the present invention is summarized in that, in the phosphor according to the first or second aspect, M ^I contains at least Zn.

Phosphor according to a fourth aspect of the present invention is the phosphor according to any one of the first to third embodiments, M ^II is summarized in that comprising at least Ga.

  The gist of the wavelength conversion member according to the fifth aspect of the present invention is that it includes the phosphor according to any one of the first to fourth aspects and a translucent medium in which the phosphor is dispersed.

  The light-emitting device according to the sixth aspect of the present invention includes a light-emitting element and the wavelength conversion member according to the fifth aspect that emits light by absorbing at least a part of light emitted from the light-emitting element. To do.

  The gist of the light emitting device according to the seventh aspect of the present invention is that, in the light emitting device according to the sixth aspect, the main light emission peak of the light emitted from the light emitting element is in the range of 350 nm to 470 nm.

FIG. 1 is an exploded perspective view, partly broken, showing a light emitting device according to an embodiment of the present invention. FIG. 2 is a cross-sectional view illustrating a light emitting device according to an embodiment of the present invention. FIG. 3 is a graph showing diffraction intensity curves obtained by powder X-ray diffraction measurement for the phosphors of Example 1 and Example 4 and Ca ₁₄ Zn ₆ Al ₁₀ O ₃₅ . FIG. 4 is a graph showing the emission spectrum and excitation spectrum of the phosphor obtained in Example 10. FIG. 5 is a graph showing the emission spectra of the phosphors obtained in Example 10, Comparative Example 1 and Comparative Example 2. FIG. 6 is a graph showing measurement results of temperature quenching of the phosphors obtained in Example 4, Example 10, and Comparative Example 3.

[Phosphor]
Hereinafter, a phosphor, a wavelength conversion member, and a light emitting device according to an embodiment of the present invention will be described in detail with reference to the drawings. In addition, the dimension ratio of drawing is exaggerated on account of description, and may differ from an actual ratio.

The phosphor according to the embodiment of the present invention is represented by the general formula (1).
AE ₁₄ M ^I ₆ M ^II ₁₀ O ₃₅ : Mn ⁴⁺ (1)
In the formula, AE represents at least one element selected from the group consisting of calcium (Ca), strontium (Sr), and barium (Ba). M ^I represents at least one element selected from the group consisting of zinc (Zn) and magnesium (Mg). M ^II represents at least one element selected from the group consisting of aluminum (Al) and gallium (Ga).

The phosphor according to the present embodiment has a structure in which tetravalent manganese ions (Mn ⁴⁺ ) are doped in a crystal of AE ₁₄ M ^I ₆ M ^II ₁₀ O ₃₅ . In the phosphor crystal having such a composition, ions serving as emission centers are tetravalent manganese ions. Then, by substituting a part and the manganese ion sites occupied by the metal element in the crystal of the _{^{AE 14 M I 6 M II 10}} O 35, manganese ions are dissolved in the crystal.

  By having a crystal structure in which such manganese ions are partially substituted, the phosphor is excited by efficiently absorbing light in the near ultraviolet to blue region emitted from the light emitting element. And when the excited fluorescent substance changes to a ground state, the red fluorescence which has a peak in 700-750 nm is emitted efficiently.

  Here, when the action of light radiation on plants is viewed from the spectral characteristics, blue light around 450 nm and red light around 660 nm are effective for photosynthesis. In addition, light in the wavelength range of 300 to 400 nm, 600 to 700 nm, and 700 to 800 nm is involved in photomorphogenesis. In particular, in terms of plant growth control, the elongation of leaves and stems that affect the shape of the plant is closely related to the photon flux ratio contained in the two wavelength regions centered at 660 nm and 730 nm. By changing the ratio, the leaf area and stem height can be controlled. Therefore, it is preferable that the light used for plant growth includes blue light having a peak at 400 to 500 nm and red light having a peak in two regions of 600 to 700 nm and 700 to 800 nm.

  As described above, the phosphor according to the present embodiment absorbs and excites a part of the light in the blue region emitted from the light emitting element, and then emits red fluorescence having a peak at 700 to 750 nm. Therefore, plants can be grown more efficiently than before by using a combination of blue light emitted from the light emitting element and red light emitted from the phosphor.

  The center particle diameter (median diameter, d50) of the phosphor particles is not particularly limited. However, the larger the average particle size of the phosphor, the smaller the defect density in the phosphor and the less energy loss during light emission, resulting in higher luminous efficiency. For this reason, from the viewpoint of improving luminous efficiency, the center particle diameter of the phosphor is preferably 1 μm or more and less than 50 μm, more preferably 5 μm or more and less than 30 μm. The central particle size of the phosphor particles can be determined by a dynamic light scattering method using a laser diffraction particle size distribution measuring device.

  Here, in the general formula (1), as described above, AE represents at least one element selected from the group consisting of Ca, Sr, and Ba. That is, AE may consist of only one element of Ca, Sr and Ba, or may consist of two or more elements. When AE consists of two or more elements, the ratio of each of the two or more elements in AE is arbitrary. In the phosphor crystal represented by the general formula (1), AE is a divalent ion.

  In particular, the AE in the general formula (1) preferably contains at least calcium (Ca). When the AE of the phosphor according to the present embodiment contains calcium, the luminous efficiency of the phosphor can be further improved.

As described above, M ^I in the general formula (1) represents at least one element selected from the group consisting of Zn and Mg. That, M ^I may consist of only one element of Zn and Mg, may consist both elements. When M ^I contains both Zn and Mg elements, the ratio of each element in M ^I is arbitrary. In the phosphor of the crystal represented by the general formula (1), M ^I is the divalent ions.

In particular, M ^I in the general formula (1) preferably contains at least zinc (Zn). By M ^I of the phosphor of this embodiment contains zinc, it is possible to further improve the luminous efficiency of the phosphor.

As described above, M ^II in the general formula (1) represents at least one element selected from the group consisting of Al and Ga. That, M ^II may consist of only one element among Al and Ga, it may consist both elements. When M ^II contains both elements of Al and Ga, the ratio of each element in M ^II is arbitrary. Incidentally, M ^II is a trivalent ion in the phosphor in a crystal represented by the general formula (1).

In particular, M ^II in the general formula (1) preferably contains at least gallium (Ga). By M ^II of the phosphor of this embodiment contains gallium, it is possible to further improve the luminous efficiency of the phosphor.

Here, the tetravalent manganese ion as the additive element can be substituted with, for example, a part of M ^II in the crystal of the AE ₁₄ M ^I ₆ M ^II ₁₀ O ₃₅ as shown in Examples described later. For example, when a part of M ^II is substituted, the substitution ratio of Mn ⁴⁺ is preferably 0.1 atomic percent or more and less than 10 atomic percent, particularly 1 atomic percent or more and less than 5 atomic percent with respect to M ^II . . Even if the substitution ratio of Mn ⁴⁺ is outside this range, the effect of the present invention can be exhibited. However, when the substitution ratio of Mn ⁴⁺ is less than 0.1 atomic%, the excitation light emitted from the light emitting element may not be efficiently absorbed. Moreover, when the substitution ratio of Mn ⁴⁺ exceeds 10 atomic%, there is a possibility that fluorescence cannot be emitted efficiently by concentration quenching.

Since M ^II in the general formula (1) is a trivalent ion, when it is substituted with Mn ⁴⁺ that is a tetravalent ion, a defect occurs due to a shift in charge. Therefore, it is preferable to perform charge compensation so that the defect does not occur. Charge compensation can be performed, for example, by a method of substituting a part of trivalent M ^II ions with divalent ions such as magnesium ions (Mg ²⁺ ).

It should be noted that each element in AE, M ^I and M ^II may be partially substituted with other elements within a range that does not cause deterioration of the light emission characteristics, and the composition ratio in the general formula (1) is changed. May be. Further, the phosphor may be subjected to a surface treatment such as coating in order to suppress reflection of excitation light and fluorescence at the interface between the phosphor and the translucent medium in the wavelength conversion member described later.

  Next, a method for manufacturing the phosphor according to this embodiment will be described. First, the raw materials of each element in the phosphor are mixed to prepare a raw material mixture. The blending ratio of the raw materials needs to be adjusted so that the elements in the mixture coincide with the composition represented by the general formula (1).

  Examples of the raw material for each element in the phosphor include a single metal constituting the phosphor, and compounds such as oxides and salts of the metal constituting the phosphor. Further, as a metal salt constituting the phosphor, carbonate is particularly preferable.

As a specific example of the raw material, when the AE of the general formula (1) contains calcium, calcium carbonate (CaCO ₃ ) can be used as the raw material. When AE contains strontium, strontium carbonate (SrCO ₃ ) can be used as the raw material. When AE contains barium, barium carbonate (BaCO ₃ ) can be used as the raw material.

If the M ^I of the general formula (1) contains a zinc may be used zinc oxide (ZnO) as its raw material. If the M ^I contains magnesium, may be used magnesium oxide (MgO) as its raw material. Further, when M ^II of the general formula (1) contains aluminum, aluminum oxide (Al ₂ O ₃ ) can be used as the raw material. When M ^II contains gallium, gallium oxide (Ga ₂ O ₃ ) can be used as the raw material. Further, manganese oxide (MnO ₂ ) or manganese carbonate (MnCO ₃ ) can be used as a raw material for manganese ions.

  Next, the mixture is put into a firing container formed of a material such as alumina or quartz. Then, the mixture in this baking container is baked at 1000-1300 degreeC in air | atmosphere atmosphere. The atmosphere during firing may be an air atmosphere or an oxygen atmosphere since manganese is doped with tetravalent. The firing temperature and firing time are desirably adjusted so that the sintering reaction of the mixture proceeds sufficiently. In this case, a fluorescent material substantially consisting only of the phosphor according to the present embodiment is obtained. However, the effect of the present invention can be exerted even if this fluorescent material contains unreacted raw materials, by-products and other impurities that remain slightly.

  Note that the mixture may be pre-baked in an air atmosphere in advance before baking the mixture under the above-described conditions. In this case, the crystallinity of the phosphor is particularly high. When the mixture is calcined, the calcining temperature during the calcining is preferably lower than the calcining temperature during the main calcining.

  Next, the sintered body obtained by sintering the mixture is pulverized and washed with water or acid to remove unnecessary components. Thus, a phosphor powder having a desired composition is obtained.

  Thus, the phosphor according to the present embodiment can be manufactured through a process of firing the raw material at a relatively low temperature of 1000 to 1300 ° C. in an air atmosphere, for example. This eliminates the need for manufacturing equipment for high-temperature heating and equipment for supplying a reducing gas, simplifies the manufacturing process, and makes it easier to manufacture compared to the prior art.

[Wavelength conversion member]
Next, an example of the wavelength conversion member of this embodiment will be described. The wavelength conversion member includes the above-described phosphor particles and a translucent medium. Furthermore, the phosphor is dispersed inside a translucent medium that constitutes the parent phase of the wavelength conversion member. Thus, by dispersing the phosphor according to the present embodiment inside the translucent medium, it is possible to improve the chemical stability and heat resistance of the phosphor.

  The refractive index of the translucent medium is preferably close to the refractive index of the phosphor. As a material for the light-transmitting medium, it is preferable to use a silicon compound or glass having a siloxane bond. These materials are excellent in heat resistance and light resistance, particularly durability to light having a short wavelength such as blue to ultraviolet light. Therefore, even if the excitation light incident on the phosphor is light in a wavelength range from general blue light to ultraviolet light, deterioration of the translucent medium is suppressed.

  Examples of silicon compounds include composite resins formed by crosslinking a silicone resin, an organosiloxane hydrolysis condensate, an organosiloxane condensate, and the like by a known polymerization method. As the polymerization method, addition polymerization such as hydrosilylation or radical polymerization can be used.

  Further, as the translucent medium, for example, an acrylic resin or an organic / inorganic hybrid material formed by mixing and bonding an organic component and an inorganic component at the nanometer level or the molecular level may be employed. .

  The content of the phosphor in the wavelength conversion member is appropriately determined in consideration of the types of the phosphor and the translucent medium, the dimensions of the wavelength conversion member, the wavelength conversion capability required for the wavelength conversion member, and the like. However, it is preferable that content of the fluorescent substance in a wavelength conversion member is the range of 5 mass%-30 mass%, for example.

  When the wavelength conversion member is irradiated with excitation light from the outside, the phosphor absorbs the excitation light and emits fluorescence having a wavelength longer than that of the excitation light. That is, the wavelength converting member can emit red fluorescence having a peak at 700 to 750 nm with high intensity.

  As described above, the wavelength conversion member includes a translucent medium constituting the parent phase, and a phosphor dispersed in the translucent medium. And at least one part of the fluorescent substance disperse | distributed to a translucent medium is formed from the fluorescent substance which concerns on this embodiment. However, the wavelength conversion member may further contain a phosphor other than the phosphor according to the present embodiment.

As phosphors other than the phosphor according to the present embodiment, red phosphor particles that emit red fluorescence and green phosphor particles that emit green fluorescence can be used. As phosphors constituting the red phosphor particles, (Sr, Ca) ₂ (Si, Al) ₅ (N, O) ₈ : Eu ²⁺ , (Ca, Sr) AlSiN ₃ : Eu ²⁺ , SrAl (Si, Al ) ₄ (N, O) ₇ : Eu ²⁺ , (Ca, Sr) S: Eu ^{2+ and the} like. As phosphors constituting the green phosphor particles, (Ba, Sr) ₂ SiO ₄ : Eu ²⁺ , Y ₃ Al ₅ O ₁₂ : Ce ³⁺ , (Ba, Sr, Ca) Si ₂ O ₂ N ₂ : Eu ²⁺ Etc. Further, as the phosphors of the green phosphor _{particles, (Ba, Sr, Ca)} 3 Si 6 O 12 N 2: Eu 2+, (Ca, Mg) 3 Sc 2 Si 3 O 12: Ce 3+, CaSc 2 ^Examples include O ₄ : Ce ³⁺ .

As will be described later, when the LED chip (light emitting element) in the light emitting device is an ultraviolet LED chip that emits ultraviolet light, the wavelength conversion member emits blue fluorescence together with the phosphor particles according to the present embodiment, for example. It is preferable to contain phosphor particles (blue phosphor particles). The phosphors of the blue phosphor ^{_{particles, BaMgAl 10 O 17: Eu 2+}} , (Sr, Ca, Ba) 10 (PO 4) 6 C l2: Eu 2+, Sr 3 MgSi 2 O 8: Eu 2+ , such as What has a composition is mentioned. Furthermore, red phosphor particles and green phosphor particles may be used in combination with the blue phosphor particles as necessary. As phosphors constituting the red phosphor particles in this case, La ₂ O ₂ S: Eu ³⁺ , (Sr, Ca) ₂ (Si, Al) ₅ (N, O) ₈ : Eu ²⁺ , (Ca, Sr ) AlSiN ₃ : Eu ²⁺ , SrAl (Si, Al) ₄ (N, O) ₇ : Eu ^{2+ and the} like. As phosphors constituting the green phosphor particles, (Ba, Sr) ₂ SiO ₄ : Eu ²⁺ , BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , Mn ²⁺ , (Ba, Sr, Ca) Si ₂ O ₂ N ₂ : Eu ²⁺ , (Ba, Sr, Ca) ₃ Si ₆ O ₁₂ N ₂ : Eu ^{2+ and the} like.

[Light emitting device]
Next, an example of the light emitting device of this embodiment will be described. As shown in FIGS. 1 and 2, the light emitting device 1 includes an LED chip 10 that is a light emitting element, a mounting substrate 20, an optical member 60, a sealing portion 50, and a wavelength conversion member 70. As described above, the wavelength conversion member 70 includes the phosphor according to the present embodiment.

  The LED chip 10 is mounted on the mounting substrate 20. The shape of the mounting substrate 20 is substantially rectangular in plan view. On the surface in the thickness direction of the mounting substrate 20, a pair of conductor layers 23 are formed for supplying power to the LED chip 10. Further, the LED chip 10 is mounted on the surface of the mounting substrate 20. The LED chip 10 and the conductor layer 23 are electrically connected by a bonding wire 14 made of a fine metal wire such as a gold fine wire or an aluminum fine wire.

  The optical member 60 is a dome-shaped member and is fixed on the surface of the mounting substrate 20. The LED chip 10 is accommodated between the optical member 60 and the mounting substrate 20. The optical member 60 has a function of controlling the orientation of light emitted from the LED chip 10.

  The sealing part 50 is formed from a translucent sealing material. Examples of the sealing material for the sealing unit 50 include silicone resins. However, not limited to the silicone resin, for example, an acrylic resin or glass may be used. The sealing unit 50 is filled in a space surrounded by the optical member 60 and the mounting substrate 20. The sealing portion 50 seals the LED chip 10 and a plurality (two in this embodiment) of bonding wires 14.

  The wavelength conversion member 70 is formed in a dome shape so as to surround the optical member 60. When the LED chip 10 emits light, the phosphor in the wavelength conversion member 70 is excited by the light (excitation light) emitted from the LED chip 10 and emits fluorescence having a wavelength longer than that of the excitation light. This long wavelength fluorescence is converted light composed of light of a color different from the emission color of the LED chip 10.

  Further, a gap 80 in which a gas such as air is enriched is interposed between the optical member 60 and the wavelength conversion member 70. Further, on the surface of the mounting substrate 20, an annular dam portion 27 that surrounds the outer periphery of the optical member 60 is formed. The dam portion 27 is formed so as to protrude upward from the surface of the mounting substrate 20. Therefore, when the optical member 60 is fixed to the mounting substrate 20, the sealing material is dammed by the dam portion 27 even if the sealing material overflows from the space surrounded by the optical member 60 and the mounting substrate 20. It can be stopped.

  The LED chip 10 preferably has a main light emission peak in the range of 350 to 470 nm. As such an LED chip 10, for example, a GaN blue LED chip that emits blue light can be used. In a GaN-based blue LED chip, an n-type SiC substrate having a lattice constant or crystal structure closer to that of GaN than a sapphire substrate and having conductivity is used as a crystal growth substrate. On this SiC substrate, for example, a light emitting part having a double hetero structure is formed. The light emitting portion is formed by an epitaxial growth method (for example, MOVPE method) using, for example, a GaN compound semiconductor material as a raw material.

  The LED chip 10 includes a cathode electrode on the surface facing the surface of the mounting substrate 20 and an anode electrode on the surface opposite to the cathode electrode. The cathode electrode and the anode electrode are composed of a laminated film of a Ni film and an Au film, for example. The material for the cathode electrode and the anode electrode is not particularly limited, and may be any material as long as good ohmic characteristics can be obtained. For example, Al may be used.

  The structure of the LED chip 10 is not limited to the above structure. For example, first, a light emitting portion or the like is formed on a crystal growth substrate by epitaxial growth. Thereafter, a support substrate such as a Si substrate that supports the light emitting unit is fixed to the light emitting unit, and the crystal growth substrate is removed, whereby the LED chip 10 may be formed.

  The mounting board 20 includes a rectangular heat transfer plate 21 and a wiring board 22. The heat transfer plate 21 is formed from a heat conductive material. Then, the LED chip 10 is mounted on the heat transfer plate 21. The wiring board 22 is, for example, a rectangular flexible printed wiring board. The wiring board 22 is fixed onto the heat transfer plate 21 via, for example, a polyolefin-based fixing sheet 29.

  A rectangular window hole 24 that exposes the mounting position of the LED chip 10 on the heat transfer plate 21 is formed at the center of the wiring board 22. Inside this window hole 24, the LED chip 10 is mounted on the heat transfer plate 21 via a submount member 30 described later. Therefore, the heat generated in the LED chip 10 is conducted to the submount member 30 and the heat transfer plate 21 without passing through the wiring board 22.

  The wiring board 22 includes an insulating base material 221 made of a polyimide film and a pair of conductor layers 23 that are formed on the insulating base material 221 and supply power to the LED chip 10. Furthermore, the wiring board 22 includes a protective layer 26 that covers each conductor layer 23 and covers a portion of the insulating base material 221 where the conductor layer 23 is not formed. The protective layer 26 is made of, for example, a white resist (resin) having light reflectivity. In this case, even if light is radiated from the LED chip 10 toward the wiring substrate 22, the light is reflected by the protective layer 26, thereby suppressing light absorption in the wiring substrate 22. Thereby, the light extraction efficiency from the LED chip 10 to the outside is improved, and the light output of the light emitting device is improved.

  Each conductor layer 23 is formed in a shape slightly smaller than half of the outer peripheral shape of the insulating base material 221. The insulating base material 221 may be formed of an FR4 substrate, an FR5 substrate, a paper phenol resin substrate, or the like.

  Each conductor layer 23 includes two terminal portions 231 each having a substantially rectangular shape in plan view. The terminal portion 231 is located in the vicinity of the window hole 24 of the wiring board 22, and the bonding wire 14 is connected to the terminal portion 231. Further, each conductor layer 23 includes one external connection electrode portion 232 having a substantially circular shape in plan view. The external connection electrode portion 232 is located near the outer periphery of the wiring board 22. The conductor layer 23 is composed of, for example, a laminated film of a Cu film, a Ni film, and an Au film.

  The protective layer 26 is patterned so that each conductor layer 23 is partially exposed from the protective layer 26. In the vicinity of the window hole 24 of the wiring board 22, the terminal portion 231 in each conductor layer 23 is exposed from the protective layer 26. Further, external connection electrode portions 232 in the respective conductor layers 23 are exposed from the protective layer 26 in the vicinity of the outer periphery of the wiring board 22.

  The LED chip 10 is mounted on the heat transfer plate 21 through the submount member 30 as described above. The submount member 30 relieves stress acting on the LED chip 10 due to the difference in linear expansion coefficient between the LED chip 10 and the heat transfer plate 21. The submount member 30 is formed in a rectangular plate shape having a size larger than the chip size of the LED chip 10.

  The submount member 30 has not only a function of relieving the stress but also a heat conduction function of conducting heat generated in the LED chip 10 in a range wider than the chip size of the LED chip 10 in the heat transfer plate 21. . In the light emitting device 1 according to this embodiment, the LED chip 10 is mounted on the heat transfer plate 21 via the submount member 30, so that the heat generated by the LED chip 10 passes through the submount member 30 and the heat transfer plate 21. Heat dissipation. Further, the submount member 30 relieves stress acting on the LED chip 10 due to a difference in linear expansion coefficient between the LED chip 10 and the heat transfer plate 21.

  The submount member 30 is preferably formed of, for example, AlN having a relatively high thermal conductivity and an insulating property. The material of the submount member 30 is not limited to AlN, and any material may be used as long as the linear expansion coefficient is relatively close to 6H—SiC, which is a material for the crystal growth substrate, and the heat conductivity is relatively high. For example, composite silicon carbide (SiC), Si, Cu, CuW, or the like may be employed as the material of the submount member 30. The submount member 30 has the above-described heat conduction function. Therefore, it is desirable that the area of the surface facing the LED chip 10 in the heat transfer plate 21 is sufficiently larger than the area of the surface facing the heat transfer plate 21 in the LED chip 10.

  As shown in FIG. 2, the cathode electrode of the LED chip 10 is overlaid on the submount member 30. Further, the cathode electrode is electrically connected to one of the two conductor layers 23 via an electrode pattern (not shown) connected to the cathode electrode and the bonding wire 14. Further, the anode electrode of the LED chip 10 is electrically connected to the conductor layer 23 not connected to the cathode electrode via the bonding wire 14.

  For joining the LED chip 10 and the submount member 30, for example, solder such as SnPb, AuSn, SnAgCu, silver paste, or the like is used. It is particularly preferable to use lead-free solder such as AuSn or SnAgCu. When the submount member 30 is made of Cu and AuSn is used for bonding the LED chip 10 and the submount member 30, a metal layer made of Au or Ag is previously formed on the bonding surface of the submount member and the LED chip. It is preferable that the pretreatment to form is performed.

  Also, it is preferable to use lead-free solder such as AuSn or SnAgCu for joining the submount member 30 and the heat transfer plate 21. When AuSn is used for joining the submount member 30 and the heat transfer plate 21, a pretreatment is performed in which a metal layer made of Au or Ag is previously formed on the joint surface between the heat transfer plate 21 and the submount member 30. It is preferred that

  In the light emitting device 1 according to the present embodiment, the thickness of the submount member 30 is larger than the thickness of the wiring board 22 as shown in FIG. That is, the upper surface of the submount member 30 protrudes above the upper surface of the protective layer 26 of the wiring board 22. For this reason, it can suppress that the light radiated | emitted from LED chip 10 is absorbed by the wiring board 22 through the inner side of the window hole 24 of the wiring board 22. FIG. Thereby, the light extraction efficiency from the LED chip 10 to the outside is further improved, and the light output of the light emitting device is improved.

  A reflective film that reflects light emitted from the LED chip 10 may be formed around the contact surface between the submount member 30 and the LED chip 10. In this case, the light emitted from the LED chip 10 is suppressed from being absorbed by the submount member 30. Thereby, the light extraction efficiency from the LED chip 10 to the outside is further improved, and the light output of the light emitting device is improved. The reflective film can be composed of a laminated film of, for example, a Ni film and an Ag film.

  The optical member 60 is formed of a light transmissive material such as silicone resin or glass. In particular, it is preferable that the optical member 60 is formed of a silicone resin because a difference in refractive index and a difference in linear expansion coefficient between the optical member 60 and the sealing portion 50 are reduced.

  The first light exit surface 602 (surface opposite to the LED chip 10) of the optical member 60 is such that light incident from the first light incident surface 601 (surface on the LED chip 10 side) into the optical member is the first light. A convex curved surface is formed so as not to be totally reflected at the boundary between the emission surface 602 and the gap 80. And the optical member 60 is arrange | positioned so that the LED chip 10 and an optical axis may correspond. Therefore, the light emitted from the LED chip 10 and incident on the first light incident surface 601 of the optical member 60 is not totally reflected at the boundary between the first light emitting surface 602 and the gap 80 and reaches the wavelength conversion member 70. Easier to reach. Therefore, the total luminous flux emitted from the light emitting device 1 increases. The optical member 60 is formed so as to have a substantially uniform thickness along the normal direction regardless of the position.

  In the wavelength conversion member 70, the second light incident surface 701 (the surface on the LED chip 10 side) is formed in a shape along the first light emitting surface 602 of the optical member 60. Therefore, regardless of the position of the first light exit surface 602, the distance between the first light exit surface 602 and the wavelength conversion member 70 in the normal direction is substantially constant. Moreover, the wavelength conversion member 70 is shape | molded so that the thickness along a normal line direction may become uniform irrespective of a position. The wavelength conversion member 70 is fixed to the mounting substrate 20 with, for example, an adhesive (for example, silicone resin, epoxy resin).

  The light emitted from the LED chip 10 enters the wavelength conversion member 70 from the second light incident surface 701 and passes through the second light emission surface 702 of the wavelength conversion member 70 (surface opposite to the LED chip 10). The light is emitted out of the conversion member 70. When light passes through the wavelength conversion member 70, a part of the light is wavelength-converted by the phosphor particles in the wavelength conversion member 70. Thereby, light of a color corresponding to the combination of the light emitted from the LED chip 10 and the type of phosphor particles in the wavelength conversion member 70 is emitted from the light emitting device 1.

  When the LED chip 10 in the light emitting device 1 is a blue LED chip that emits blue light, the wavelength conversion member 70 uses phosphor particles according to the present embodiment. In this case, the blue light emitted from the LED chip 10 without wavelength conversion and the red light emitted from the phosphor particles according to this embodiment in the wavelength conversion member 70 are emitted from the wavelength conversion member 70.

  When the light-emitting device is used as plant-growing illumination, other combinations are not particularly limited as long as light from the phosphor according to the present embodiment is used as a red component of 700 to 800 nm. For example, a combination using a blue LED chip that emits blue light, a phosphor that emits red light of 600 to 700 nm, and a phosphor according to the present embodiment can be used. In addition, a combination of an LED chip that emits ultraviolet light, a phosphor that emits blue light of 400 to 500 nm, a phosphor that emits red light of 600 to 700 nm, and the phosphor according to the present embodiment may be used. it can. However, the present invention is not limited to the above combinations.

  And the light-emitting device which concerns on this embodiment radiates | emits simultaneously the blue light radiated | emitted from LED chip etc. and the red light emitted from the fluorescent substance particle which concerns on this embodiment in a wavelength conversion member as mentioned above. be able to. Therefore, for example, when used for lighting for plant growth, it becomes possible to grow plants more efficiently than in the past.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.

[Example 1]
CaCO ₃ powder, ZnO powder, Al ₂ O ₃ powder and MnO ₂ powder were weighed as shown in Table 1 and mixed uniformly. Subsequently, the obtained mixed powder was put in a platinum baking container and heated in the atmosphere at a temperature of 1200 ° C. for 6 hours. And the particle | grains of the fluorescent substance of a present Example which have the composition shown in Table 1 were obtained by grind | pulverizing the obtained sintered compact.

[Examples 2 to 13]
Except that CaCO ₃ powder, SrCO ₃ powder, BaCO ₃ powder, ZnO powder, MgO powder, Al ₂ O ₃ powder, Ga ₂ O ₃ powder, and MnO ₂ powder were weighed as shown in Table 1, the same as Example 1 was carried out. Thus, phosphor particles of each example having the composition shown in Table 1 were obtained.

[Powder X-ray diffraction measurement]
Powder X-ray diffraction measurement was performed on the phosphors obtained in Examples 1 to 13. In the powder X-ray diffraction measurement, CuKα rays were used.

As an example of the measurement result of the powder X-ray diffraction, FIG. 3 shows the X-ray diffraction patterns of the phosphors obtained in Example 4 and Example 10. From the spectrum shown in FIG. 3, it can be seen that the phosphors of Example 4 and Example 10 are phosphors having the same crystal structure as that of the known compound Ca ₁₄ Zn ₆ Al ₁₀ O ₃₅ .

[Measurement of emission spectrum and excitation spectrum]
For the phosphors obtained in Examples 1 to 13, the emission spectrum and the excitation spectrum were measured. As a measuring device, a spectrofluorophotometer FP-6500 manufactured by JASCO Corporation was used. When measuring the fluorescence spectrum, the wavelength of the excitation light applied to the phosphor was 450 nm. The monitor wavelength at the time of measuring the excitation spectrum was the peak wavelength in the emission spectrum.

  In FIG. 4, the emission spectrum A and the excitation spectrum B of the phosphor obtained in Example 10 are shown. As a result, the phosphor obtained in Example 10 exhibits an emission spectrum A in a red region having a peak at 712 nm. Moreover, the excitation spectrum B of the phosphor showed high intensity in the near ultraviolet to blue region.

Next, in order to compare emission spectra, Ca ₁₄ Zn ₆ (Ga _0.97 Mn _0.03 ) ₁₀ O _{35 of} Example 10, CaAlSiN ₃ : Eu ²⁺ (Comparative Example 1), 3.5 MgO · 0 The emission spectrum with .5MgF · GeO ₂ : Mn ⁴⁺ (Comparative Example 2) was measured. FIG. 5 shows emission spectra when the phosphors of Example 10, Comparative Example 1, and Comparative Example 2 are excited at 450 nm. As shown in FIG. 5, the phosphors of Comparative Example 1 and Comparative Example 2 show an emission peak near 650 nm. On the other hand, since the phosphor of Example 10 has an emission peak at 712 nm, it can be seen that the phosphor contains many components from 700 nm to 800 nm.

  Table 2 shows the relative emission intensity and emission peak wavelength when excited at 450 nm for the phosphors of Examples 1 to 13. The relative light emission intensity is a relative value when the light emission intensity of Example 1 is 100%.

As shown in Table 2, the emission peak wavelength exceeded 710 nm in all examples. In particular, in the phosphor having a composition in which all AEs in the general formula (1) are calcium, all of the M ^I are zinc, and the M ^II contains at least Ga, strong emission intensity was obtained. In addition, particularly strong emission intensity was obtained with a phosphor having a composition in which all of AE is calcium, all of M ^I is zinc, and all of M ^II is gallium.

[Internal quantum efficiency measurement]
The internal quantum efficiency was measured when the phosphors obtained in Example 4 and Example 10 were excited at 450 nm. The internal quantum efficiency was measured using a quantum efficiency measurement system QE1100 manufactured by Otsuka Electronics Co., Ltd. Table 3 shows the measurement results of the internal quantum efficiency. As shown in Table 3, the internal quantum efficiencies of Examples 4 and 10 doped with manganese ions under excitation with blue light were as high as 65 to 70%.

[Evaluation of temperature quenching]
While quenching the phosphors obtained in Example 4 and Example 10 from room temperature (298 K) to 423 K (150 ° C.), temperature quenching when excited at 450 nm was evaluated. Specifically, the phosphor was irradiated with excitation light (450 nm) while heating the phosphor from 298 K to 423 K using a heating mechanism, and the peak height of the emission spectrum was examined. A spectrofluorometer FP-6500 manufactured by JASCO Corporation was used as an emission spectrum measuring apparatus. In addition to the phosphors obtained in Example 4 and Example 10, temperature quenching of Y ₃ Al ₅ O ₁₂ : Ce ³⁺ (P46 phosphor, Comparative Example 3) was also measured.

  In FIG. 6, the measurement result of the temperature quenching in the fluorescent substance obtained in Example 4 and Example 10 and the fluorescent substance of Comparative Example 3 is shown. In FIG. 6, the measurement data is plotted with the horizontal axis representing the phosphor temperature and the vertical axis representing the peak height of the emission spectrum. The peak height of the emission spectrum is shown as a relative value when the peak height at room temperature is 100%. As shown in FIG. 6, the phosphors of Example 4 and Example 10 doped with manganese ions have a high emission peak height (about 80% or more at room temperature) at 423 K, and have high heat resistance. In terms of surface quality, the phosphor was better than Comparative Example 3.

  The entire contents of Japanese Patent Application No. 2012-238581 (application date: October 30, 2012) and Japanese Patent Application No. 2013-015017 (application date: January 30, 2013) are incorporated herein by reference.

  Although the contents of the present invention have been described with reference to the embodiments, the present invention is not limited to these descriptions, and it is obvious to those skilled in the art that various modifications and improvements can be made.

The phosphor of the present invention has the same crystal structure as Ca ₁₄ Zn ₆ Al ₁₀ O ₃₅ and has a crystal structure in which a part of the constituent elements is substituted with manganese ions. Therefore, light in the near ultraviolet to blue region emitted from the light emitting element is efficiently absorbed and excited. Furthermore, when the excited phosphor transitions to the ground state, it efficiently emits red fluorescence having a peak at 700 to 750 nm. And the wavelength conversion member and light-emitting device using this fluorescent substance can radiate | emit red light with high light emission intensity.

1 Light Emitting Device 10 LED Chip (Light Emitting Element)
70 Wavelength conversion member

Claims (7)

General formula:
AE ₁₄ M ^I ₆ M ^II ₁₀ O ₃₅ : Mn ⁴⁺
(Wherein AE represents at least one element selected from the group consisting of Ca, Sr and Ba, M ^I represents at least one element selected from the group consisting of Zn and Mg, and M ^II represents from Al and Ga) Represents at least one element selected from the group consisting of
A phosphor having a composition represented by:   The phosphor according to claim 1, wherein the AE contains at least Ca. The phosphor according to claim 1 or 2, wherein the M ^I contains at least Zn. The phosphor according to any one of claims 1 to 3, wherein the M ^II includes at least Ga. The phosphor according to any one of claims 1 to 4,
A translucent medium in which the phosphor is dispersed;
A wavelength conversion member comprising: A light emitting element;
The wavelength conversion member according to claim 5, which emits light by absorbing at least part of light emitted by the light emitting element;
A light emitting device comprising:   The light emitting device according to claim 6, wherein a main light emission peak of light emitted from the light emitting element is in a range of 350 nm to 470 nm.

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