JP4389513B2 - Light emitting device, lighting device, and image display device - Google Patents

Description

  The present invention relates to a light-emitting device, and more specifically, a first light emitter that emits light from ultraviolet light to visible light region by a power source, and absorbs light in the visible light region from the ultraviolet light to generate long-wavelength visible light. By combining with a second phosphor as a wavelength conversion material having a phosphor containing a phosphor containing a luminescent center ion as a base compound that emits light, it emits light with high color purity and high intensity regardless of the use environment. The present invention relates to a light emitting device capable of performing the above.

In order to generate white and other various colors with high luminance and high color purity by mixing blue, red, and green, a light emitting device in which the light emission color of an LED or LD is converted with a phosphor has been proposed. . For example, in US Pat. No. 6,294,800, as a substance capable of generating white light emission upon irradiation with light in a 330 to 420 nm region typified by light from an LED, Ca ₈ Mg
A substance combining a green phosphor, a red phosphor and a blue phosphor containing (SiO ₄ ) ₄ Cl ₂ : Eu ²⁺ , Mn ²⁺ is disclosed, and the blue phosphor (Sr, Ba, Ca) is disclosed. ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ and BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ are mentioned.

However, up to now, as a material for converting LED light into blue visible light or a second light emitter for the first light emitter such as an LED, US Pat. No. 6,294,800 and US Pat. In a light emitting device such as (Sr, Ba, Ca) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ described in US Pat. No. 6,466,135, light emission intensity and color purity cannot be said to be sufficient. ,
Further improvements are demanded as light sources such as displays, backlight sources, and traffic lights.

In general, other divalent luminescent metal ions such as Eu ²⁺ can be substituted at the A site in the crystal of A ₅ (PO ₄ ) ₃ Cl (A is an alkaline earth metal). However, it is known that it can be used as a fluorescent lamp phosphor by utilizing the fact that it is excited by Hg resonance ultraviolet light having a wavelength of 254 nm and emits light. Also recently, A ₅ (PO ₄ ) ₃ Cl has been added to the 360-42 LED.
A patent has been filed that states that it emits blue light by excitation of light near 0 nm. In US Pat. No. 6,294,800, (Sr, Ba, Ca) ₅ (PO ₄ ) ₃ C
Although it is described that l: Eu is used, there is no description regarding the composition of alkaline earth metal and Eu. In addition, US Pat. No. 6,466,135 describes the use of a general formula (Sr, Ba, Ca) _5-x Eu _x (PO ₄ ) ₃ Cl containing a large amount of Sr. and, specifically, _{(Sr 1-yz Ba y Ca} z) 5-x Eu 2+ x (PO 4) 3 Cl (0.0
1 ≦ x ≦ 0.2, 0 ≦ y ≦ 0.1, and 0 ≦ z ≦ 0.1). However, in such a composition, the y value in CIE chromaticity coordinates is described. Since it was small, sufficient luminance could not be obtained.
US Pat. No. 6,294,800 US Pat. No. 6,466,135

  The present invention has been made in view of the above-described prior art to develop a light emitting device having extremely high emission intensity and good color purity. Therefore, the present invention is easy to manufacture and has a high emission intensity. An object of the present invention is to provide a double light emitting device that is high and has high color purity at a relatively low cost.

As a result of intensive studies to solve the above problems, the present inventor has found that a strong emission intensity by excitation of light in the vicinity of 400 nm in a specific composition range in the A ₅ (PO ₄ ) ₃ Cl (A is alkaline earth metal) system. The present invention has been completed by finding that the result of obtaining an appropriate y value in the CIE chromaticity coordinates and a high color purity is obtained. That is, in the light-emitting device including the first light emitter that generates light of 350 to 415 nm and the second light emitter that generates visible light by irradiation of light from the first light emitter, When a phosphor containing a crystal phase having the following specific chemical composition is used as the illuminant, the phosphor is irradiated with light in the vicinity of 350 to 415 nm, and emits visible light with high color purity and high intensity. The inventors have found that the object can be achieved, specifically, that the object can be achieved by using a crystal phase having a basic composition of Ca ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ . . Accordingly, the present invention provides a light emitting device including a first light emitter that generates light of 350 to 415 nm and a second light emitter that generates visible light when irradiated with light from the first light emitter. The gist of the present invention is a light emitting device characterized in that the phosphor of 2 contains a phosphor having a crystal phase having a chemical composition of the general formula [1].

(In the above general formula [1], M represents at least one element selected from the group consisting of M g, Sr and Ba, X represents a C l. Further, a is, 0.5 ≦ a ≦ 2, b is a number that satisfies (5-a) × 0.8 ≦ b ≦ 5-a, c is 2.7 ≦ c ≦ 3.3, and d is a number that satisfies 0.9 ≦ d ≦ 1.1. .)

  According to the present invention, it is possible to provide a light emitting device having high emission intensity and good color purity.

  The present invention provides a light emitting device having a first light emitter that emits light of 350 to 415 nm and a second light emitter that generates visible light by irradiation of light from the first light emitter. The light-emitting device comprises a phosphor having a crystal phase having a chemical composition represented by the general formula [1].

  Here, the element M in the formula [1] represents a metal element other than Eu and Ca. Regarding the element M, from the viewpoint of emission intensity, the ratio of the total of Ba, Mg, Sr, Zn, and Mn to the element M is usually 70 mol% or more, and in particular, the total element M of Ba, Mg, Zn, and Sr Is preferably 70 mol% or more, more preferably 90 mol% or more of the total amount of Ba, Mg, Zn and Sr in the element M, and all of the elements M are Ba, Mg, Sr, It is more preferable to use at least one element selected from the group consisting of Zn and Mn, and it is most preferable that all of the elements M be at least one element selected from the group consisting of Ba, Mg, Zn and Sr.

When a metal element other than the above is included in the crystal as the metal element in element M, the metal element is not particularly limited, but contains the same valence as Ca and these five metal elements, that is, a divalent metal element. In this case, the crystal structure is easily retained, which is desirable. Divalent metal element and luminescent center Eu
^A small amount of a metal element such as monovalent, trivalent, pentavalent, or hexavalent metal may be introduced in order to assist crystallization of the composite oxide by diffusion in the solid during ²⁺ firing. One example is Ca ₅ (PO ₄ ) ₃ C.
l: A portion of Ca ²⁺ in the Eu phosphor can be replaced with equimolar amounts of Li ⁺ and Ga ³⁺ while maintaining the charge compensation effect. A small amount of a metal element that can be a sensitizer may be substituted.

X in the general formula [1] is a monovalent anionic group other than PO ₄ . With respect to X, from the viewpoint of light emission intensity and the like, 50 mol% or more of X is preferably a halogen atom, more preferably 70 mol% or more, and particularly preferably 90 mol% or more. Examples of the halogen atom include Cl, F, Br and the like, and Cl is preferred. When 50 mol% or more of X is a halogen atom, X may contain a hydroxyl group or the like as the remaining anionic group. In the most preferred embodiment, 50 mol% or more, particularly 70 mol% or more, more preferably 90 mol% or more of the anionic group X is Cl. In this case, examples of the remaining group include other halogen atoms and OH groups.

The molar ratio a of Eu in the general formula [1] is set to 0.1 ≦ a ≦ 1.5 . In view of the balance of light emission intensity and color purity, and most preferably to 0.1 or more. If the content of the emission center ion Eu ²⁺ is less than the above range, the emission intensity tends to be small, but if the value of a is too large, the emission intensity tends to decrease due to a phenomenon called concentration quenching. preferably 2 or less, more preferably 1.5 or less, in terms of balance and the like of the emission intensity and color purity, 1 hereinafter is most preferred.

The molar ratio b of Ca in the general formula [1] is usually (5-a) × 0.5 ≦ b ≦ 5-a, preferably (5) from the viewpoint of the balance between emission intensity and color purity. −a) × 0.6 ≦ b ≦ 5-a, more preferably (5-a) × 0.7 ≦ b ≦ 5-a, but (5-a) × 0.8 ≦ b ≦ 5-a Most preferably, a. In general, a crystal phase having a basic composition of (Sr, Ba, Ca, Mg) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ can take a wide range of molar ratios of Ca. By adopting a relatively large numerical value such as the above, a significantly high emission intensity can be obtained. Note that the value of a + b may be set to 5 so that the metal element M is not included.

  When the y value in the CIE chromaticity coordinates, which is an indicator of the color purity of the phosphor, becomes too large, the blue color purity becomes small. Therefore, when a phosphor having a large y value is used as a backlight light source for a display, There are problems such as a narrow color reproduction range of the display. On the other hand, if the y value is too small, the color purity of blue is increased, so that the color reproduction range of the display is widened, but there is a problem that the luminance is lowered because the visibility is lowered. Therefore, it is important that the y value serving as an indicator of the emission intensity and color purity of the phosphor is balanced, and the lower limit of the y value is usually 0.02 or more, preferably 0.035 or more, and the upper limit. Is 0.2 or less, preferably 0.1 or less, more preferably 0.052 or less.

  In the general formula [1], c and d satisfy 2.7 ≦ c ≦ 3.3 and 0.9 ≦ d ≦ 1.1, but the lower limit of c is preferably 2.8 ≦ c. 2.9 ≦ c is more preferable, and the upper limit is preferably c ≦ 3.2, and more preferably c ≦ 3.1. The lower limit of d is preferably 0.93 ≦ d, more preferably 0.95 ≦ d, and the upper limit is preferably d ≦ 1.07, more preferably d ≦ 1.05.

In the basic crystal Eu _a Ca _b M _5-ab (PO ₄ ) _c X _d of the general formula [1], even if some lattice defects occur, there is no significant effect on the fluorescence performance of the present purpose. It can be used within the range of inequality of b, c, d.

In general, a crystal of A ₅ (PO ₄ ) ₃ Cl (A is an alkaline earth metal) has a hexagonal crystal structure, and its space group is P6 ₃ / m.

The crystal structure of the phosphor in the present invention is usually represented by the chemical composition formula A ₅ (PO ₄ ) ₃ Cl shown above.
It is an apatite structure represented by. The Ca site of Ca ₅ (PO ₄ ) ₃ Cl contains Ba and Sr.
, Mg, Zn, Mn and the like can be substituted in a wide composition range. Further, if the amount is small, metals having different valences such as Na and La can be substituted. The Cl site can be substituted with anionic species such as F, Br, and OH, and the structure is maintained. In the present invention, among these substituted substances, a substituted substance using Ca as a cation species is usually used as a matrix, and further, it corresponds to a crystal phase in which Eu ²⁺ is substituted at the cation site as an activator.

  The phosphor used in the present invention is excited by light of 350 to 415 nm from the first light emitter, and generates visible light. The phosphor generates visible light having a very strong emission intensity by excitation of light of 350 to 415 nm.

The phosphor used in the present invention includes an M source, a X source, a PO ₄ source compound, a Ca source compound, and a luminescent center ion (Eu) element source compound as shown in the general formula [1]. After pulverizing using a dry pulverizer such as a hammer mill, roll mill, ball mill, jet mill, etc., mix with a blender such as a ribbon blender, V-type blender or Henschel mixer, or after mixing, use a dry pulverizer. Use dry method to pulverize, or add these compounds in a medium such as water and pulverize and mix them using a wet pulverizer such as a medium agitating pulverizer, or use a dry pulverizer to remove these compounds. After the pulverization, the prepared pulverized mixture is heated and fired by a wet method in which a slurry prepared by adding and mixing in a medium such as water is spray-dried or the like. Ri can be produced.

  Among these pulverization and mixing methods, in particular, in the element source compound of the luminescent center ion, it is preferable to use a liquid medium because it is necessary to uniformly mix and disperse a small amount of the compound over the whole. The latter wet method is preferable from the viewpoint of obtaining uniform mixing in the element source compound as a whole, and the heat treatment method is usually 700 to 1500 ° C. in a heat-resistant container such as alumina or quartz crucible or tray. The heating is preferably performed at a temperature of 900 to 1300 ° C. for 10 minutes to 24 hours in a single or mixed atmosphere of a gas such as air, oxygen, carbon monoxide, carbon dioxide, nitrogen, hydrogen, and argon. In addition, after heat processing, washing | cleaning, drying, a classification process, etc. are made | formed as needed.

  As the heating atmosphere, an atmosphere necessary for obtaining an ion state (valence) in which the element of the emission center ion contributes to light emission is selected. In the case of divalent Eu or the like in the present invention, a neutral or reducing atmosphere such as carbon monoxide, nitrogen, hydrogen, and argon is preferable, but it can be selected even under an oxidizing atmosphere such as air and oxygen. .

Here, as the compounds of M source, X source, Ca source, and Eu source, oxides, hydroxides, carbonates, nitrates, sulfates, oxalates of M, X, Ca, and Eu, Examples of the PO ₄ source compound include hydrogen phosphates such as element M and NH ₄ , phosphates, metaphosphates, pyrophosphates, P ₂ O ₅ , and PX _3. , PX ₅ , M ₂ PO ₄ X, phosphoric acid, metaphosphoric acid, pyrophosphoric acid, etc., and examples of the X source compound include MX, NH ₄ X, HX, M ₂ PO ₄ X, etc. Among them, the chemical composition, reactivity, and non-generation of NO _x , SO _x, etc. during firing are selected.

Specific examples of preferred Ca source compounds for Ca include CaO, Ca (OH) ₂ , CaCO ₃ , Ca (NO ₃ ) ₂ , Ca (OCO) ₂ .H ₂ O, Ca (OCOCH _{3 2}・ 0
. Examples thereof include 5H ₂ O and CaCl ₂ .

Specific examples of Ba, Mg, Sr, Zn, or Mn synthetic raw material compounds in metal element group M include BaO, Ba (OH) ₂ .8H ₂ O, BaCO ₃ , B
a (NO ₃ ) ₂ , BaSO ₄ , Ba (OCO) ₂ .2H ₂ O, Ba (OCOCH ₃ ) ₂ , BaC
l ₂ etc., and Mg source compounds include MgO, Mg (OH) ₂ , MgCO ₃ , Mg (OH
₂ ) 3MgCO ₃ .3H ₂ O, Mg (NO ₃ ) ₂ .6H ₂ O, Mg (OCO) ₂ .2H ₂ O, Mg (OCOCH ₃ ) ₂ .4H ₂ O, MgCl _2, etc. Source compounds include SrO, Sr (OH) ₂ , SrCO ₃ , Sr (NO ₃ ) ₂ .4H ₂ O, Sr (OCO) ₂ .H ₂ O, Sr (
OCOCH ₃ ) ₂ .H ₂ O, SrCl _{2 and the} like, and Zn source compounds include ZnO, Zn (OH) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ .6H ₂ O, Zn (OCO) ₂ , Zn (OCOCH ₃ ) ₂ , ZnCl _{2 and the} like, and as the Mn source compound, MnO ₂ , Mn ₂ O ₃ , Mn ₃ O ₄ , MnO, Mn (OH) ₂ , MnCO ₃ , Mn (NO ₃ ) ₂ , Mn (OCOCH ₃ ) ₂ · 2H ₂ O, Mn (
OCOCH ₃ ) ₃ · nH ₂ O, MnCl ₂ · 4H ₂ O and the like.

Further, with respect to Eu, which is preferable as the element of the luminescent center ion, specific examples of the element source compound include Eu ₂ O ₃ , Eu (OCOCH ₃ ) ₃ .4H ₂ O, EuCl ₃ .6H ₂ O, Eu ₂ (OCO) ₃ · 6H ₂ O and the like.

In the present invention, the first light emitter that irradiates the phosphor with light generates light having a wavelength of 350 to 415 nm. Preferably, a light emitter that generates light having a peak wavelength in the wavelength range of 350 to 415 nm is used. Specific examples of the first light emitter include a light emitting diode (LED) or a laser diode (LD). Laser diodes are preferred because they consume less power. Of these, GaN LEDs and LDs using GaN compound semiconductors are preferred. This is because GaN-based LEDs and LDs have significantly higher light emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and are extremely bright with very low power when combined with the phosphor. This is because light emission can be obtained. For example, for a current load of 20 mA, the GaN system usually has a light emission intensity 100 times or more that of the SiC system. A GaN-based LED or LD preferably has an Al _x Ga _Y N light emitting layer, a GaN light emitting layer, or an In _x Ga _Y N light emitting layer. Among GaN-based LEDs, In _X
Those having a Ga _Y N light-emitting layer are particularly preferred because the light emission intensity is very strong.
In particular, a multi-quantum well structure composed of an In _x Ga _y N layer and a GaN layer is particularly preferable because the emission intensity is very high. In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics. A GaN-based LED has these light-emitting layer, p-layer, n-layer, electrode, and substrate as basic components, and the light-emitting layer is composed of n-type and p-type Al _x Ga _y N layers, GaN layers, or In _x. Those having a heterostructure sandwiched by Ga _Y N layers or the like have high luminous efficiency, and those having a heterostructure having a quantum well structure have higher luminous efficiency and are more preferable.

  In the present invention, it is particularly preferable to use a surface-emitting type illuminant, particularly a surface-emitting GaN-based laser diode, as the first illuminant because the luminous efficiency of the entire light-emitting device is increased. A surface-emitting type illuminant is an illuminant that emits strong light in the surface direction of a film. In a surface-emitting GaN-based laser diode, the crystal growth of a light-emitting layer or the like is controlled, and a reflective layer or the like is successfully performed. By devising, the light emission in the surface direction can be made stronger than the edge direction of the light emitting layer. When the surface emitting type is used, the light emission cross-sectional area per unit light emission amount can be increased compared to the type that emits light from the edge of the light emitting layer. As a result, the phosphor of the second light emitter is irradiated with the light Since the irradiation area can be made very large with the same amount of light and the irradiation efficiency can be improved, stronger light emission can be obtained from the phosphor that is the second light emitter.

  When a surface-emitting type is used as the first light emitter, the second light emitter is preferably a film. As a result, the cross-sectional area of the light from the surface-emitting type light emitter is sufficiently large. Therefore, when the second light emitter is formed into a film in the direction of the cross section, the irradiation cross-section area of the phosphor from the first light emitter is irradiated. Becomes larger per unit amount of phosphor, so that the intensity of light emitted from the phosphor can be further increased.

Further, when a surface-emitting type is used as the first light emitter and a film-like one is used as the second light emitter, the second light emitter directly in the form of a film on the light-emitting surface of the first light emitter. It is preferable to have a shape in which is contacted. Contact here refers to creating a state in which the first light emitter and the second light emitter are in perfect contact with each other without air or gas. As a result, it is possible to avoid a light amount loss in which light from the first light emitter is reflected by the film surface of the second light emitter and oozes out, so that the light emission efficiency of the entire apparatus can be improved.

FIG. 1 is a schematic perspective view showing the positional relationship between the first light emitter and the second light emitter in an example of the light emitting device of the present invention. In FIG. 1, 1 is a film-like second light emitter having the phosphor, 2 is a surface-emitting GaN-based LD as the first light emitter, and 3 is a substrate. To create a state of being in contact with each other, may be contacted by the adhesive or other means to each other in their surfaces in advance, respectively Ku separate Nitsu LD2 and the second light emitter 1, the light-emitting surface of the LD2 second light emitter may be a film (molded) is not the above. As a result, the LD 2 and the second light emitter 1 can be brought into contact with each other.

  The light from the first illuminant and the light from the second illuminant are usually directed in all directions. However, when the phosphor powder of the second illuminant is dispersed in the resin, the light is out of the resin. A part of the light is reflected when exiting, so the direction of the light can be adjusted to some extent. Accordingly, since light can be guided to a certain degree in an efficient direction, it is preferable to use a phosphor in which the phosphor powder is dispersed in a resin as the second luminous body. Further, when the phosphor is dispersed in the resin, the total irradiation area of the light from the first light emitter to the second light emitter is increased, so that the light emission intensity from the second light emitter can be increased. It also has the advantage of being able to Examples of resins that can be used in this case include silicon resins, epoxy resins, polyvinyl resins, polyethylene resins, polypropylene resins, polyester resins, and the like, but the dispersibility and stability of the phosphor powder are good. In this respect, silicon resin or epoxy resin is preferable. When the powder of the second luminous body is dispersed in the resin, the weight ratio of the powder of the second luminous body to the whole of the resin is usually 10 to 95%, preferably 20 to 90%, more preferably. Is 30-80%. If the phosphor is too much, the luminous efficiency may be reduced due to aggregation of the powder, and if it is too little, the luminous efficiency may be lowered due to light absorption or scattering by the resin.

  The light emitting device of the present invention includes the phosphor as a wavelength conversion material and a light emitting element that emits light of 350 to 415 nm, and the phosphor absorbs light of 350 to 415 nm emitted from the light emitting element. In addition, it is a light emitting device that has good color rendering properties and can generate high-intensity visible light regardless of the use environment, and a light source such as a backlight light source and a traffic light, and an image display device such as a color liquid crystal display. And suitable for light sources such as lighting devices such as surface emitting.

  The light emitting device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic cross-sectional view showing an embodiment of a light emitting device having a first light emitter (350-415 nm light emitter) and a second light emitter. 4 is a light emitting device, 5 is a mount lead, 6 is an inner lead, 7 is a first light emitter (350-415 nm light emitter), 8 is a phosphor-containing resin portion as a second light emitter, 9 Is a conductive wire, and 10 is a mold member.

As shown in FIG. 2, the light emitting device as an example of the present invention has a general bullet shape, and a first light emitter made of a GaN-based light emitting diode or the like is disposed in the upper cup of the mount lead 5. (350-415 nm illuminant) 7 is a phosphor formed as a second illuminant by mixing and dispersing the phosphor in a binder such as silicon resin, epoxy resin or acrylic resin and pouring it into the cup. It is fixed by being covered with the body-containing resin portion 8. On the other hand, the first light emitter 7 and the mount lead 5, and the first light emitter 7 and the inner lead 6 are each electrically connected by a conductive wire 9, and these are entirely covered with a mold member 10 made of epoxy resin or the like, Protected.

  Further, as shown in FIG. 3, the surface emitting illumination device 11 incorporating the light emitting element 1 has a large number of light emission on the bottom surface of a rectangular holding case 12 whose inner surface is light-opaque such as a white smooth surface. The device 13 is arranged with a power source and a circuit (not shown) for driving the light emitting element 13 provided outside thereof, and a milky white acrylic plate or the like is provided at a position corresponding to the lid portion of the holding case 12. The diffusion plate 14 is fixed for uniform light emission.

  Then, the surface emitting illumination device 11 is driven to apply light to the first light emitter of the light emitting element 13 to emit light of 350 to 415 nm, and a part of the light emission is used as the second light emitter. The phosphor in the phosphor-containing resin part absorbs and emits visible light, while light emission with high color rendering properties is obtained by mixing with blue light or the like that is not absorbed by the phosphor. 14, is emitted upward in the drawing, and illumination light with uniform brightness is obtained within the surface of the diffusion plate 14 of the holding case 12.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

Calcium chloride dihydrate; 0.0141 mol, europium chloride hexahydrate; 0.00014 mol was weighed and dissolved in 20 ml of water. To this aqueous solution, 0.00854 mol of 85% phosphoric acid as phosphoric acid was added, and the mixed solution was transferred to a magnetic dish to make the total solution volume 30-30 ml. This solution was heated and dried with stirring. The dried solid was collected and pulverized in an agate mortar. A portion of this pulverized product was transferred to an alumina crucible and fired at 1000 ° C. for 2 hours under a nitrogen gas flow containing 4% hydrogen to obtain phosphor Ca _4.95 Eu _0.05 (PO ₄ ) ₃ Cl (second phosphor) Phosphor to be used). The X-ray diffraction pattern of this phosphor was identical in crystal structure with that of Ca ₅ (PO ₄ ) ₃ Cl, and it was found that the target crystal phase was formed. The fired solid was pulverized in an agate mortar, and the phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode, and the emission spectrum was measured. Table 1 shows the chromaticity coordinate values x and y calculated from the wavelength of the emission peak, the relative emission intensity, and the emission spectrum.

Calcium chloride dihydrate; 0.01426 mol, europium chloride hexahydrate; 0.00007 mol, 85% phosphoric acid is 0.00863 mol as phosphoric acid. A phosphor having the chemical composition shown in -1 was produced. The X-ray diffraction pattern of this phosphor was identical in crystal structure with that of Ca ₅ (PO ₄ ) ₃ Cl, and it was found that the target crystal phase was formed. The fired solid was pulverized in an agate mortar, and the phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode, and the emission spectrum was measured. Table 1 shows the chromaticity coordinate values x and y calculated from the wavelength of the emission peak, the relative emission intensity, and the emission spectrum.

Calcium chloride dihydrate; 0.01436 mol, europium chloride hexahydrate; 0.00003 mol, 85% Phosphoric acid is used as phosphoric acid to make 0.00862 mol. A phosphor having the chemical composition shown in -1 was produced. The X-ray diffraction pattern of this phosphor was identical in crystal structure with that of Ca ₅ (PO ₄ ) ₃ Cl, and it was found that the target crystal phase was formed. The fired solid was pulverized in an agate mortar, and the phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode, and the emission spectrum was measured. Table 1 shows the chromaticity coordinate values x and y calculated from the wavelength of the emission peak, the relative emission intensity, and the emission spectrum.

Calcium chloride dihydrate; 0.0131 mol, magnesium chloride dihydrate; 0.00146 mol, europium chloride hexahydrate; 0.00007 mol were weighed and dissolved in 20 ml of water. To this aqueous solution, 0.00877 mol of 85% phosphoric acid as phosphoric acid was added, and the mixed solution was transferred to a magnetic dish to make the total solution amount to 30 to 40 ml. This solution was heated and dried with stirring. The dried solid was collected and pulverized in an agate mortar. A part of the pulverized product was transferred to an alumina crucible and fired at 1000 ° C. for 2 hours under a nitrogen gas flow containing 4% hydrogen to produce phosphor Ca _4.475 Mg _0.5 Eu _0.025 (PO ₄ ) ₃ Cl. The X-ray diffraction pattern of this phosphor is Ca ₅
It was found that the crystal structure was in agreement with that of (PO ₄ ) ₃ Cl, and the target crystal phase was formed. The fired solid was pulverized in an agate mortar, and the phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode, and the emission spectrum was measured. Table 1 shows the chromaticity coordinate values x and y calculated from the wavelength of the emission peak, the relative emission intensity, and the emission spectrum.

Calcium chloride dihydrate: 0.0138 mol, europium chloride hexahydrate; 0.000283 mol, 85% phosphoric acid was changed to 0.00847 mol as phosphoric acid. A phosphor having the chemical composition shown in -1 was produced. The X-ray diffraction pattern of this phosphor was identical in crystal structure with that of Ca ₅ (PO ₄ ) ₃ Cl, and it was found that the target crystal phase was formed. The fired solid was pulverized in an agate mortar, and the phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode, and the emission spectrum was measured. Table 1 shows the chromaticity coordinate values x and y calculated from the wavelength of the emission peak, the relative emission intensity, and the emission spectrum.

Calcium chloride dihydrate; 0.01327 mol, europium chloride hexahydrate; 0.000552 mol, 85% Phosphoric acid was used as phosphoric acid to make 0.00828 mol. A phosphor having the chemical composition shown in -1 was produced. The X-ray diffraction pattern of this phosphor was identical in crystal structure with that of Ca ₅ (PO ₄ ) ₃ Cl, and it was found that the target crystal phase was formed. The fired solid was pulverized in an agate mortar, and the phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode, and the emission spectrum was measured. Table 1 shows the chromaticity coordinate values x and y calculated from the wavelength of the emission peak, the relative emission intensity, and the emission spectrum.

Calcium chloride dihydrate; 0.01171 mol, europium chloride hexahydrate; 0.00130 mol, 85% Phosphoric acid was used as phosphoric acid to make 0.00781 mol. A phosphor having the chemical composition shown in -1 was produced. The X-ray diffraction pattern of this phosphor was identical in crystal structure with that of Ca ₅ (PO ₄ ) ₃ Cl, and it was found that the target crystal phase was formed. The fired solid was pulverized in an agate mortar, and the phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode, and the emission spectrum was measured. Table 1 shows the chromaticity coordinate values x and y calculated from the wavelength of the emission peak, the relative emission intensity, and the emission spectrum.

Calcium chloride dihydrate; 0.00949 mol, europium nitrate hexahydrate; 0.00
A phosphor having the chemical composition shown in Table 1 was produced in the same manner as in Example 1 except that 237 mol and 85% phosphoric acid was changed to 0.00713 mol as phosphoric acid. The X-ray diffraction pattern of this phosphor was identical in crystal structure with that of Ca ₅ (PO ₄ ) ₃ Cl, and it was found that the target crystal phase was formed. The fired solid was pulverized in an agate mortar, and the phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode, and the emission spectrum was measured. Table 1 shows the chromaticity coordinate values x and y calculated from the wavelength of the emission peak, the relative emission intensity, and the emission spectrum.
(Comparative Example 1)
BaCO ₃ ; 0.0103 mol, basic magnesium carbonate (Mg mole number 0.0103
Mol), and γ-Al ₂ O ₃ ; 0.0570 mol, and Eu ₂ O ₃ ; 0.00057 mol as an element source compound of the luminescent center ion together with pure water in an alumina container and a wet ball mill of beads. After mixing, drying and passing through a nylon mesh, the obtained pulverized mixture was calcined in an alumina crucible by heating at 1500 ° C. for 2 hours under a nitrogen gas flow containing 4% hydrogen. Subsequently, a blue-emitting phosphor Ba _0.9 Eu _0.1 MgAl ₁₀ O ₁₇ was produced by washing with water, drying, and classification. The fired solid was pulverized in an agate mortar, and the phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode, and the emission spectrum was measured. Table 1 shows the chromaticity coordinate values x and y calculated from the wavelength of the emission peak, the relative emission intensity, and the emission spectrum.
(Comparative Example 2)
Calcium chloride dihydrate; 0.00077 mol, barium chloride dihydrate; 0.0070 mol, europium chloride hexahydrate; 0.00004 mol were weighed and dissolved in 20 ml of water. To this aqueous solution, 0.00469 mol of 85% phosphoric acid as phosphoric acid was added, and the mixed solution was transferred to a magnetic dish to make the total solution volume 30-30 ml. This solution was heated and dried with stirring. The dried solid was collected and pulverized in an agate mortar. A part of the pulverized product was transferred to an alumina crucible and fired at 1000 ° C. for 2 hours under a nitrogen gas flow containing 4% hydrogen to produce phosphor Ca _0.5 Ba _4.475 Eu _0.025 (PO ₄ ) ₃ Cl. The X-ray diffraction pattern of this phosphor is (Ba _4.99
It was found that the crystal structure coincided with that of Eu _0.01 ) (PO ₄ ) ₃ Cl. The fired solid was pulverized with an agate mortar, the phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of the GaN-based light emitting diode, and the emission spectrum was measured. Table 1 shows the chromaticity coordinate values x and y calculated from the wavelength of the emission peak, the relative emission intensity, and the emission spectrum.
(Comparative Example 3)
Calcium nitrate tetrahydrate; 0.00165 mol, magnesium nitrate hexahydrate; 0.01495 mol, europium chloride hexahydrate; 0.00008 mol were weighed and dissolved in 20 ml of water. To this aqueous solution, 0.00994 mol of 85% phosphoric acid as phosphoric acid was added, and the mixed solution was transferred to a magnetic dish to make the total solution amount to 30 to 40 ml. This solution is heated and dried with stirring. The dried solid was collected and pulverized in an agate mortar. A portion of this pulverized product was transferred to an alumina crucible and fired at 1000 ° C. for 2 hours under a nitrogen gas flow containing 4% hydrogen to obtain phosphor Ca _0.5.
Mg _4.475 Eu _0.025 (PO ₄ ) ₃ Cl was produced. It was found that the X-ray diffraction pattern of this phosphor was identical in crystal structure with that of Mg ₃ (PO ₄ ) ₂ . The fired solid was pulverized with an agate mortar, the phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of the GaN-based light emitting diode, and the emission spectrum was measured. Table 1 shows the chromaticity coordinate values x and y calculated from the wavelength of the emission peak, the relative emission intensity, and the emission spectrum.

The typical perspective view which shows an example of the light-emitting device which made the film-like fluorescent substance contact the surface emitting type GaN-type diode. It is typical sectional drawing which shows one Example of the light-emitting device of this invention. The typical sectional view showing an example of the surface emitting illumination device of the present invention.

Explanation of symbols

1; second light emitter 2; surface-emitting GaN-based LD
3; Substrate 4; Light emitting device 5; Mount lead 6; Inner lead 7; First light emitter (light emitter of 350 to 415 nm)
8; Resin part containing phosphor in the present invention 9; Conductive wire 10; Mold member 11; Surface-emitting illumination device 12 incorporating a light-emitting element; Holding case 13; Light-emitting device 14;

Claims (11)

In a light-emitting device including a first light-emitting body that generates light of 350 to 415 nm and a second light-emitting body that generates visible light when irradiated with light from the first light-emitting body, the second light-emitting body includes: A light-emitting device comprising a phosphor having a crystal phase having a chemical composition represented by the general formula [1].
(In the above general formula [1], M represents at least one element selected from the group consisting of M g, Sr and Ba, X represents a C l. Further, a is, 0.5 ≦ a ≦ 2, b is a number that satisfies (5-a) × 0.8 ≦ b ≦ 5-a, c is 2.7 ≦ c ≦ 3.3, and d is a number that satisfies 0.9 ≦ d ≦ 1.1. .) The light emitting device according to claim 1, wherein a satisfies 0.5 ≦ a ≦ 1.5. Element M, the light-emitting device according to claim 1 or 2, characterized in that it consists of Mg or Ba. 4. The light emitting device according to claim 1, wherein the first light emitter is a laser diode or a light emitting diode. The light-emitting device according to claim 1, wherein the first light-emitting body is formed using a GaN-based compound semiconductor. 6. The light-emitting device according to claim 1, wherein the first light emitter is a surface-emitting GaN-based laser diode. The light emitting device according to any one of claims 1 to 6, wherein the second light emitter has a film shape. The light emitting device according to claim 7, wherein a film surface of the second light emitter is brought into direct contact with a light emitting surface of the first light emitter. 9. The light emitting device according to claim 1, wherein the second light emitter is obtained by dispersing phosphor powder in a resin. A lighting device comprising the light emitting device according to claim 1. An image display device comprising the light emitting device according to claim 1.