JP4617888B2 - Phosphor, and light emitting device, lighting device, and image display device using the same - Google Patents

Description

The present invention relates to a highly efficient light-emitting device obtained by combining a phosphor that emits light in the near ultraviolet to visible region and a phosphor that absorbs this light and emits visible light having a longer wavelength, and the phosphor itself.
In general, white light essential for display and illumination is obtained by combining light emission of blue, green, and red by the additive mixing principle of light. In the display, in order to efficiently reproduce a wide range of colors on the chromaticity coordinates, the blue, green, and red light emitters must have as high emission intensity as possible and good color purity. In general lighting, depending on the light emission efficiency and application, it is necessary that the color of the illuminated object looks the same as when illuminated by natural light, that is, so-called color rendering is high. Fluorescent lamps, which are typical illuminations, mainly use ultraviolet light with a wavelength of 254 nm as a source of excitation, mixing three types of phosphors that produce 450, 540, and 610 nm light emissions that are sensitive to the human eye. Used to achieve high color rendering lighting. However, in the present situation, phosphors having high emission efficiency have not been developed when the wavelength of excitation light is in the near ultraviolet to visible region. In particular, there is a demand for the development of red phosphors having excellent performance because the emission efficiency of red phosphors is lower than that of blue and green for excitation light in this wavelength range. If any two or three of the 450, 540, and 610 nm light emission can be obtained from one phosphor, the blending process is simplified and the performance is expected to be stable compared to mixing three types of phosphors. It has not been realized.

Various phosphors that emit blue, green, and red light in combination with a light source that emits light in the near ultraviolet to visible region are exemplified in Patent Document 1. Among them, it is described that alkaline earth metal silicate phosphors emit light in blue and red, and Patent Document 2 discloses (Ba, Ca, Sr, Mg) -Si activated by Eu ^2+. In the case of only Ba and Ca in the -O system, light is emitted at 505 nm, and when Sr is added, the light emission wavelength is shifted to 580 nm. Non-Patent Document 1 reports on (Ba, Ca, Sr) ₃ MgSi ₂ O ₈ : Eu, Mn. In Non-Patent Document 2, B
It is described that a ₃ MgSi ₂ O ₈ : Eu, Mn has an emission peak at 442,505,620 nm and the crystal structure is merwinite.
JP-T-2004-505470 Special table 2004-501512 gazette J. et al. Electrochem. Soc, Vol. 115, No7, 733-738 (1968) Appl. Phys. Lett. , Vol. 84, no. 15, 2931-2933 (2004)

  The object is to develop a high-efficiency red light-emitting phosphor and a white phosphor for use in a display or illumination that emits light with high efficiency in combination with a light source emitting near-ultraviolet to visible light.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an alkaline earth silicate phosphor having a new composition and a specific crystal structure enhances red or white light against excitation light in the near ultraviolet to visible region. The present invention was completed by finding that light is emitted efficiently.
Specifically, an M ₂ SiO ₄ type silicate containing Ba and Ca activated by Eu and Mn was found, and the present invention was achieved. In particular, the red phosphor of the present invention has a feature that it emits redness that is felt bright because its emission peak wavelength is in the range of 590-620 nm.

That is, the present invention may have a crystal phase having a chemical composition represented by the following general formula [1], a phosphor, characterized in that emits red to white in wavelength 400nm excitation and its first aspect, 350- In a light emitting device including a first light emitter that generates light of 430 nm and a second light emitter that generates visible light by irradiation of light from the first light emitter, the second light emitter includes: the light-emitting device, wherein the a phosphors as its second aspect.

Eu _a Mn _b M ¹ _c M ² _d M ³ O _e [1]

(Wherein, ^{M 1} is, Ba, Ca, Sr, V , Cr, Fe, Co, Ni, Cu, Zn, Mo, Ru, Pd, Ag, Cd, Sn, Sm, Tm, Yb, W, Re, Os , Ir, Pt, a divalent element selected from the group consisting of Hg, and Pb, Ba, comprising Ca, and more than 85 mol% of at least one element selected from the group consisting of Sr, the total of Ba and Ca The proportion of Ca with respect to the sum of Ba and Ca (molar ratio) is 0.1 or more and 0.9 or less, and M ² is composed of Li, Na, K, Rb, and Cs. A monovalent element selected from the group, a trivalent element selected from the group consisting of B, Al, Ga, In, Ta, Nb, Rh, Y and Sc, and a group consisting of P, Sb and Bi At least selected from the group consisting of pentavalent elements Both are one element. ^{M 3} are, Si, Ge, Zn, and at least one tetravalent element selected from the group consisting of Ti and Hf, the proportion Si is is not less than 80 mol% .a Is 0.02 ≦ a ≦ 0.5 , b is 0.02 ≦ b ≦ 0.6 , c and d are 0 ≦ d / (c + d) ≦ 0.1 , and a, b, c and d are 1.8. ≦ (a + b + c + d) ≦ 2.2, e is a number satisfying 3.6 ≦ e ≦ 4.4.

  According to the present invention, a red or white phosphor having high luminance can be obtained, and a light emitting device having high color rendering properties can be provided.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
The present invention is a phosphor having a crystal phase having a chemical composition of the following general formula [1], a phosphor having a crystal phase having a chemical composition of the following general formula [1], and a phosphor having a crystal phase of 350 to 430 nm. And a light emitting device for irradiating light.

M ¹ in the formula [1] is a divalent element and contains at least one element selected from the group consisting of Ba, Ca, and Sr in an amount of 85 mol% or more, and the ratio of Ca to the total of Ba and Ca. (Molar ratio) is 0.1 or more and 0.9 or less. That is, most or all of them are composed of at least one element selected from the group consisting of Ba, Ca, and Sr. Other divalent elements can be included as long as the performance is not impaired. V, Cr, Fe, Co, Ni, Cu, Zn, Mo, Ru, Pd, Ag, Cd, Sn, Sm, Tm, Yb, W, Re, Os, Ir, Pt, Hg, Pb and the like may be mentioned, and at least one selected from these element groups may be contained in a total amount of 15 mol% or less in M ¹ . Among these, V, Zn, Mo
, Sn, Sm, Tm, Yb, W, Pb, etc. hardly affect the performance, and 15 mo in M ¹ in total
It can be contained at a ratio of 1% or less.

In M ¹ in the formula [1], the ratio (molar ratio) of Ca to the total of Ba and Ca is 0.
Although it is 1 or more and 0.9 or less, it is preferable that it is 0.2 or more as a minimum of the molar ratio of Ca with respect to the sum total of the molar ratio of Ba and Ca from surfaces, such as red or white luminescence intensity, Is preferably 0.8 or less, and the proportion of the total of Ba and Ca in M ¹ is 70.
It is preferably at least mol%, more preferably at least 90 mol%, even more preferably 100 mol%.

M ² in the formula [1] is a monovalent element, represents at least one element selected from the group of trivalent element, and pentavalent element, for example, Li, Na, K, Rb, Cs, Examples include, but are not limited to, B, Al, Ga, In, P, Sb, Bi, Ta, Nb, Rh, and trivalent rare earth elements such as Y and Sc. In the sense of helping the crystallization of divalent element and silicates by solid diffusion within the time the firing of the activation element Eu ²⁺ and Mn ²⁺ in M ^1, 1 monovalent original as elements in M ²
Elementary , trivalent elements , and pentavalent elements can be introduced in small amounts. M ² constituent elements are mainly made of elements replacing the M ¹ site, the ratio of the number of moles of M ² to the total number of moles of M ¹ and M ² d /
(C + d) is 0 ≦ d / (c + d) ≦ 0.2, however, 0 ≦ d / (c + d) ≦ 0.1 is preferable from the viewpoint of red or white emission intensity, and d / (c + d) = 0 is more preferable.

M ³ in the formula [1] represents a tetravalent element group including 90 mol% or more of Si 及 beauty Ge in total, including terms such as red or white light emission intensity, M ³ is a Si least 80 mol% It is preferable that M ³ is made of Si. As tetravalent elements other than Si and Ge,
Zn, Ti, Hf, etc. are mentioned, and these may be included in the range which does not impair the performance in terms of red or white emission intensity.

Z in the formula [1] is at least one element selected from the group consisting of a −1 valent element , a −2 valent element, H, and N, for example, a −2 valent element similar to oxygen. In addition to certain S, Se, and Te, it may be a univalent element such as F, Cl, Br, or I, or may contain an OH group, and some of the oxygen groups are ON groups or N It may be changed to the basis. Further, Z may be contained to such an extent that it has little influence on the fluorescence performance, that is, the impurity level to the total element ratio is about 2 mol% or less. This corresponds to a molar ratio of Z to (Z + oxygen atom) of 0.035 or less. Therefore, the range of f / (e + f), which is the molar ratio of Z to (Z + oxygen atom), is 0 ≦ f / (e + f) ≦ 0.035. From the viewpoint of phosphor performance, f / (e + f) ≦ 0.01 is preferable, and f / (e + f) = 0 is preferable in normal use.

Regarding the Eu molar ratio a in the formula [1], a is a number satisfying 0.001 ≦ a ≦ 0.6, but if the molar ratio a of the luminescent center ion Eu ²⁺ is too small, the emission intensity On the other hand, if the amount is too large, the emission intensity tends to decrease due to a phenomenon called concentration quenching or temperature quenching. Therefore, the lower limit is preferably 0.005 ≦ a, and 0.02 ≦ a is more preferable, and the upper limit is more preferably a ≦ 0.5.

The Mn molar ratio b in the formula [1] is a factor that determines whether to emit red light or white light. When b is 0, a red peak is not obtained and only a blue or blue-green peak is obtained. However, when b takes a small positive value, a red peak appears in the blue and green peaks, and the whole emits white light. When b takes a larger positive value, the blue and green peaks almost disappear, and the red peak. Is the main. The range of b is a red phosphor or a white phosphor, and b is 0 <b ≦ 0.7. Energy Eu ²⁺ phosphor has excited by the irradiation of the excitation light source is moved to Mn ^2+, it believed that Mn ²⁺ is red-emitting, energy mainly by the composition of M ¹ and M ² Since the degree of movement is slightly different, the boundary value of b for switching from the red phosphor to the white phosphor is somewhat different depending on the composition of M ¹ and M ² . Therefore, a good range of b of red light emission and white light emission cannot be strictly distinguished, but as the white phosphor, 0 <b ≦ 0.2 is preferable, 0.02 ≦ b ≦ 0.2 is more preferable, As red fluorescent substance, 0.05 <= b <= 0.7 is preferable and 0.1 <= b <= 0.6 is more preferable.

In the crystal phase Eu _a Mn _b M ¹ _c M ² _d M ³ O _e Z _f of the general formula [1], Eu ²⁺ and Mn ²⁺
Is replaced by the M ¹ is composed of a bivalent element, M ³ is mainly occupied by Si, anion are mainly oxygen, divalent elements M ² is a main element, 1 other than tetravalent element valence element, trivalent element, and consists of pentavalent element, the basic ^{composition, (M 1 + M 2)} , M 3, but the total molar ratio of oxygen atoms are of 2,1,4 respectively Even if some cation deficiency or anion deficiency occurs, there is no significant effect on the fluorescence performance for this purpose. Therefore, when the total molar ratio of M ³ mainly occupied by Si is fixed to 1 in the chemical formula, (M ¹ + M ² ) The molar ratio (a + b + c + d) is in the range of 1.8 ≦ (a + b + c + d) ≦ 2.2, preferably 1.9 or more and 2.1 or less, more preferably (a + b + c + d) = 2. Further, the total molar ratio of the sites on the anion side (e + f) is usually in the range of 3.6 ≦ (e + f) ≦ 4.4, preferably 3.8 or more and 4.2 or less, more preferably E = 4 and f = 0.

The phosphor used in the present invention comprises an M ¹ source, an M ² source, an M ³ source, and Eu and Mn element source compounds as shown in the general formula [1] below ( The mixture prepared by the mixing method of A) or (B) can be produced by heat treatment and baking.
(A) Dry pulverizer such as hammer mill, roll mill, ball mill, jet mill, etc., or pulverization using mortar and pestle, etc. and mixer such as ribbon blender, V-type blender, Henschel mixer, or mortar and pestle Dry mixing method combined with mixing.
(B) Using a pulverizer or a mortar and pestle, etc., add water etc. and mix in a slurry or solution state with a pulverizer, mortar and pestle, or evaporating dish and stirrer, spray drying, heating Wet mixing method that is dried by drying or natural drying.

  Among these mixing methods, in particular, in the element source compound of the activator element, it is preferable to use a liquid medium because it is necessary to uniformly mix and disperse a small amount of the compound, and other elements The latter wet method is also preferred from the viewpoint of obtaining uniform mixing throughout the source compound, and as the heat treatment method, in a heat-resistant container such as a crucible or a tray using a material having low reactivity with the phosphor, Usually, it is made by heating at a temperature of 750 to 1400 ° C., preferably 900 to 1300 ° C., for 10 minutes to 24 hours in a single or mixed atmosphere of a gas such as 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 ionic state (valence) in which the activating element contributes to light emission is selected. In the case of divalent Eu and Mn in the present invention, a neutral or reducing atmosphere such as carbon monoxide, nitrogen, hydrogen, and argon is preferable, but a reducing atmosphere containing carbon monoxide and hydrogen is more preferable. More preferably, carbon is present in the atmosphere. Specifically, it is achieved by heating using a carbon heater furnace, heating using a container such as a carbon crucible in a reducing atmosphere, heating in which carbon beads or the like coexist in the reducing atmosphere, and the like.

Here, as the element source compounds of M ¹ source, M ² source, M ³ source, and activator element, M ¹ , M ² , M ³ , each oxide of the activator element, hydroxide Products, carbonates, nitrates, sulfates, oxalates, carboxylates, halides, etc. Among these, reactivity to composite oxides and non-generation of NOx, SOx, etc. during firing Etc. are selected.
The Ba listed as M ^1, Ca, the Sr, if specific examples thereof M ¹ source compound, as a Ba source _{compound, BaO, Ba (OH) 2} · 8H 2 O, BaCO 3
, Ba (NO ₃ ) ₂ , BaSO ₄ , Ba (OCO) ₂ .2H ₂ O, Ba (OCOCH ₃ ) ₂ , B
aCl _{2 and the} like, and Ca source compounds include CaO, Ca (OH) ₂ , CaCO ₃ , Ca (
NO ₃ ) ₂ · 4H ₂ O, CaSO ₄ · 2H ₂ O, Ca (OCO) ₂ · H ₂ O, Ca (OCOCH ₃ ) ₂ · H ₂ O, CaCl _2, etc. SrO, Sr (OH) ₂ · 8H
₂ O, SrCO ₃ , Sr (NO ₃ ) ₂ , SrSO ₄ , Sr (OCO) ₂ .H ₂ O, Sr (OCO
CH ₃ ) ₂ · 0.5H ₂ O, SrCl _{2 and the} like.

Specific examples of the M ³ source compounds for the Si and Ge mentioned as M ³ include SiO ₂ , H ₄ SiO ₄ , Si (OCOCH ₃ ) _4, etc. Examples of the Ge source compound include GeO ₂ , Ge (OH) ₄ , Ge (OCOCH ₃ ) ₄ , and GeCl ₄ .
Further, with respect to Eu and Mn mentioned as the activation elements, specific examples of the element source compounds are Eu ₂ O ₃ , Eu ₂ (SO ₄ ) ₃ , Eu ₂ (OCO) ₆ , EuCl _2. , EuCl ₃ , Eu (NO ₃ ) ₃ .6H ₂ O, Mn (NO ₃ ) ₂ .6H ₂ O, MnO ₂ , Mn ₂ O ₃ , Mn ₃
Examples include O ₄ , MnO, Mn (OH) ₂ , MnCO ₃ , Mn (OCOCH ₃ ) ₂ .2H ₂ O, Mn (OCOCH ₃ ) ₃ .nH ₂ O, MnCl ₂ .4H ₂ O, and the like.

The inventors of the present application have found that a phosphor having a specific crystal structure has a particularly high emission intensity in addition to the above composition range, and completed the present invention. The crystal structure is generally defined using a crystal system or a space group, but the crystal phase in the present invention has a crystal system and a space due to a crystal structure distortion (subtle structural change) accompanying a change in composition. Because the group changes, it is not possible to define a unique structure. Therefore, an X-ray diffraction pattern necessary for specifying a crystal phase contributing to light emission is disclosed. In order to specify that the crystal structures of the two compounds are usually the same based on the X-ray diffraction pattern, the angles (2θ) of about six diffraction peaks including the strongest diffraction peak based on the crystal structure should be the same. However, when the constituent element ratios are different as in the compound of the present invention, the angle of the diffraction peak shifts even if the crystal structure is the same, and therefore the specific angle of the diffraction peak cannot be defined as a numerical value. Accordingly, the inventors focused on the diffraction peak plane distance calculated using the Bragg equation, and specified the diffraction peak angle range by the following display method.
Bragg's equation d = λ / {2 × sin (θ)} (Equation 1)
θ = arcsin {λ / (2 × d)} (Formula 2)
d: Surface spacing (Å)
θ: Bragg angle (°)
λ: CuKα X-ray wavelength = 1.54184
(Equation 2) is a variation of (Equation 1). If the interplanar spacing range of the reference diffraction peak is defined as 4.17 ° to 3.95 °, the range of the diffraction angle (2θ) is 21.3 ° to 22.5 ° from (Equation 2).

From the observed angle (θ0) of the reference diffraction peak, the plane spacing (d0) of the reference diffraction peak is expressed by (Expression 3) below from (Expression 1).
d0 = λ / {2 × sin (θ0)} (Expression 3)
Five peaks other than the reference diffraction peak are defined as P1, P2, P3, P4, and P5 from the low angle side, and the angle ranges in which the respective peaks appear are sequentially defined as R1, R2, R3, R4, and R5.
The angle range R1 in which P1 appears is determined as follows. When the diffraction plane has a plane spacing of 0.720 times the plane spacing (d0) derived from the reference diffraction peak, and the deviation of the plane spacing due to structural distortion is 1.5%, the starting angle (R1s) of the angle range R1 The end angle (R1e) is derived from (Equation 1) as follows.

R1s: 2 × arcsin {λ / (2 × d0 × 0.720 × 1.015)}
R1e: 2 × arcsin {λ / (2 × d0 × 0.720 × 0.985)}
Substituting (Equation 3) for each,
R1s: 2 × arcsin {sin (θ0) / (0.720 × 1.015)}
R1e: 2 × arcsin {sin (θ0) / (0.720 × 0.985)}
It becomes.

Similarly, the angle range in which P2, 3, 4, and 5 appear is defined as 0.698 times, 0.592 times, 0.572 times, and 0.500 times the plane spacing derived from the reference diffraction peak. Assuming that the deviation of the surface interval due to the strain of 1.5% is uniform, each angle range is as follows.
R2s: 2 × arcsin {sin (θ0) / (0.698 × 1.015)}
R2e: 2 × arcsin {sin (θ0) / (0.698 × 0.985)}
R3s: 2 × arcsin {sin (θ0) / (0.592 × 1.015)}
R3e: 2 × arcsin {sin (θ0) / (0.592 × 0.985)}
R4s: 2 × arcsin {sin (θ0) / (0.572 × 1.015)}
R4e: 2 × arcsin {sin (θ0) / (0.572 × 0.985)}
R5s: 2 × arcsin {sin (θ0) / (0.500 × 1.015)}
R5e: 2 × arcsin {sin (θ0) / (0.500 × 0.985)}
That is, it can be confirmed that the specific crystal structure referred to in the present invention exists by confirming that each peak from the reference peaks P0 to P5 appears in the above angle range in the obtained X-ray diffraction measurement result. This crystal phase is a crystal phase different from merwinite described in Non-Patent Document 1 and Non-Patent Document 2. The angle ranges R1 to R5 are more preferably as follows, in which the deviation of the interplanar spacing accompanying the structural strain is uniformly 1.0%.

R1: 2 × arcsin {sin (θ0) / (0.720 × 1.010)} to 2 × arcsin {sin (θ0) / (0.720 × 0.990)}
R2: 2 × arcsin {sin (θ0) / (0.698 × 1.010)} to 2 × arcsin {sin (θ0) / (0.698 × 0.990)}
R3: 2 × arcsin {sin (θ0) / (0.592 × 1.010)} to 2 × arcsin {sin (θ0) / (0.592 × 0.990)}
R4: 2 × arcsin {sin (θ0) / (0.572 × 1.010)} to 2 × arcsin {sin (θ0) / (0.572 × 0.990)}
R5: 2 × arcsin {sin (θ0) / (0.500 × 1.010)} to 2 × arcsin {sin (θ0) / (0.500 × 0.990)}
The method for producing the crystalline phase that characterizes the present invention is not limited, but for example, a raw material having a small particle size of 10 μm or less is used. The desired crystal phase can be obtained by the absence of local agglomerates that appear to be inhomogeneous and by firing in a reducing atmosphere using a carbon crucible.

Selected Ba, Sr, and from C a or Ranaru group since it became clear that contain more than mentioned manner phosphor having high emission intensity obtained by the present invention certain crystal phase were all above It can be said that it is a phosphor having an alkaline earth silicate crystal phase containing at least one element and including the specific crystal phase described above.
In the present invention, the first light emitter that irradiates the phosphor with light generates light having a wavelength of 350 to 430 nm. Preferably, a light emitter that generates light having a peak wavelength in the wavelength range of 350 to 430 nm is used. Specific examples of the first light emitter include a light emitting diode (LED) or a laser diode (LD). A laser diode is more preferable because it consumes less power. Among them, GaN LEDs and LDs using GaN compound semiconductors are preferable. 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, those having an In _X Ga _Y N light-emitting layer are particularly preferable because the emission intensity is very strong, and in GaN-based LDs, multiple quantum of In _X Ga _Y N layer and GaN layer The well structure is particularly preferable because the emission intensity is very strong. 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. These light-emitting layer GaN-based LED is, p layer, n layer, electrode, and that where the substrate as a basic component, Al _X Ga _Y N layer of the light-emitting layer n-type and p-type, GaN layer, or In _X Those having a heterostructure sandwiched between Ga _Y N layers and 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, 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 denotes a film-like second light emitter having the phosphor, 2 denotes a surface-emitting GaN-based LD as the first light emitter, and 3 denotes a substrate. In order to create a state in which they are in contact with each other, the LD 2 and the second light emitter 1 may be formed separately, and their surfaces may be brought into contact with each other by an adhesive or other means, or on the light emitting surface of the LD 2. The second light emitter may be formed (molded). 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 the resin that can be used in this case include various resins such as silicon resin, epoxy resin, polyvinyl resin, polyethylene resin, polypropylene resin, and polyester resin, which are preferable in terms of good dispersibility of the phosphor powder. Is a silicon resin or an epoxy resin. 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 generates 350-430 nm light, and the phosphor absorbs 350-430 nm light emitted from the light-emitting element. In addition, the phosphor having a good color rendering property and capable of generating high-intensity visible light regardless of the use environment, and the phosphor having the crystal phase of the present invention constituting the light-emitting device has a wavelength of 350 to 430 nm. By emitting light from the first light-emitting body that generates the light, light is emitted in a wavelength region representing red or white. The light-emitting device of the present invention is suitable for a light source such as a backlight source, a light source such as a traffic light, an image display device such as a color liquid crystal display, and a lighting device such as a surface light source.

  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 (350-430 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 (350-430 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. (350-430 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-impermeable such as a white smooth surface. The device 13 is arranged with a power supply and a circuit (not shown) for driving the light emitting device 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, by driving the surface emitting illumination device 11 and applying a voltage to the first light emitter of the light emitting element 13, light of 350 to 430 nm is emitted, 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.

Ba (NO ₃ ) ₂ aqueous solution, Ca (NO ₃ ) ₂ · 4H ₂ O aqueous solution, Eu (NO ₃ ) ₃ · 6H ₂ O aqueous solution, Mn (NO ₃ ) ₂ · 6H ₂ O aqueous solution, and colloidal Silica (SiO ₂ ) suspensions (Ba (NO ₃ ) ₂ , Ca (NO ₃ ) ₂ .4H ₂ O, Eu (NO ₃ ) ₃ .6H ₂ O, Mn (NO ₃ ) ₂ .6H ₂ O, SiO ₂ molar ratio of 0.64: 0.96: 0.2: 0.2: 1) was mixed in a platinum container, dried and heated at 1050 ° C. for 2 hours under a nitrogen gas flow containing 4% hydrogen. The phosphor Ba _0.64 Ca _0.96 Eu _0.2 Mn _0.2 SiO ₄ (phosphor used for the second light emitter) was manufactured. The emission spectrum was measured when this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode. Table 1 shows the wavelength of the emission peak, the intensity of the emission peak when the intensity of the emission peak of Comparative Example 2 described later is 100, and the half-value width. This phosphor has a sufficiently wide half-value width, gives good color rendering properties, and emits a shallow red light having a peak wavelength in the range of 590 to 620 nm.

(Comparative Example 1)
Ba (NO ₃ ) ₂ aqueous solution, Ca (NO ₃ ) ₂ .4H ₂ O aqueous solution, Eu (NO ₃ ) ₃ .6H ₂ O aqueous solution, and colloidal silica (SiO ₂ ) suspension (Ba (NO ₂ ) ₃ ) ₂ , Ca (N
The molar ratio of O ₃ ) ₂ · 4H ₂ O, Eu (NO ₃ ) ₃ · 6H ₂ O, SiO ₂ is 0.72: 1.08:
The phosphor Ba _0.72 Ca _1.08 Eu _0.2 SiO ₄ was produced in the same manner as in Example 1 except that 0.2: 1) was used as the stock solution. The emission spectrum was measured when this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode. Table 1 shows the wavelength, relative intensity, and half-value width of the emission peak. It can be seen that when Mn is not added in the composition of Example 1, no red peak appears.

(Comparative Example 2)
An aqueous solution of Ba (NO ₃ ) _2, an aqueous solution of Eu (NO ₃ ) ₃ .6H ₂ O, an aqueous solution of Mn (NO ₃ ) ₂ .6H ₂ O, and a suspension of colloidal silica (SiO ₂ ) (Ba (NO ₃ ) ₂ , Eu (N
The molar ratio of O ₃ ) ₃ · 6H ₂ O, Mn (NO ₃ ) ₂ · 6H ₂ O, SiO ₂ is 1.6: 0.2: 0.
Phosphor Ba _1.6 was obtained in the same manner as in Example 1 except that 2: 1) was used as the stock solution.
Eu _0.2 Mn _0.2 SiO ₄ was produced. The emission spectrum was measured when this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode. Table 1 shows the wavelength, relative intensity, and half-value width of the emission peak. It can be seen that the red peak does not appear when Ca is not added in the composition of Example 1.

(Comparative Example 3)
An aqueous solution of Ca (NO ₃ ) ₂ .4H ₂ O, an aqueous solution of Eu (NO ₃ ) ₃ .6H ₂ O, Mn (NO ₃
) (Suspension of SiO ₂₎ (Ca (NO ₃₎ an aqueous solution of ₂ · 6H ₂ O and colloidal silica, ₂
-4H ₂ O, Eu (NO ₃ ) ₃ · 6H ₂ O, Mn (NO ₃ ) ₂ · 6H ₂ O, SiO ₂ molar ratio 1.6: 0.2: 0.2: 1) A phosphor Ca _1.6 Eu _0.2 Mn _0.2 SiO ₄ was produced in the same manner as in Example 1 except that the above was used. The emission spectrum was measured when this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode. Table 1 shows the wavelength, relative intensity, and half-value width of the emission peak. It can be seen that the red peak does not appear when Ba is not added in the composition of Example 1.

Ba (NO ₃ ) ₂ aqueous solution, Ca (NO ₃ ) ₂ · 4H ₂ O aqueous solution, Eu (NO ₃ ) ₃ · 6H ₂ O aqueous solution, Mn (NO ₃ ) ₂ · 6H ₂ O aqueous solution, and colloidal Silica (SiO ₂ ) suspensions (Ba (NO ₃ ) ₂ , Ca (NO ₃ ) ₂ .4H ₂ O, Eu (NO ₃ ) ₃ .6H ₂ O, Mn (NO ₃ ) ₂ .6H ₂ O, The phosphor Ba _0.84 Ca _0.56 Eu _0.3 Mn was prepared in the same manner as in Example 1 except that the molar ratio of SiO ₂ was 0.84: 0.56: 0.3: 0.3: 1). _0.3 SiO ₄ was produced. 4 which is the dominant wavelength in the ultraviolet region of GaN-based light-emitting diodes
The emission spectrum was measured when the phosphor was excited at 00 nm. Table 1 shows the wavelength, relative intensity, and half-value width of the emission peak. This phosphor has a sufficiently wide half-value width, gives good color rendering properties, and emits a shallow red light having a peak wavelength in the range of 590 to 620 nm.

Ba (NO ₃ ) ₂ aqueous solution, Ca (NO ₃ ) ₂ · 4H ₂ O aqueous solution, Eu (NO ₃ ) ₃ · 6H ₂ O aqueous solution, Mn (NO ₃ ) ₂ · 6H ₂ O aqueous solution, and colloidal Silica (SiO ₂ ) suspensions (Ba (NO ₃ ) ₂ , Ca (NO ₃ ) ₂ .4H ₂ O, Eu (NO ₃ ) ₃ .6H ₂ O, Mn (NO ₃ ) ₂ .6H ₂ O, the molar ratio of SiO ₂ is 0.75: 0.5: 0.3: 0.45: except using as 1) was charged stock, phosphor Ba _0.75 in the same manner as in example 1 Ca _0.5 Eu _0.3 Mn _0.45 SiO ₄ was produced. 4 which is the dominant wavelength in the ultraviolet region of GaN-based light-emitting diodes
The emission spectrum was measured when the phosphor was excited at 00 nm. FIG. 4 shows the emission spectrum. In order to remove the influence of the excitation light source on the emission spectrum, measurement is performed by introducing a filter that cuts light of 420 nm or less. Table 1 shows the wavelength, relative intensity, and half-value width of the emission peak. This phosphor has a sufficiently wide half-value width, gives good color rendering properties, and emits a shallow red light having a peak wavelength in the range of 590 to 620 nm.

Ba (NO ₃ ) ₂ aqueous solution, Ca (NO ₃ ) ₂ · 4H ₂ O aqueous solution, Eu (NO ₃ ) ₃ · 6H ₂ O aqueous solution, Mn (NO ₃ ) ₂ · 6H ₂ O aqueous solution, and colloidal Silica (SiO ₂ ) suspensions (Ba (NO ₃ ) ₂ , Ca (NO ₃ ) ₂ .4H ₂ O, Eu (NO ₃ ) ₃ .6H ₂ O, Mn (NO ₃ ) ₂ .6H ₂ O, The phosphor Ba _1.11 Ca _0.74 Eu _0.06 Mn was prepared in the same manner as in Example 1 except that the molar ratio of SiO ₂ was 1.11: 0.74: 0.06: 0.09: 1). _0.09 SiO ₄ was produced. The emission spectrum was measured when this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode. FIG. 5 shows the emission spectrum. Table 2 shows the maximum peak of this phosphor when the chromaticity coordinate x value, the y value, the wavelength of the maximum peak, and the intensity of the maximum peak of the phosphor of Comparative Example 5 described later are 100. Intensity (hereinafter referred to as the maximum peak relative intensity), the ratio of the intensity at 600 nm to the intensity of the maximum peak, which serves as a guide to know how much red component is present in the emission spectrum, and the half width of the peak group Indicates. It can be seen that the blue, green and red components are sufficiently present, the spectral width is very wide, and the white light emission has a high color rendering property.

  Note that the maximum peak refers to the peak with the highest intensity when there are a plurality of peaks in the emission spectrum, and refers to that in the case of a single peak. Further, the half width of the peak group is a guideline for knowing how widely the emission spectrum is distributed and how high the color rendering is, and as shown in FIG. It is defined as the sum of the widths of the wavelength regions having half or more intensity.

Ba (NO ₃ ) ₂ aqueous solution, Ca (NO ₃ ) ₂ · 4H ₂ O aqueous solution, Eu (NO ₃ ) ₃ · 6H ₂ O aqueous solution, Mn (NO ₃ ) ₂ · 6H ₂ O aqueous solution, and colloidal Silica (SiO ₂ ) suspensions (Ba (NO ₃ ) ₂ , Ca (NO ₃ ) ₂ .4H ₂ O, Eu (NO ₃ ) ₃ .6H ₂ O, Mn (NO ₃ ) ₂ .6H ₂ O, The phosphor Ba _0.68 Ca _1.02 Eu _0.2 Mn was prepared in the same manner as in Example 1 except that the molar ratio of SiO ₂ was 0.68: 1.02: 0.2: 0.1: 1). _0.1 SiO ₄ was produced. 4 which is the dominant wavelength in the ultraviolet region of GaN-based light-emitting diodes
The emission spectrum was measured when the phosphor was excited at 00 nm. Table 2 shows the x value, y value, wavelength of the maximum peak, relative intensity of the maximum peak, the ratio of the intensity at 600 nm to the intensity of the maximum peak, and the half width of the peak group. It can be seen that the red component is sufficiently present, the spectral width is very wide, and the white light emission has high color rendering properties.

(Comparative Example 4)
Ba (NO ₃ ) ₂ aqueous solution, Ca (NO ₃ ) ₂ .4H ₂ O aqueous solution, Eu (NO ₃ ) ₃ .6H ₂ O aqueous solution, and colloidal silica (SiO ₂ ) suspension (Ba (NO ₂ ) ₃ ) ₂ , Ca (N
The molar ratio of O ₃ ) ₂ · 4H ₂ O, Eu (NO ₃ ) ₃ · 6H ₂ O, SiO ₂ is 0.72: 1.08:
The phosphor Ba _0.72 Ca _1.08 Eu _0.2 SiO ₄ was produced in the same manner as in Example 1 except that 0.2: 1) was used as the stock solution. The emission spectrum was measured when this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode. Table 2 shows the x value, y value, wavelength of the maximum peak, relative intensity of the maximum peak, the ratio of the intensity at 600 nm to the intensity of the maximum peak, and the half width of the peak group. It can be seen that when Mn is not added in the composition of Example 5, a white spectrum is not obtained.

(Comparative Example 5)
An aqueous solution of Ba (NO ₃ ) _2, an aqueous solution of Eu (NO ₃ ) ₃ .6H ₂ O, an aqueous solution of Mn (NO ₃ ) ₂ .6H ₂ O, and a suspension of colloidal silica (SiO ₂ ) (Ba (NO ₃ ) ₂ , Eu (N
The molar ratio of O ₃ ) ₃ · 6H ₂ O, Mn (NO ₃ ) ₂ · 6H ₂ O, SiO ₂ is 1.7: 0.2: 0.
Phosphor Ba _1.7 as in Example 1 except that 1: 1) is used as the stock solution.
Eu _0.2 Mn _0.1 SiO ₄ was produced. The emission spectrum was measured when this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode. Table 2 shows the x value, y value, wavelength of the maximum peak, relative intensity of the maximum peak, the ratio of the intensity at 600 nm to the intensity of the maximum peak, and the half width of the peak group. It can be seen that the white spectrum is not obtained unless Ca is added in the composition of Example 5.

(Comparative Example 6)
An aqueous solution of Ca (NO ₃ ) ₂ .4H ₂ O, an aqueous solution of Eu (NO ₃ ) ₃ .6H ₂ O, Mn (NO ₃
) (Suspension of SiO ₂₎ (Ca (NO ₃₎ an aqueous solution of ₂ · 6H ₂ O and colloidal silica, ₂
· 4H ₂ O, Eu (NO ₃ ) ₃ · 6H ₂ O, Mn (NO ₃ ) ₂ · 6H ₂ O, SiO ₂ molar ratio 1.7: 0.2: 0.1: 1) A phosphor Ca _1.7 Eu _0.2 Mn _0.1 SiO ₄ was produced in the same manner as in Example 1 except that the above was used. The emission spectrum was measured when this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode. Table 2 shows the x value, y value, wavelength of the maximum peak, relative intensity of the maximum peak, the ratio of the intensity at 600 nm to the intensity of the maximum peak, and the half width of the peak group. It can be seen that the white spectrum is not obtained unless Ba is added in the composition of Example 5.

Ba (NO ₃ ) ₂ aqueous solution, Ca (NO ₃ ) ₂ · 4H ₂ O aqueous solution, Eu (NO ₃ ) ₃ · 6H ₂ O aqueous solution, Mn (NO ₃ ) ₂ · 6H ₂ O aqueous solution, and colloidal Silica (SiO ₂ ) suspensions (Ba (NO ₃ ) ₂ , Ca (NO ₃ ) ₂ .4H ₂ O, Eu (NO ₃ ) ₃ .6H ₂ O, Mn (NO ₃ ) ₂ .6H ₂ O, The phosphor Ba _0.93 Ca _0.62 Eu _0.3 Mn was prepared in the same manner as in Example 1 except that the molar ratio of SiO ₂ was 0.93: 0.62: 0.3: 0.15: 1). _0.15 SiO ₄ was produced. The emission spectrum was measured when this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode. Table 2 shows the x value, y value, wavelength of the maximum peak, relative intensity of the maximum peak, the ratio of the intensity at 600 nm to the intensity of the maximum peak, and the half width of the peak group. It can be seen that the red component is sufficiently present, the spectral width is very wide, and the white light emission has high color rendering properties.

Ba (NO ₃ ) ₂ aqueous solution, Ca (NO ₃ ) ₂ .4H ₂ O aqueous solution, Zn (NO ₃ ) ₂ .6H ₂ O aqueous solution, Eu (NO ₃ ) ₃ .6H ₂ O aqueous solution, Mn ( NO ₃ ) ₂ · 6H ₂ O aqueous solution and colloidal silica (SiO ₂ ) suspension (Ba (NO ₃ ) ₂ , Ca (NO ₃ ) ₂ · 4H ₂ O, Zn (NO ₃ ) ₂ · 6H ₂ O, Eu (NO ₃ ) ₃ · 6H ₂ O, Mn (NO ₃ ) ₂ · 6H ₂ O, S
Phosphor Ba _1.133 Ca in the same manner as in Example 1 except that the molar ratio of iO ₂ is 1.133: 0.378: 0.189: 0.2: 0.1: 1). _0.378 Zn _0.189 Eu _0.2 Mn _0.1 SiO ₄ was produced. The emission spectrum was measured when this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode. Table 2 shows the x value, y value, wavelength of the maximum peak, relative intensity of the maximum peak, the ratio of the intensity at 600 nm to the intensity of the maximum peak, and the half width of the peak group. It can be seen that the red component is sufficiently present, the spectral width is very wide, and the white light emission has high color rendering properties.

The molar ratio of BaCO ₃ , CaCO ₃ , Eu ₂ O ₃ , MnCO ₃ .nH ₂ O, SiO ₂ is 1.08.
: 0.72: 0.075: 0.05: 1 and weighed NH ₄ C as flux
1 was added and mixed with a ball mill for 1 hour. The prepared powder is put in an alumina crucible, and the whole crucible is put in a carbon crucible and heated at 1200 ° C. for 6 hours under a nitrogen gas flow containing 4% hydrogen to obtain phosphor Ba _1.08 Ca _0.72 Eu _0.15 Mn _0.05 SiO ₄ . Manufactured. X-ray diffraction measurement of this phosphor was performed under the following conditions. Using a Bragg-Brentano type powder X-ray diffractometer comprising a CuKα X-ray source optically adjusted so that the diffraction angle error within the scanning range is Δ2θ = 0.05 ° or less, and the diffraction angle error due to sample eccentricity is Powder X-ray diffraction measurement was performed under the condition that an angle reproducibility of Δ2θ = 0.05 ° or less was guaranteed using 111 peaks of standard silicon. Also, the divergence angle of the divergence slit is adjusted so that the X-ray irradiation width does not exceed the width of the sample during measurement, and the diffraction peak position (peak top) and diffraction intensity (height) are the values of the measurement results in the fixed slit mode. I read. FIG. 7 shows the results of X-ray diffraction measurement. Table 3 shows that the obtained phosphor satisfies the conditions described in claim 6, and it was confirmed that the phosphor contained the specific phase described above. FIG. 8 shows an emission spectrum when this phosphor is excited at 400 nm, which is the dominant wavelength in the near ultraviolet region of the GaN-based light emitting diode. In order to remove the influence of the excitation light source on the emission spectrum, light of 420 nm or less is cut. Table 4 shows the chromaticity coordinates x and y values, emission peak wavelength, and emission peak intensity of this phosphor.

The molar ratio of BaCO ₃ , CaCO ₃ , Eu ₂ O ₃ , MnCO ₃ .nH ₂ O, SiO ₂ is 1.35.
: Phosphor Ba _1.35 Ca _0.45 Eu _0.15 Mn _0.05 SiO ₄ was obtained in the same manner as in Example 8 except that the weight was adjusted to 0.45: 0.075: 0.05: 1. Table 3 shows the X-ray diffraction measurement results, but this example satisfies the conditions of claim 6. FIG. 8 shows the emission spectrum, and Table 4 summarizes the characteristics.

The molar ratio of BaCO ₃ , CaCO ₃ , SrCO ₃ , Eu ₂ O ₃ , MnCO ₃ .nH ₂ O, SiO ₂ is 1.20: 0.4: 0.2: 0.075: 0.05: 1. A phosphor Ba _1.20 Ca _0.4 Sr _0.2 Eu _0.15 Mn _0.05 SiO ₄ was obtained in the same manner as in Example 8 except that the amount was measured.
Table 3 shows the X-ray diffraction measurement results, but this example satisfies the conditions of claim 6. FIG. 8 shows the emission spectrum, and Table 4 summarizes the characteristics.

The molar ratio of BaCO ₃ , CaCO ₃ , SrCO ₃ , Eu ₂ O ₃ , MnCO ₃ .nH ₂ O, SiO ₂ is 1.08: 0.36: 0.36: 0.075: 0.05: 1. A phosphor Ba _1.08 Ca _0.36 Sr _0.36 Eu _0.15 Mn _0.05 SiO ₄ was obtained in the same manner as in Example 8 except that the measurement was performed as described above. Table 3 shows the X-ray diffraction measurement results, but this example satisfies the conditions of claim 6. FIG. 8 shows the emission spectrum, and Table 4 summarizes the characteristics.

The figure which shows an example of the light-emitting device which made the film-like fluorescent substance contact or shape | mold to the surface emitting type GaN-type diode. It is typical sectional drawing which shows one Example of the light-emitting device comprised from the fluorescent substance in this invention, and a 1st light-emitting body (350-430 nm light-emitting body). The typical sectional view showing an example of the surface emitting illumination device of the present invention. The emission spectrum of the phosphor of Example 3 when irradiated with light having a wavelength of 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode. The emission spectrum of the phosphor of Example 4 when irradiated with light of 400 nm, which is the dominant wavelength in the ultraviolet region of the GaN-based light emitting diode. The figure which showed the method of measuring the half width of a peak group X-ray diffraction measurement results The emission spectrum of the phosphor of Example 8 when irradiated with light having a wavelength of 400 nm which is the dominant wavelength in the ultraviolet region of the GaN-based light emitting diode.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 2nd light-emitting body 2 Surface emitting type GaN-type LD
3 Substrate 4 Light emitting device 5 Mount lead 6 Inner lead 7 First light emitter (light emitter of 350 to 430 nm)
DESCRIPTION OF SYMBOLS 8 Resin part containing fluorescent substance in the present invention 9 Conductive wire 10 Mold member 11 Surface emitting illumination device incorporating light emitting element 12 Holding case 13 Light emitting device 14 Diffusion plate

Claims (13)

It has a crystal phase having a chemical composition represented by the following general formula [1], a phosphor, characterized in that emits red to white in wavelength 400nm excitation.
Eu _a Mn _b M ¹ _c M ² _d M ³ O _e [1]
(Wherein, ^{M 1} is, Ba, Ca, Sr, V , Cr, Fe, Co, Ni, Cu, Zn, Mo, Ru, Pd, Ag, Cd, Sn, Sm, Tm, Yb, W, Re, Os , Ir, Pt, a divalent element selected from the group consisting of Hg, and Pb, Ba, comprising Ca, and more than 85 mol% of at least one element selected from the group consisting of Sr, the total of Ba and Ca The proportion of Ca with respect to the sum of Ba and Ca (molar ratio) is 0.1 or more and 0.9 or less, and M ² is composed of Li, Na, K, Rb, and Cs. A monovalent element selected from the group, a trivalent element selected from the group consisting of B, Al, Ga, In, Ta, Nb, Rh, Y and Sc, and a group consisting of P, Sb and Bi At least selected from the group consisting of pentavalent elements Both are one element. ^{M 3} are, Si, Ge, Zn, and at least one tetravalent element selected from the group consisting of Ti and Hf, the proportion Si is is not less than 80 mol% .a Is 0.02 ≦ a ≦ 0.5 , b is 0.02 ≦ b ≦ 0.6 , c and d are 0 ≦ d / (c + d) ≦ 0.1 , and a, b, c and d are 1.8. ≦ (a + b + c + d) ≦ 2.2, e is a number satisfying 3.6 ≦ e ≦ 4.4. Wherein in the chemical composition of the general formula [1], 0.8 der following ratio (molar ratio) of 0.2 or more Ca to the sum of Ba and Ca in ^{M 1} is, an ^{M 3} is Si, a , B, c and d are 1.9 ≦ (a + b + c + d) ≦ 2.1, e is 3 . The phosphor according to claim 1, wherein the number satisfies 8 ≦ e ≦ 4.2 . M so that the phosphor satisfies the chemical composition of the general formula [1]. ¹ Source, M ² Source, M ³ 3. The phosphor according to claim 1, wherein the phosphor is produced by mixing an element source of Eu and Mn as a source and an activating element, and firing the mixture in a reducing atmosphere. The phosphor according to any one of claims 1 to 3 , which emits white light. The phosphor according to any one of claims 1 to 3 , which emits red light. A phosphor-containing resin, wherein the phosphor according to any one of claims 1 to 5 is dispersed in a resin. In a light-emitting device including a first light-emitting body that generates light of 350 to 430 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 the phosphor according to any one of claims 1 to 5 . The light emitting device according to claim 7 , wherein the first light emitter is a laser diode or a light emitting diode. The light emitting device according to claim 7 or 8, characterized in that a GaN-based compound semiconductor as the first luminous body. The light emitting device according to any one of claims 7-9, characterized in that emits white light. The light emitting device according to any one of claims 7-9, characterized in that emits red light. Lighting apparatus characterized by having a light-emitting device according to any one of claims 7-11. The image display apparatus characterized by having a light-emitting device according to any one of claims 7-11.

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