JP2010199273A - Light-emitting device and lighting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wavelength converter, a light emitting device and an illuminating device capable of improving luminous efficiency.
A light emitting element 17 that emits light having a wavelength of 370 to 420 nm, a substrate 15 on which the light emitting element 17 is placed, and a wavelength converter 19 that converts the wavelength of light emitted from the light emitting element 17 are provided. The wavelength converter 19 includes, from the light emitting element 17 side, a red phosphor layer 19a in which a red light emitting phosphor is dispersed in a transparent matrix, and a green in which a green light emitting phosphor is dispersed in a transparent matrix. The phosphor layer 19b and the blue phosphor layer 19c in which a blue light-emitting phosphor is dispersed in a transparent matrix are sequentially laminated, and the average particle size of the red light-emitting phosphor in the red phosphor layer 19a is 30 μm or more. Yes, the average particle diameter of the red light emitting phosphor in the red phosphor layer 19a is larger than the average particle diameter of the blue light emitting phosphor in the blue phosphor layer 19c.
[Selection] Figure 1

Description

  The present invention relates to a light-emitting device equipped with a wavelength converter that converts the wavelength of light emitted from a light source such as an LED (Light Emitting Diode) and outputs output light including the wavelength-converted light, and The present invention relates to a lighting device including a plurality of the light emitting devices.

  A light-emitting element made of a semiconductor material (hereinafter also referred to as “LED chip”) is small in size, has high power efficiency, and vividly colors. LED chips have excellent features such as long product life, strong resistance to repeated on / off lighting, and low power consumption, so they are expected to be applied to backlight sources such as liquid crystals and lighting sources such as fluorescent lamps. Has been.

  The LED chip converts a part of the light of the LED chip with a phosphor, and mixes and emits the wavelength-converted light and the light of the LED that is not wavelength-converted, thereby producing a color different from that of the LED light. It is applied to light emitting devices that emit light.

As such a light emitting device, for example, a phosphor emitting yellow light such as a YAG phosphor represented by a composition formula of (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ is arranged on a blue LED chip. Is known.

  In this light emitting device, when the light emitted from the LED chip is irradiated onto the yellow component phosphor, the phosphor emitting yellow light is excited to emit visible light, and this visible light is used as an output. However, when the brightness of the LED chip is changed, the light quantity ratio between blue and yellow changes, so that there is a problem that the color tone of white changes and the color rendering property is inferior.

  Therefore, in order to solve such problems, a purple LED chip having a peak of 400 nm or less is used as the LED chip, and the wavelength converter employs a structure in which three kinds of phosphors are mixed in a polymer resin. However, it has been proposed to emit white light by converting violet light into red, green, and blue wavelengths (see Patent Document 1). Thereby, a color rendering property can be improved.

  However, the light emitting device described in Patent Document 1 has a problem in that the luminous efficiency of white light cannot be improved because the quantum efficiency of the phosphor that emits red light in the ultraviolet region near 400 nm of excitation light is low.

In view of such circumstances, phosphors that emit red light have been developed, and conventionally, silicates that emit red light represented by the chemical formula Ba _3-xy Eu _x Mn _y MgSi ₂ O ₈ have been developed. System phosphors are known (for example, Non-Patent Document 1).

  In addition, a phosphor containing Eu has been developed as a phosphor emitting in yellow to green (hereinafter referred to as yellow-green) that can be used in combination with an LED chip having a peak wavelength of 400 nm or less as a light emitting element ( Patent Document 2).

This Patent Document 2 discloses a phosphor represented by Sr2 _-xy Ba _x Eu _y SiO ₄ , wherein the molar ratio of Sr to the molar ratio of Si, the molar ratio of Ba, and the molar ratio of Eu. A phosphor having a total ratio (Sr + Ba + Eu) / Si of 2 is disclosed.

JP 2002-314142 A JP 2004-115633 A

Journal of Electrochemical Society, 1968, P773-778

However, as a phosphor emitting red light of the wavelength converter described in Patent Document 1, an alkali represented by the chemical formula of Ba _3-xy Eu _x Mn _y MgSi ₂ O ₈ described in Non-Patent Document 1 is used. As an earth metal silicate phosphor and a phosphor emitting green light, an alkaline earth metal silicate system represented by the chemical formula of Sr _2-xy Ba _x Eu _y SiO ₄ described in Patent Document 2 Even when a phosphor and a phosphor emitting blue light are mixed together in a polymer resin to produce a wavelength converter, there is still a problem that the luminous efficiency of the light emitting device is still low.

  An object of this invention is to provide the light-emitting device and illuminating device which can improve luminous efficiency.

  A light-emitting device of the present invention includes a light-emitting element that emits light having a wavelength of 370 to 420 nm, a base on which the light-emitting element is mounted, and a wavelength converter that converts the wavelength of light emitted from the light-emitting element. The wavelength converter includes, from the light emitting element side, a red phosphor layer in which a phosphor emitting red light is dispersed in a transparent matrix, and a phosphor emitting green light is dispersed in a transparent matrix. The green phosphor layer and the blue phosphor layer in which the phosphor emitting blue light is dispersed in the transparent matrix are sequentially laminated, and the average particle size of the phosphor emitting red light in the red phosphor layer is 30 μm or more. The average particle size of the phosphor emitting red light in the red phosphor layer is larger than the average particle size of the phosphor emitting blue light in the blue phosphor layer.

  In the light-emitting device of the present invention, the wavelength from the light-emitting element is 370 to 700 when the red phosphor layer emits red light having a large average particle size of 30 μm or more (hereinafter sometimes referred to as red light-emitting phosphor). Light of 420 nm (hereinafter sometimes referred to as purple light) is sufficiently hit, and the red light-emitting phosphor sufficiently absorbs light from the light-emitting element, and red light is sufficiently emitted from the red light-emitting phosphor. The violet light that has passed between the phosphors hits the phosphor that emits green light in the green phosphor layer (hereinafter sometimes referred to as green light-emitting phosphor), and emits green light. Further, red light is emitted from the red phosphor layer. The purple light that has passed between the phosphors and between the green-emitting phosphors in the green phosphor layer hits a fine blue phosphor in the blue phosphor layer (hereinafter sometimes referred to as a blue-emitting phosphor). A fine blue-emitting phosphor. Absorption to blue to emit light, the light purple emitted is suppressed to the outside from the wavelength converter, it is possible to improve the luminous efficiency of white light.

  In the light-emitting device of the present invention, the average particle size of the phosphor emitting green light in the green phosphor layer is 30 μm or more, and the average particle size of the phosphor emitting green light in the green phosphor layer is The average particle size of the phosphor that emits blue light in the blue phosphor layer is larger. In such a light-emitting device, the red light-emitting phosphor having an average particle diameter of 30 μm or more is sufficiently exposed to purple light from the light-emitting element, and the red light-emitting phosphor sufficiently emits red light and has a large particle diameter. Purple light that has passed between the red light-emitting phosphors sufficiently hits a large green light-emitting phosphor having an average particle size of 30 μm or more, and can be sufficiently absorbed by the green light-emitting phosphor to emit green light sufficiently. Furthermore, the purple light that has passed between the large red light emitting phosphors in the red phosphor layer and between the green light emitting phosphors in the green phosphor layer sufficiently hits the fine blue light emitting phosphors, and the fine blue light emitting phosphors. In this case, the blue light is sufficiently absorbed and the violet light emitted from the wavelength converter to the outside is suppressed, and the light emission efficiency of white light can be improved.

  In the light emitting device of the present invention, the phosphor that emits red light and the phosphor that emits green light are made of an alkaline earth metal silicate, and the phosphor that emits blue light is made of a halophosphate. Features.

  An illumination device according to the present invention includes a plurality of the light-emitting devices described above. Since such a lighting device includes a plurality of the light emitting devices, color rendering can be improved.

  In the light emitting device of the present invention, the red light emitting phosphor in the red phosphor layer is sufficiently irradiated with purple light from the light emitting element, and the red light emitting phosphor sufficiently emits red light and passes between the red light emitting phosphors. Purple light hits the green light emitting phosphor in the green phosphor layer and green is emitted, and further purple light that has passed through the red light emitting phosphor in the red phosphor layer and the green light emitting phosphor in the green phosphor layer Blue light is emitted by hitting the fine blue light emitting phosphor in the blue phosphor layer, and the blue light is sufficiently absorbed by the fine blue light emitting phosphor to emit blue light, and the purple light emitted from the wavelength converter is suppressed. Thus, the luminous efficiency of white light can be improved.

  Since the lighting device of the present invention includes a plurality of light emitting devices with high white light emission efficiency, color rendering can be improved.

It is a schematic sectional drawing which shows the structure of a light-emitting device. It is a graph which shows the result of the fluorescence spectrum at the time of changing the average particle diameter and layer structure of a fluorescent substance. It is a graph which shows the result of the fluorescence spectrum at the time of changing the average particle diameter and layer structure of a fluorescent substance. It is explanatory drawing which shows the layer structure of a wavelength converter.

  A light-emitting device of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an embodiment of a light emitting device 11 of the present invention. According to FIG. 1, a light emitting device 11 of the present invention includes a substrate (base) 15 having an electrode 13 formed on the lower surface, a light emitting element 17 provided on the substrate 15, and a light emitting element 17 on the substrate 15. A wavelength converter 19 formed so as to cover and a reflection member 21 that reflects light is provided. Reference numeral 22 denotes a wire, reference numeral 16 denotes an adhesive, and reference numeral 25 denotes a resin layer.

  In the present invention, the wavelength converter 19 includes a red phosphor layer 19a in which a phosphor emitting red light (red light emitting phosphor) is dispersed in a transparent matrix, and a phosphor emitting green light (green light emitting fluorescence) in the transparent matrix. The green phosphor layer 19b in which the phosphor is dispersed and the blue phosphor layer 19c in which the phosphor emitting blue light (blue light emitting phosphor) is dispersed in the transparent matrix are sequentially laminated. The wavelength converter 19 includes a red phosphor layer 19a, a green phosphor layer 19b, and a blue phosphor layer 19c from the light emitting element 17 side.

  Further, the average particle diameter of the red light emitting phosphor in the red phosphor layer 19a is 30 μm or more, and the average particle diameter of the red light emitting phosphor in the red phosphor layer 19a is the blue light emitting fluorescence in the blue phosphor layer 19c. It is larger than the average particle size of the body.

  Further, the average particle diameter of the green light emitting phosphor in the green phosphor layer 19b is 30 μm or more, and the average particle diameter of the green light emitting phosphor in the green phosphor layer 19b is the blue light emission in the blue phosphor layer 19c. It is desirable that it is larger than the average particle diameter of the phosphor.

  The blue light emitting phosphor is a phosphor (not shown) that emits fluorescence (blue) having a wavelength of 430 nm to 490 nm, and the green light emitting phosphor is a phosphor (green) that emits fluorescence (green) having a wavelength of 520 nm to 570 nm. The red light emitting phosphor is a phosphor (not shown) that emits fluorescence (red) having a wavelength of 600 nm to 650 nm.

  The blue light-emitting phosphor is made of, for example, a material having high quantum efficiency that is excited by light having a wavelength of around 400 nm. On the other hand, the green light emitting phosphor is made of, for example, a material excited by light having a wavelength of 400 nm to 460 nm. The red light-emitting phosphor is made of a material that is excited not only by a wavelength of 400 nm to 460 nm but also by light in the vicinity of 550 nm.

  Each of the layers 19a, 19b, 19c constituting the wavelength converter 19 can uniformly disperse and carry the phosphor and suppress the photodegradation of the phosphor. Therefore, in the transparent matrix such as a polymer resin or a glass material. Are formed by dispersing phosphors. As a glass material such as a polymer resin film or a sol-gel glass thin film, a material having high transparency and durability that is not easily discolored by heating or light is desirable.

  As the polymer resin film, the material is not particularly limited, for example, epoxy resin, silicone resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, cellulose acetate, polyarylate, In addition, derivatives of these materials are used. In particular, it is preferable to have high light transmittance in a wavelength region of 350 nm or more. In addition to such transparency, a silicone resin is more preferably used from the viewpoint of heat resistance.

  Examples of the glass material include silica, titania, zirconia, and composite materials thereof. Compared to a polymer resin film, it has a high durability against light, particularly ultraviolet rays, and further has a high durability against heat, so that the product life can be extended. In addition, since the glass material can improve stability, a highly reliable light-emitting device can be realized.

  The wavelength converter 19 can be formed by a coating method using a glass material such as a sol-gel glass film or a polymer resin film. Although it will not be limited if it is a general coating method, the application | coating by a dispenser is preferable. For example, it can be produced by mixing a phosphor with a liquid uncured resin, a glass material, or a resin and a glass material plasticized with a solvent. As the uncured resin, for example, a silicone resin can be used. These resins may be of a type that is cured by mixing two liquids, or a type that is cured by one liquid. The body may be kneaded, or the phosphor may be kneaded in either one of the liquids. In addition, as a resin made plastic with a solvent, for example, an acrylic resin can be used.

  Each layer 19a, 19b, 19c constituting the wavelength converter 19 is obtained by forming it into a film shape by using a coating method such as a dispenser in an uncured state, or pouring it into a predetermined mold and hardening it. It is done. As a method of curing the resin and the glass material, there are a method of using heat energy and light energy, and a method of volatilizing the solvent. The wavelength converter 19 can be produced by laminating the red phosphor layer 19a, the green phosphor layer 19b, and the blue phosphor layer 19c produced by such a method in this order. The produced wavelength converter 19 is laminated on the resin layer 25 so as to form the red phosphor layer 19a, the green phosphor layer 19b, and the blue phosphor layer 19c from the light emitting element 17 side, thereby producing a light emitting device. Can be configured.

  The conductor forming the electrode 13 has a function as a conductive path for electrically connecting the light emitting element 17, is drawn from the lower surface of the base body 15 to the upper surface, and is electrically connected to the light emitting element 17 by the wire 22. Has been. As the conductor, for example, a metallized layer containing metal powder such as W, Mo, Cu, or Ag can be used. When the substrate 15 is made of ceramic, the conductor is formed on the upper surface of the wiring conductor by heat-treating a metal paste made of tungsten (W) or molybdenum (Mo) -manganese (Mn) or the like at a high temperature. In this case, a lead terminal made of copper (Cu) or iron (Fe) -nickel (Ni) alloy or the like is molded and fixed inside the substrate 15.

  Since the substrate 15 is required to have high thermal conductivity and high total reflectance, for example, a polymer resin in which metal oxide fine particles are dispersed is suitably used in addition to a ceramic material such as alumina or aluminum nitride. .

  The light-emitting element 17 uses a light-emitting element including a semiconductor material that emits light having a central wavelength of 370 to 420 nm (purple light) because the phosphor can be excited efficiently. As a result, it is possible to increase the intensity of the output light and obtain a light emitting device with higher luminous efficiency.

The light emitting element 17 preferably emits the center wavelength. However, the light emitting element substrate has a structure (not shown) including a light emitting layer made of a semiconductor material on the surface of the light emitting element substrate in that it has high quantum efficiency. preferable. Examples of such semiconductor materials include various semiconductors such as ZnSe and nitride semiconductors (GaN and the like), but the type of the semiconductor material is not particularly limited as long as the emission wavelength is in the above wavelength range. A stacked structure including a light-emitting layer made of a semiconductor material may be formed over a light-emitting element substrate using a crystal growth method such as a metal organic chemical vapor deposition method (MOCVD method) or a molecular beam epitaxial growth method. In order to form a nitride semiconductor with good crystallinity with high productivity, for example, when a light emitting layer made of a nitride semiconductor is formed on the surface of the light emitting element substrate, sapphire, spinel, SiC, Si, ZnO, ZrB ₂ , GaN Alternatively, a material such as quartz is preferably used.

  If necessary, a reflecting member 21 that reflects light is provided on the side surfaces of the light emitting element 17 and the wavelength converter 19, and the light escaping to the side surface can be reflected forward to increase the intensity of the output light. Examples of the material of the reflecting member 21 include aluminum (Al), nickel (Ni), silver (Ag), chromium (Cr), titanium (Ti), copper (Cu), gold (Au), iron (Fe), and these. These laminated structures and alloys, ceramics such as alumina ceramics, or resins such as epoxy resins can be used.

  The light-emitting device of this embodiment is obtained by installing the wavelength converter 19 on the light-emitting element 17 as shown in FIG. As a method of installing the wavelength converter 19 on the light emitting element 17, it is possible to install the cured sheet-like wavelength converter 19 on the light emitting element 17.

The lighting device of the present invention is configured by arranging a plurality of light emitting devices as shown in FIG. 1 on a substrate, for example, and electrically connecting these light emitting devices. Further, a plurality of light emitting elements 17, a wavelength converter 19, and a reflecting member 21 are formed on the surface of the substrate 15 to form a plurality of light emitting devices, and these light emitting devices are electrically connected to form an illumination device. Also good.
(Description of red-emitting phosphor)
Red-emitting phosphor, having an average particle diameter D ₅₀ consists of phosphor 30～45Myuemu, average particle size can be measured by a laser diffraction scattering method. The quantum efficiency of the red light emitting phosphor is 35 to 45%.

The red light-emitting phosphor is made of an alkaline earth metal silicate and contains, for example, M ¹ (M ¹ is Ba, Ba and Sr, or Ba and Ca), Eu, Mg, Mn, and Si as essential components. It is a phosphor. And the molar ratio of Eu with respect to 1 mol of Si is 0.14 or less, and the molar ratio of Mn with respect to 1 mol of Si is 0.07 or less.

Red-emitting phosphor, for ^{_{example, M 1 3-a Eu a}} Mg 1-b Mn b chemical composition of _Si c _{O 8} (provided that, a 0 <a ≦ 0.264, b is 0 <b ≦ 0.132 , C is a value satisfying 1.905 ≦ c ≦ 2.025). The phosphor represented by this chemical composition is close to the stoichiometric composition, so that crystals capable of converting excitation light into red can be formed with good reproducibility, and the crystal phase can be easily controlled. Generation of converted light other than red can be suppressed.

Molar ratio a of Eu ^is in _{M 1 3-a Eu a Mg} 1-b Mn b Si c O 8 0 < should satisfy a ≦ 0.264. However, if the molar ratio a of the luminescent center ion Eu ²⁺ is too small, the quantum efficiency tends to be small. On the other hand, if the amount is too large, the quantum efficiency tends to decrease due to a phenomenon called concentration quenching. The lower limit is preferably 0.06 ≦ a. In particular, a is preferably in the range of 0.1 ≦ a ≦ 0.2.

The molar ratio of Mn should satisfy 0 <b ≦ 0.132. However phosphor energy Eu ²⁺ excited by irradiation of the excitation light source is moved to Mn ^2+, because the Mn ²⁺ is believed to have red light emission, the degree of energy transfer varies depending on the composition of the Mn . Therefore, in order to obtain high red quantum efficiency, it is preferable that 0.01 ≦ b ≦ 0.1. Further, b preferably satisfies 0.075 ≦ b ≦ 0.1.

  Further, c may satisfy 1.905 ≦ c ≦ 2.025.

The red light-emitting phosphor has a chemical composition of M ¹³ _-xy Eu _x MgMn _y Si _z O ₈ (where x is 0 <x ≦ 0.2, y is 0 <y ≦ 0.1, z Is a value satisfying 1.905 ≦ z ≦ 2.025).
(Description of green light emitting phosphor)
Green-emitting phosphor of the present invention has an average particle diameter D ₅₀ consists of phosphor 30～45Myuemu, the average particle size can be measured by a laser diffraction scattering method. The quantum efficiency of the green light emitting phosphor is 40 to 50%.

The green light emitting phosphor of the present invention is made of an alkaline earth metal silicate, and is, for example, a phosphor containing M ² (M ² is at least one selected from Sr, Ba and Ca), Eu and Si. is there. This green light-emitting phosphor has a crystal represented by (M ² , Eu) ₂ SiO ₄ as a main crystal, and is 2 according to the X-ray absorption near edge structure (XANES) of the green light-emitting phosphor. The concentration of divalent Eu ions relative to the total amount of valent Eu ions and trivalent Eu ions is 90% or more.

Furthermore, the phosphor has a molar ratio of ^{M 2} for Si 1 mol, the sum of the molar ratio of Eu for Si 1 mole ^{((M 2 + Eu) /} Si) is less than 2.

That is, in the phosphor represented by Sr _2-xy Ba _x Eu _y SiO ₄ in Patent Document 2, the sum of the molar ratios of Sr, Ba, and Eu with respect to 1 mol of Si (also simply referred to as the sum of the molar ratios). (Sr + Ba + Eu) / Si is 2, but the concentration of divalent Eu ions is 90% or more with respect to the total amount of divalent Eu ions and trivalent Eu ions, that is, Eu ²⁺ / (Eu ²⁺ + Eu ³⁺ ) In the region of ≧ 0.9, the sum of the molar ratios (Sr + Ba + Eu) / Si is set to be smaller than 2 and further set to 1.94 or less. Luminous efficiency superior to the total (Sr + Ba + Eu) / Si = 2 phosphor can be realized.

The value of the total molar ratio (Sr + Ba + Eu) / Si referred to here is not a value obtained from the constituent element composition of the Sr _2-xy Ba _x Eu _y SiO ₄ crystal in the phosphor, but the configuration of the entire green light emitting phosphor. The value obtained from the elemental composition.

In an ideal (M ² , Eu) ₂ SiO ₄ crystal that emits fluorescence, for example, Sr _2−xy Ba _x Eu _y SiO ₄ crystal, the stoichiometric ratio is the sum of the molar ratios (Sr + Ba + Eu) / Si = 2. Therefore, although it seems desirable that the composition of the phosphor is also the sum of the molar ratio (Sr + Ba + Eu) / Si = 2, the reason is currently unknown, but rather the sum of the molar ratio (Sr + Ba + Eu) The total molar ratio of phosphors (Sr + Ba + Eu) / the total molar ratio deviating from the stoichiometric ratio (Sr + Ba + Eu) / Si <2, especially 1.94 or less, It has been clarified that a phosphor having a high quantum efficiency can be obtained by setting the range of 1.78 to 1.94. In particular, it is desirably 1.89 to 1.91.

Further, the value of x can be arbitrarily selected within a range of 0 to 1, and when x = 0, the phosphor can be yellow, and when x = 1, the phosphor can be yellow to green (hereinafter, yellow). (Sometimes green). Here, water resistance can be improved by setting x ≦ 1.
(Description of blue-emitting phosphor)
Blue-emitting phosphor of the present invention has an average particle diameter D ₅₀ consists of phosphor 2 to 10 [mu] m, average particle size can be measured by a laser diffraction scattering method. Further, the quantum efficiency of the blue light emitting phosphor is set to 35 to 45%.

Blue-emitting phosphors are (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₁₇ : Eu, Sr ₁₀ (PO _{4) 6 Cl 12: Eu,} 10 (Sr, Ca, Ba, Eu) · 6PO 4 · Cl 2, (Sr, Ca, Ba, Mg) 5 (PO 4) 3 (Cl, Br): Eu, and the like Used. The blue phosphor is a halophosphate represented by [(M, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu,] (M is at least one selected from Ca, Sr and Ba). Is preferably used.

  In such a light emitting device, a part of the wavelength of the purple light emitted from the light emitting element 17 that is a light source is converted into another wavelength by each phosphor, and output light including the light whose wavelength has been converted is output. The light emitted from the light-emitting element 17 having a certain wavelength is converted into light having another wavelength to emit light.

  In the light emitting device of the present invention, the purple light from the light emitting element 17 sufficiently hits the red light emitting phosphor having a large average particle diameter of 30 μm or more in the red phosphor layer 19a. Are sufficiently absorbed by the red light-emitting phosphor, red light is sufficiently emitted from the red light-emitting phosphor, and purple light that has passed between the red light-emitting phosphors in the red phosphor layer 19a is contained in the green phosphor layer 19b. The blue light emitted from the green light-emitting phosphor emits green light, and the purple light that passes between the red light-emitting phosphors in the red phosphor layer 19a and between the green light-emitting phosphors in the green phosphor layer 19b is further reflected in the blue phosphor layer 19c. It hits the fine blue light-emitting phosphor inside, and it is sufficiently absorbed by the fine blue light-emitting phosphor to emit blue light, suppressing the purple light emitted from the wavelength converter 19 to the outside and improving the light emission efficiency of white light it can.

  Further, the average particle diameter of the green light emitting phosphor in the green phosphor layer 19b is set to 30 μm or more, and the average particle diameter of the green light emitting phosphor in the green phosphor layer 19b is set to be the blue light emitting phosphor in the blue phosphor layer 19c. By making the average particle size larger than the average particle size, the red light emitting phosphor having a large average particle size of 30 μm or more is sufficiently exposed to purple light from the light emitting element 17, and the red light emitting phosphor sufficiently emits red light. At the same time, the purple light that has passed between the red-emitting phosphors having a large particle size sufficiently hits the green-emitting phosphor having an average particle size of 30 μm or more and is sufficiently absorbed by the green-emitting phosphor. Further, the purple light that has passed between the large red light emitting phosphors in the red phosphor layer 19a and between the large green light emitting phosphors in the green phosphor layer 19b becomes fine blue light emitting phosphors. Enough hits and fines Blue to emit light is sufficiently absorbed by the blue-emitting phosphor, light purple emitted from the wavelength converter 19 to the outside can be suppressed, thereby improving the luminous efficiency of white light.

  First, the light emitting device 11 of FIG. 1 was manufactured. An alumina substrate was used as the substrate (base) 15, a light emitting element in which a nitride semiconductor was epi-formed on a sapphire substrate was used as the light emitting element 17 provided on the substrate 15, and aluminum (Al) was used as the reflecting member 21.

  First, the wavelength converter 19 was produced. The wavelength converter 19 includes, from the light emitting element 17 side, a red phosphor layer 19a in which a red light emitting phosphor is dispersed in a transparent matrix, a green phosphor layer 19b in which a green light emitting phosphor is dispersed in a transparent matrix, and a transparent matrix. A blue phosphor layer 19c having a blue light emitting phosphor dispersed therein was sequentially laminated.

  The red phosphor layer 19a is prepared by adding 0.339 g of a red light-emitting phosphor having an average particle size of 40 μm to 1 g of a material constituting the transparent matrix (Toshiba silicone resin: Shin-Etsu Chemical CY52-205), and stirring with a deaerator. A phosphor paste was prepared by mixing.

Examples of red emitting ^phosphor, in the chemical composition of _{M 1 3-a Eu a Mg} 1-b Mn b Si c O 8, a = 0.2, b = 0.075, expressed by c = 1.905 A thing was used.

  The green phosphor layer 19b is prepared by adding 0.301 g of a green light emitting phosphor having an average particle size of 40 μm to 1 g of a material constituting a transparent matrix (silicone resin: Shin-Etsu Chemical CY52-205) and mixing with a stirring deaerator. Thus, a phosphor paste was produced.

The green light-emitting phosphor has a chemical composition of Sr2 _-xy Ba _x Eu _y SiO ₄ and is represented by x = 0.536, y = 0.05, (Sr + Ba + Eu) /Si=1.90. I used something.

  The blue phosphor layer 19c is prepared by adding 0.278 g of a blue light-emitting phosphor having an average particle diameter of 3 μm to 1 g of a material constituting a transparent matrix (silicone resin: Shin-Etsu Chemical CY52-205) and mixing with a stirring deaerator. Thus, a phosphor paste was produced.

As the blue light-emitting phosphor, a material represented by (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu was used.

  In addition, the average particle diameter of each fluorescent substance was controlled by the mesh diameter which mesh-passes the produced fluorescent substance powder.

  First, a phosphor paste for forming a blue phosphor layer was applied to a glass plate and heated at 150 ° C. for 2 minutes to solidify the silicone resin to form a blue phosphor layer having a thickness of 0.52 mm. Furthermore, a phosphor paste for forming a green phosphor layer is applied on the solidified blue phosphor layer, heated at 150 ° C. for 2 minutes to solidify the silicone resin, and a green phosphor layer having a thickness of 0.05 mm is formed. did. Furthermore, a phosphor paste for forming a red phosphor layer is applied on the solidified green phosphor layer, heated at 150 ° C. for 2 minutes to solidify the silicone resin, and a red phosphor layer having a thickness of 0.18 mm is formed. And the wavelength converter was produced.

  As shown in FIG. 1, this wavelength converter was disposed on a resin layer 25 covering the light emitting element 17 to produce a light emitting device.

  The obtained light-emitting device was measured with a fluorescence spectrophotometer (manufactured by Shimadzu Corporation), and the fluorescence spectrum result was described in Example 1 of FIG. Further, except that the average particle size of the red light emitting phosphor, the green light emitting phosphor, and the blue light emitting phosphor is changed as shown in Table 1, a wavelength converter is produced in the same manner as described above, and a light emitting device is produced. ,evaluated.

  In the examples and comparative examples, the thicknesses of the produced wavelength converters were the same, and the amounts of the phosphors used were also the same. These results are shown in FIGS. FIG. 4 shows the layer structure of the wavelength converter corresponding to the layer structure shown in Table 1.

  In the results of the fluorescence spectra of FIG. 2 and FIG. 3, the LED element has a wavelength near 400 nm, the blue light-emitting phosphor has a wavelength near 450 nm, the green light-emitting phosphor has a wavelength near 550 nm, and the red light-emitting phosphor has a wavelength near 600 nm.

  2 and 3, when the average particle diameter of the red light emitting phosphor is 30 μm or more and larger than the average particle diameter of the blue light emitting phosphor (Examples 1 to 4), conventional blue, green, and red light emission Compared with the case where a wavelength converter formed by mixing phosphors in a single layer (Comparative Examples 2, 4, 7, 9, 11), the intensities of all of the blue, green, and red fluorescence peaks are increased. This shows that the luminous efficiency of white light is improved.

  On the other hand, when the layer structure is the reverse of the present invention (Comparative Examples 1, 3, 6, 8, 10), the intensity of the blue fluorescence peak is increased, but the intensity of the green and red fluorescence peaks is decreased. Therefore, it can be seen that the light emission efficiency of white light decreases because the color of white light changes.

DESCRIPTION OF SYMBOLS 11 ... Light-emitting device 13 ... Electrode 15 ... Board | substrate 17 ... Light-emitting element 19 ... Wavelength converter 19a ... Red fluorescent substance layer 19b ... Green fluorescent substance layer 19c ... Blue Phosphor layer

Claims (4)

  A light emitting device comprising: a light emitting element that emits light having a wavelength of 370 to 420 nm; a base on which the light emitting element is mounted; and a wavelength converter that converts the wavelength of light emitted from the light emitting element. The wavelength converter includes, from the light emitting element side, a red phosphor layer in which a phosphor emitting red light is dispersed in a transparent matrix, a green phosphor layer in which a phosphor emitting green light is dispersed in a transparent matrix, and a transparent matrix A blue phosphor layer in which phosphors emitting blue light are dispersed is sequentially laminated, and an average particle diameter of phosphors emitting red light in the red phosphor layer is 30 μm or more, and the red phosphors A light emitting device, wherein an average particle diameter of a phosphor emitting red light in a layer is larger than an average particle diameter of a phosphor emitting blue light in the blue phosphor layer.   The average particle diameter of the phosphor emitting green light in the green phosphor layer is 30 μm or more, and the average particle diameter of the phosphor emitting green light in the green phosphor layer is blue in the blue phosphor layer. The light-emitting device according to claim 1, wherein the light-emitting device has an average particle diameter larger than that of the phosphor that emits light.   3. The phosphor according to claim 1, wherein the phosphor emitting red light and the phosphor emitting green light are made of an alkaline earth metal silicate, and the phosphor emitting blue light is made of a halophosphate. The light-emitting device of description.   A lighting device comprising a plurality of light-emitting devices according to claim 1.

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