TWI394815B - Phosphor composition and method for producing the same, and light-emitting device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light-emitting device which emits a high luminous flux of high color rendering properties, especially, a light-emitting device which emits warm white light.SOLUTION: The light-emitting device includes a luminous element and a phosphor layer. The luminous element is a blue luminous element that emits light which has the luminescence peak in a wavelength region of 440 nm or more and less than 500 nm. The phosphor layer includes: a green phosphor which contains Euor Ceas the emission major ions; and a red phosphor of a nitride or an oxynitride containing Euas the emission major ions. The green phosphor and the red phosphor emit light by being excited by the light emitted by the blue luminous element. The light-emitting device outputs light which includes light components emitted from the green phosphor, the red phosphor and the blue luminous element. The green phosphor has the excitation peak at the shorter wavelength side than the excitation wavelength which is the peak of the light emitted by the blue luminous element. The red phosphor is a nitride-aluminosilicate-based red phosphor.

Description

Phosphor composition, method for producing the same, and light-emitting device using the same

The present invention relates to a novel phosphor composition, a method of manufacturing the same, and a light-emitting device using the same; the phosphor composition can be applied to, for example, a white light-emitting diode (hereinafter, referred to as white) Various light-emitting devices such as LEDs, and the present invention relates in particular to a phosphor composition which is excited by near-ultraviolet light, violet or blue light to emit warm orange or red light.

Fluoride-based phosphors are known as follows. Such a nitride phosphor can be excited by ultraviolet light to near-ultraviolet light to purple-blue light, and emits warm-colored visible light having a light-emitting peak in a wavelength region of 580 nm or more and less than 660 nm, and thus is known to be applicable to, for example, white light. A light source such as an LED light source.

(1) M ₂ Si ₅ N ₈ :Eu ²⁺ (refer to Japanese Patent Laid-Open Publication No. 2003-515665)

(2) MSi ₇ N ₁₀ :Eu ²⁺ (refer to Japanese Patent Laid-Open Publication No. 2003-515665)

(3) M ₂ Si ₅ N ₈ : Ce ³⁺ (refer to Japanese Laid-Open Patent Publication No. 2002-322474)

(4) Ca _1.5 Al ₃ Si ₉ N ₁₆ :Ce ³⁺ (refer to Japanese Laid-Open Patent Publication No. 2003-203504)

(5) Ca _1.5 Al ₃ Si ₉ N ₁₆ :Eu ²⁺ (refer to Japanese Laid-Open Patent Publication No. 2003-124527)

(6) CaAl ₂ Si ₁₀ N ₁₆ :Eu ²⁺ (refer to Japanese Laid-Open Patent Publication No. 2003-124527)

(7) Sr _1.5 Al ₃ Si ₉ N ₁₆ :Eu ²⁺ (refer to Japanese Laid-Open Patent Publication No. 2003-124527)

(8) MSi ₃ N ₅ :Eu ²⁺ (refer to Japanese Laid-Open Patent Publication No. 2003-206481)

(9) M ₂ Si ₄ N ₇ :Eu ²⁺ (refer to Japanese Laid-Open Patent Publication No. 2003-206481)

(10) CaSi ₆ AlON ₉ :Eu ²⁺ (refer to Japanese Laid-Open Patent Publication No. 2003-206481)

(11) Sr ₂ Si ₄ AlON ₇ :Eu ²⁺ (refer to Japanese Laid-Open Patent Publication No. 2003-206481)

(12) CaSiN ₂ :Eu ²⁺ (cf. SS Lee, S. Lim, SS Sun and JF Wager, Proceedings of SPIE-the International Society for OptiCal Engineering, Vol. 3241 (1997), p. 75-83).

Here, the above M represents at least one of alkaline earth metal elements (Mg, Ca, Sr, Ba) or zinc (Zn).

In the conventional nitride phosphor, a nitride or a metal of the element M, a nitride of niobium and/or a nitride of aluminum are used as a raw material of a phosphor precursor, and an element containing an emission center ion is mainly used. The compounds are produced by reacting together in a nitriding gas atmosphere. Further, conventional light-emitting devices are constructed using such a nitride phosphor.

However, since the requirements for the above-described light-emitting device are diversified year by year, it is expected that a novel phosphor different from the above-described conventional nitride phosphor can be obtained. In particular, in the above-mentioned warm color luminescent component, in which a luminescent device having a large amount of red luminescent component is in high demand, there is a strong expectation for its development, but there are few phosphor materials currently applicable thereto. Therefore, development of novel phosphor materials and novel light-emitting devices having a large amount of warm-colored light-emitting components is expected.

Moreover, in the conventional method for producing a nitride phosphor, it is difficult to obtain and manufacture a high-purity material, and an alkaline earth metal nitride or an alkaline earth metal which is difficult to operate in the atmosphere due to chemical instability is used as a Since the main raw material of the phosphor is produced, it is difficult to mass-produce a high-purity phosphor, and the production yield is lowered, and the price of the phosphor is increased, which is a problem.

Further, since the conventional light-emitting device has a small variety of applicable phosphor materials, the material selectivity is small, and it is limited to a supplier of a certain number of phosphors, which also causes the price of the light-emitting device to be high. Further, the warm color-based luminescent component (especially red) has a strong illuminating intensity, and the number of inexpensive illuminating devices having a large special color evaluation number R9 is small, which is also a problem.

The present invention has been made to solve the above problems, and an object thereof is to provide a completely novel phosphor composition which can emit warm color light, and more particularly to provide a phosphor composition which emits red light. Further, it is an object of the present invention to provide a method for producing a phosphor composition which is suitable for mass production of the nitride-based phosphor composition of the present invention and which can be produced at low cost. Furthermore, the present invention also provides an inexpensive light-emitting device in which the warm-colored luminescent component (especially red) has a strong illuminating intensity and a special color rendering number R9 is large.

Further, regarding the technique for measuring the internal quantum efficiency and the external quantum efficiency of the phosphor of the present invention, a technique capable of performing high-precision measurement has been established, and a part of the phosphor for a fluorescent lamp is irradiated with light of a specific excitation wavelength ( 254 nm ultraviolet excitation), the absolute values of internal quantum efficiency and external quantum efficiency are known (for example, refer to Okubo and Akira, "Lighting Society", Heisei 11, Vol. 83, No. 2, p. ).

The present invention is a phosphor composition, which is a composition represented by a structural formula of aM ₃ N ₂ ‧bAlN‧cSi ₃ N ₄ as a main body of a phosphor precursor, characterized in that M in the above structural formula is used It is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and a, b, and c respectively satisfy 0.2≦a/(a+b)≦0.95, 0.05≦b/(b+ c) ≦0.8, 0.4≦c/(c+a)≦0.95.

Further, the present invention is a light-emitting device characterized by using the above-described phosphor composition as a light-emitting source.

Moreover, the present invention provides a method for producing a phosphor composition, which comprises producing the phosphor composition characterized by containing at least 1 selected from the group consisting of Mg, Ca, Sr, Ba, and Zn. The compound formed by heating the oxide of the element, the ruthenium compound, the aluminum compound, the compound containing the element forming the luminescent center ion, and the carbon-containing raw material are reacted in a nitriding gas atmosphere.

Moreover, the present invention provides a light-emitting device including a phosphor layer containing a nitride phosphor and a light-emitting element having an emission peak in a wavelength region of 360 nm or more and less than 500 nm, and the nitride phosphor The light emitted by the light-emitting element excites light, and at least the light-emitting component emitted by the nitride phosphor serves as output light of the light-emitting device. The light-emitting device is characterized in that the nitride phosphor is Eu ^{2+ .} a phosphor activated by the structural formula (M _1-x Eu _x )AlSiN ₃ , wherein the M is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and the aforementioned x satisfies 0.005 ≦ x ≦ 0.3 .

Moreover, the present invention provides a light-emitting device including a phosphor layer containing a nitride phosphor and a light-emitting element, wherein the light-emitting element has an emission peak in a wavelength region of 360 nm or more and less than 500 nm, and the nitride phosphor is subjected to the aforementioned The light emitted by the light-emitting element is excited to emit light, and at least the light-emitting component emitted by the nitride phosphor is used as the output light of the light-emitting device. The light-emitting device is characterized in that the nitride phosphor includes a layer of Eu ^{2+ .} a nitride phosphor or an oxynitride phosphor which has an emission peak in a wavelength region of 600 or more and less than 660 nm, and an alkaline earth which is activated by Eu ²⁺ and has a luminescence peak in a wavelength region of 500 or more and less than 600 nm. The metal-based orthosilicate phosphor is excited by the light emitted from the light-emitting element, and the internal quantum efficiency of the phosphor is 80% or more.

Embodiments of the present invention will be described below.

(Embodiment 1)

First, an embodiment of the phosphor composition of the present invention will be described. An example of the phosphor composition of the present invention contains a phosphor precursor and a luminescent center ion, and is a main body containing a composition represented by a structural formula of aM ₃ N ₂ ‧ bAlN‧ cSi ₃ N ₄ as a phosphor precursor. In the above structural formula, M is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and a, b, and c satisfy 0.2 ≦ a / (a + b) ≦ 0.95, 0.05 ≦ b / ( b+c) ≦0.8, 0.4≦c/(c+a)≦0.95. When such a composition is used as a phosphor precursor, when Eu ²⁺ ions are added as a luminescent center, the phosphor composition is excited by ultraviolet, near-ultraviolet, violet, or blue light to become a warm color that emits orange or red. A light-emitting phosphor.

Here, as the main body, the content is more than 50% by weight, and the content is preferably 75% by weight or more, more preferably 85% by weight or more.

From the viewpoints of luminous efficiency or luminescent color tone, it is preferable that the above a, b, and c satisfy 0.2 ≦ a / (a + b) ≦ 0.6, 0.3 ≦ b / (b + c) ≦ 0.8, 0.4 ≦ c / (c+a) ≦ 0.8, more preferably 0.2 ≦ a / (a + b) ≦ 0.3, 0.6 ≦ b / (b + c) ≦ 0.8, 0.4 ≦ c / (c + a) ≦ 0.6 Value.

The above-mentioned phosphor precursor may be a composition represented by a structural formula of MAlSiN ₃ .

Further, another example of the phosphor precursor of the present invention does not contain M ₂ Si ₅ N ₈ , MSi ₇ N ₁₀ , M _1.5 Al ₃ Si ₉ N ₁₆ , MAl ₂ Si ₁₀ N ₁₆ , MSi ₃ N ₅ , A composition represented by a structural formula of M ₂ Si ₄ N ₇ , MSi ₆ AlON ₉ , M ₂ Si ₄ AlON ₇ , and MSiN ₂ , which is selected from the group consisting of an alkaline earth metal nitride and a zinc nitride. Nitride and yttria, tantalum nitride, aluminum nitride, mixed in a molar ratio of 2 (1-x): 3x: 2:6 (x is 0≦x≦0.1), A composition produced by firing at 1600 ° C in a nitrogen-hydrogen mixed gas for 2 hours.

From the viewpoint of luminous efficiency or luminescent color tone, it is preferable that the above-mentioned element M is at least one element selected from the group consisting of Ca and Sr, and is also an element for the purpose of obtaining a phosphor that emits red light of good purity. It is preferred that the main component of M is Ca or Sr. The element M may be composed of a mixture of at least two elements of the aforementioned element group.

Further, the main component of the element M is Ca or Sr, and means that half or more (preferably 80 atom% or more) of the element M is Ca or Sr. Further, in consideration of raw material management or manufacturing, it is preferable that the element M is one of the aforementioned element groups, for example, the elements M are all composed of Ca or Sr.

Further, the composition represented by the above-mentioned MAlSiN ₃ structural formula preferably includes a compound represented by the above chemical formula MAlSiN ₃ , and it is more preferable to use the above compound as a main component. The phosphor compound of the present embodiment preferably contains no impurities, but may contain a metal impurity element or a vaporized impurity element in an amount of less than 10 atomic % corresponding to at least one of the elements M, Al, Si or N. At least one. Further, if the above composition is represented by the chemical formula MAlSiN ₃ , as long as it is in the range of not more than 10 atomic %, even if Al, Si or N of the above chemical formula MAlSiN ₃ is excessive or insufficient, as long as the phosphor precursor is a chemical formula of MAlSiN ₃ The compound represented is the subject. That is to say, in order to improve the luminescence properties of the phosphor, it is possible to add a trace amount or a small amount of impurities or a slight deviation from the stoichiometric theoretical composition.

For example, in order to slightly improve the luminescent properties of the phosphor composition of the present embodiment, one part of Si may be substituted with at least one of elements which may be tetravalent, such as Ge or Ti, and one part of Al may be substituted for 3 At least one of the elements of the valence, such as B, Ga, In, Sc, Y, Fe, Cr, Ti, Zr, Hf, V, Nb, Ta, and the like. Here, the above part means, for example, that the number of atoms of Si or Al is less than 30 atom%.

The substantial composition range of the above composition is MAl _{1 ± 0.3} Si _{1 ± 0.3} N _{3 (1 ± 0.3)} O _{0 to 0.3} , preferably the structural formula MAl _{1 ± 0.1} Si _{1 ± 0.1} N _{3 (1 ± 0.1)} O _{0 ~0.1} indicates the composition range.

Further, the above composition is particularly preferably represented by a structural formula or a chemical formula of SrAlSiN ₃ or CaAlSiN ₃ . For example, it may be a composition having a plurality of alkaline earth metal elements such as (Sr, Ca)AlSiN ₃ , (Sr, Mg)AlSiN ₃ , (Ca, Mg)AlSiN ₃ , (Sr, Ca, Ba)AlSiN ₃ . Further, O (oxygen) in the above structural formula is an impurity element which is mixed when the phosphor composition is produced.

In the crystal lattice of the compound constituting the phosphor precursor, at least one ion (luminescence center ion) which can serve as an emission center is added to constitute a phosphor composition. If a luminescent center ion is added to the phosphor precursor, it will constitute a fluorescent body that emits fluorescence.

The luminescent center ion may be appropriately selected from metal ions selected from various rare earth ions or transition metal ions. Specific examples of the luminescent center ion include Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , and Er ³⁺ . Trivalent rare earth metal ions such as Tm ³⁺ and Yb ³⁺ , divalent rare earth metal ions such as Sm ²⁺ , Eu ²⁺ , and Yb ²⁺ , divalent transition metal ions such as Mn ²⁺ , Cr ³⁺ or Fe ^{3 +} such as a trivalent transition metal ion or a tetravalent transition metal ion such as Mn ⁴⁺ .

The phosphor composition of the present embodiment is preferably an ion having at least one of Ce ³⁺ and Eu ²⁺ selected from the viewpoint of luminous efficiency. Further, if it is a phosphor containing such an ion, it can be a preferred phosphor suitable for a white LED. When Eu ²⁺ is used as the luminescent center ion, a phosphor that emits warm light can be obtained, and it can be used as a luminescent device, particularly a illuminating device. If Ce ³⁺ is used as the luminescent center ion, a phosphor that emits blue-green light can be obtained, which is suitable for a high color rendering light-emitting device, particularly a phosphor for illumination devices.

The phosphor composition of the present embodiment preferably has an ^ion selected from at least one of Ce ³⁺ , Eu ²⁺ , Eu ^{3+ ,} and Tb ³⁺ as a luminescent center ion from the viewpoint of luminescent color. If Ce ^{3+ is} used as the luminescent center ion, a high-efficiency phosphor emitting at least blue-green light can be obtained. If Eu ²⁺ is used as the luminescent center ion, high-efficiency fluorescence emitting orange-red light can be obtained. In the case of Eu ³⁺ as the luminescent center ion, a high-efficiency phosphor that emits red light can be obtained. If Tb ^{3+ is} used as the luminescent center ion, a high-efficiency phosphor that emits green light can be obtained. In any of the phosphors, red or green or blue, which is a high color purity of the three primary colors of light, or orange-colored light, which is required to be large, is applied, and is suitable for use as a phosphor for a light-emitting device.

The preferred addition amount of the luminescent center ion varies depending on the type of the luminescent center ion. For example, when Eu ²⁺ or Ce ^{3+ is} used as the luminescent center ion, the amount of the luminescent center ion added to the element M is preferably 0.1. Atomic % to 30 atom%, more preferably 0.5 atom% to 10 atom%. If the amount added is less than this or more than this, it cannot be a phosphor which combines both good luminescent color and high brightness. Further, basically, it is preferable to add the luminescent center ion in such a manner as to replace the lattice position of one of the elements M, but it is also possible to replace one of the lattice positions of Al or Si.

The phosphor composition of the present embodiment may be a phosphor that co-activates a plurality of luminescent center ions. Examples of the phosphor which is co-activated by the luminescent center ion include a phosphor which is co-activated by Ce ³⁺ ion and Eu ²⁺ ion, a phosphor which is coactivated with Eu ²⁺ ion and Dy ³⁺ ion, and Eu. A phosphor that is co-activated with ²⁺ ions and Nd ³⁺ ions, a phosphor that is coactivated with Ce ³⁺ ions and Mn ²⁺ ions, a phosphor that is coactivated with Eu ²⁺ ions and Mn ²⁺ ions, and the like. In this way, the energy transfer phenomenon from one of the luminescent center ions to the other ion can be utilized to obtain a phosphor whose shape of the excitation spectrum or the luminescence spectrum is controlled, or to use the excitation phenomenon due to heat to obtain afterglow ( Afterglow) long long afterglow phosphor.

Preferred phosphors for use in the light-emitting device of the present invention are as follows. Such a phosphor can be obtained by changing the numerical values of the above a, b, c or the element ratio of the element M or the type or amount of the luminescent center.

(1) A warm color system having a luminescence peak in a wavelength region of 580 nm or more and less than 660 nm (from the viewpoint of color purity and visibility required for a light-emitting device, preferably 610 or more and less than 650 nm), in particular, red light emission Fluorescent body.

(2) A phosphor which can be excited by irradiation of near-ultraviolet light or ultraviolet light of 350 nm or more and less than 420 nm (from the viewpoint of the excitation characteristics required for the light-emitting device, preferably 380 nm or more and less than 410 nm).

(3) A phosphor that can be excited by blue light irradiation of 420 nm or more and less than 500 nm (from the viewpoint of the excitation characteristics required for the light-emitting device, preferably 440 nm or more and less than 480 nm).

(4) A phosphor that can be excited by irradiation with green light of 550 nm or more and less than 560 nm.

In addition, the properties of the phosphor composition of the present embodiment are not particularly limited, and may be a single crystal block, a ceramic molded body, a film having a thickness of several nm to several μm, a thick film having a thickness of 10 μm to several 100 μm, a powder, or the like. However, when it is applied to a light-emitting device, it is preferably a powder, and a powder having a center particle diameter (D ₅₀ ) of 0.1 to 30 μm is more preferable, and a powder having a center particle diameter (D ₅₀ ) of 0.5 to 20 μm is _more preferable. Further, the shape of the particles of the phosphor composition itself is not particularly limited, and may be any of a spherical shape, a plate shape, and a rod shape.

The phosphor composition of the present embodiment obtained as described above can be excited by at least 250 to 600 nm of ultraviolet to near ultraviolet to blue to green to yellow to orange, and at least can emit blue, green or red light. Fluorescent body. A red-emitting phosphor having an emission peak in a wavelength region of 610 to 650 nm can also be obtained. Further, the excitation spectrum and the luminescence spectrum shape of the above-mentioned red-emitting phosphor having Eu ²⁺ ions as an illuminating center are similar to the conventional Eu-based Sr ₂ Si ₆ N ₈ nitride silicate. ^{The 2+} activated phosphor has an excitation spectrum similar to that of the luminescence spectrum.

Hereinafter, a method of producing the phosphor composition of the present embodiment will be described.

<Manufacturing Method 1 of the Present Invention>

The phosphor composition of the present embodiment can be produced, for example, by the production method described below.

First, an alkaline earth metal M nitride (M ₃ N ₂ ) or a zinc nitride (Zn ₃ N ₂ ), tantalum nitride (Si ₃ N ₄ ), or aluminum nitride (AlN) is prepared for forming a firefly. The raw material of the light body matrix. Among them, nitrides of alkaline earth metals or nitrides of zinc are not commonly used as ceramic raw materials, and are not only difficult to obtain, but also expensive, and easily deteriorated by reaction with water vapor in the atmosphere, and are difficult to handle in the atmosphere.

Further, various rare earth metals or transition metals or the like are used as a raw material for adding a luminescent center ion. The element is, for example, a lanthanide or transition metal having an atomic number of 58 to 60 or 62 to 71, particularly Ce, Pr, Eu, Tb, and Mn. The compound containing such an element may be an oxide, a nitride, a hydroxide, a carbonate, an oxalate, a nitrate, a sulfate, a halide, a phosphate or the like of the above lanthanoid or transition metal. Specifically, there are, for example, cerium carbonate, cerium oxide, cerium nitride, metal cerium, manganese carbonate, and the like.

Next, the phosphor raw materials are weighed so that the atomic ratio of each atom is a(M _1-x Lc _x ) ₃ N ₂ ‧bAlN‧cSi ₃ N ₄ and mixed to obtain a mixed raw material. Wherein M is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and a, b, and c satisfy 0.2 ≦ a / (a + b) ≦ 0.95, 0.05 ≦ b / (b +c) ≦0.8, 0.4≦c/(c+a)≦0.95, Lc represents an element as a luminescent center ion, and x represents 0<x<0.3, preferably 0.001≦x≦0.2, more preferably The value of 0.005≦x≦0.1. For example, the atomic ratio can be defined as M _1-x Lc _x AlSiN ₃ .

Next, the mixed raw material is fired in an atmosphere of a vacuum atmosphere, a neutral atmosphere (inert gas or nitrogen), or a reducing atmosphere (CO, nitrogen-hydrogen mixed gas, etc.).

Further, in the above-described ambient atmosphere, it is preferable to use a simple equipment, and it is preferably an atmospheric environment atmosphere, but it may be any of a high-pressure atmosphere, a pressurized atmosphere, a reduced-pressure atmosphere, and a vacuum atmosphere. In order to improve the performance of the phosphor, it is preferred that the reaction atmosphere is a high-pressure atmosphere, for example, 2 to 100 atm, and if considering the operation of the ambient atmosphere, it is preferably a nitrogen gas mainly composed of 5 to 20 atmospheres. The atmosphere of the environment. According to this high-pressure atmosphere, it is possible to prevent or suppress the decomposition of the nitride phosphor composition during high-temperature firing, and to suppress the phosphor composition deviation, thereby producing a high-performance phosphor composition.

Further, as the luminescent center ion, in order to generate a large amount of ions such as Ce ³⁺ , Eu ²⁺ , Tb ³⁺ , and Mn ²⁺ , a preferable atmosphere is a reducing atmosphere. The firing temperature is, for example, 1300 to 2,000 ° C. In order to improve the performance of the phosphor, it is preferably 1600 to 2000 ° C, more preferably 1700 to 1900 ° C. If it is to be mass-produced, it is preferably 1400 to 1800 ° C, more preferably 1600 to 1700 ° C. The firing time is, for example, 30 minutes to 100 hours, and if productivity is considered, the preferred firing time is 2 to 8 hours. The firing can be carried out in fractions in a different ambient atmosphere or in the same ambient atmosphere. The fired product obtained by the firing is a phosphor composition.

Further, the phosphor composition of the present embodiment is not limited to being produced by the above-described production method. It can be produced not only by the solid phase reaction described above, but also by, for example, a gas phase reaction, a liquid phase reaction or the like.

Further, nitrides such as Si ₃ N ₄ or AlN are not as difficult to obtain as nitrides of alkaline earth metals, but it is difficult to obtain high purity. In the case where most of the above-mentioned nitrides such as Si ₃ N ₄ or AlN are oxidized to SiO ₂ or Al ₂ O ₃ in a large part of the atmosphere, the purity is slightly lowered. For the above reasons, the phosphor composition of the present embodiment may have substantially the above-described atomic ratio composition, and in the structural formula MAlSiN ₃ , a part of Si ₃ N ₄ or AlN is oxidized to SiO _{2 .} Or the case of Al ₂ O ₃ .

<Manufacturing Method 2 of the Present Invention>

The phosphor composition of the present embodiment can be produced, for example, by the production method described below.

In the production method 2 of the present invention, a composition in which the composition represented by the a(M _1-x Lc _x ) ₃ N ₂ ‧bAlN‧cSi ₃ N ₄ structural formula is a phosphor precursor is produced. An oxide obtained by heating at least one element M selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and a telluride, an aluminide, a compound containing an element forming a luminescent center ion, and a raw material of carbon, in nitrogen The reaction in a gaseous atmosphere.

An example of the production method 2 of the present invention is an alkaline earth metal oxide or a zinc compound (preferably heatable) which can form a metal oxide MO (wherein M is Mg, Ca, Sr, Ba, and Zn) by heating. The alkaline earth metal compound which forms CaO or SrO is reduced and nitrided by reacting with carbon in a nitriding atmosphere, and the alkaline earth metal compound or the zinc compound and the nitride, the aluminide, and the luminescence are formed. The compound of the element of the central ion is reacted.

The manufacturing method 2 of the present invention may be referred to as a reduction nitridation method for producing the aforementioned a(M _1-x Lc _x ) ₃ N ₂ ‧bAlN‧cSi ₃ N ₄ (especially M _1-x Lc _x AlSiN ₃ ) fluorescent light A method of manufacturing a body, particularly a method suitable for industrial production of a powdered phosphor composition.

The manufacturing method 2 of the present invention will be described in detail below.

First, a compound, a telluride or an aluminide which forms an oxide of the above-mentioned element M by heating is prepared as a raw material for forming a phosphor precursor. A compound (described later) which forms an oxide of the above-mentioned element M by heating is preferably used as a ceramic material. This raw material is not only easy to obtain but also inexpensive, and is stable in the atmosphere and easy to handle in the atmosphere.

Further, various rare earth metals or transition metals or the like are prepared as a raw material to be added to the luminescent center ions. Also, carbon is prepared as a reducing agent.

Next, the phosphor raw materials and the reducing agent are weighed so that the atomic ratio of each atom is, for example, a(M _1-x Lc _x ) ₃ N ₂ ‧bAlN‧cSi ₃ N ₄ and reacted with the carbon of the reducing agent. Carbon monoxide gas (CO) is generated to completely remove the proportion of oxygen in the phosphor raw material, and mixed to obtain a mixed raw material. Here, Lc represents a metal element which becomes an emission center ion, and x represents a value satisfying 0 < x < 0.3, preferably 0.001 ≦ x ≦ 0.2, more preferably 0.005 ≦ x ≦ 0.1.

Next, the mixed raw materials are fired in a nitriding gas atmosphere to cause a reaction. Here, the nitriding gas system refers to a gas which can be generated by a nitriding reaction.

Further, as a light-emitting center ion, in order to generate a large amount of ions such as Ce ³⁺ , Eu ²⁺ , Tb ³⁺ , and Mn ²⁺ , a preferred ambient atmosphere is a reducing atmosphere, for example, a nitrogen-hydrogen mixed atmosphere. The firing temperature is, for example, 1300 to 2,000 ° C. In order to improve the performance of the phosphor, it is preferably 1600 to 2000 ° C, more preferably 1700 to 1900 ° C. If it is to be mass-produced, it is preferably 1400 to 1800 ° C, more preferably 1600 to 1700 ° C. The firing time is, for example, 30 minutes to 100 hours, and if productivity is considered, the preferred firing time is 2 to 8 hours. The firing can be carried out in fractions in a different ambient atmosphere or in the same ambient atmosphere. The fired product obtained by the firing is a phosphor composition.

The compound which can form the oxide MO of the element M by heating is not particularly limited, and is preferably selected from the group consisting of alkaline earth metals or from the viewpoints of easiness of obtaining a high-purity compound, ease of availability in the atmosphere, and price. An alkaline earth metal compound or a zinc compound of at least one of zinc carbonate, oxalate, nitrate, acetate, oxide, peroxide, or hydroxide, more preferably an alkali earth metal carbonate or oxalate Oxides, especially carbonates of alkaline earth metals, are preferred.

The properties of the alkaline earth metal are not particularly limited, and may be appropriately selected from a powder form, a block form, and the like. Further, in order to obtain a powdery phosphor, a preferred property is a powder.

The telluride is not particularly limited as long as it can form the phosphor composition of the present embodiment by the above reaction, and is preferably used for the same reason as the above-described alkaline earth metal or for producing a high-performance phosphor. The material is tantalum nitride (Si ₃ N ₄ ) or bismuth imide (Si(NH) ₂ ), more preferably tantalum nitride.

The properties of the above-mentioned telluride are not particularly limited, and can be appropriately selected from a powder form, a block form, and the like. Further, in order to obtain a powdery phosphor, a preferred property is a powder.

In the production method 2 of the present invention, the supply source of the ruthenium may be a ruthenium monomer. In this case, the ruthenium monomer may be reacted with nitrogen or the like in an atmosphere of a nitriding gas to form a niobium nitride (such as tantalum nitride), and then reacted with the alkaline earth metal nitride or aluminide or the like. Therefore, the production method 2 of the present invention also includes the above-described telluride being a single monomer.

The aluminide is not particularly limited as long as the phosphor composition of the present embodiment can be formed by the above reaction, and aluminum nitride (AlN) is preferred for the same reason as the above-described telluride.

The properties of the aluminide described above are not particularly limited, and may be appropriately selected from a powder form, a block form, and the like. Further, in order to obtain a powdery phosphor, a preferred property is a powder.

In the production method 2 of the present invention, the supply source of aluminum may be a metal monomer. In this case, the aluminum metal may be reacted with nitrogen or the like in an atmosphere of a nitriding gas to form a nitride of aluminum (such as aluminum nitride), and then reacted with the above-described alkaline earth metal nitride or telluride. Therefore, the manufacturing method 2 of the present invention also includes the case where the aluminide is aluminum metal.

The properties of the carbon are not particularly limited, and solid carbon is preferred, and carbon black, high-purity carbon powder, carbon block or the like can be used. Among them, graphite is particularly preferable. However, amorphous carbon (coal, coke, charcoal, gaseous carbon, etc.) can also be used. Further, a carburizing gas such as natural gas, methane (CH ₄ ), propane (C ₃ H ₈ ), or butane (C ₄ H ₁₀ ) may be used as a carbon source. Further, when a carbonaceous firing vessel or a heating element is used in a vacuum atmosphere or an inert atmosphere atmosphere, a part of carbon is evaporated, and such evaporated carbon can also be used as a reducing agent in theory. .

The size and shape of the above solid carbon are not particularly limited. From the viewpoint of easiness of obtaining, a fine powder, a powder or a particle having a solid carbon size and shape of a longest diameter or a longest side of 10 nm to 1 cm may be used as the other solid carbon. Solid carbon of various shapes such as powder, granule, block, plate, or rod can be used. The purity of the solid carbon is not particularly limited. However, in order to obtain a high-quality nitride phosphor, the purity of the solid carbon is preferably as high as possible, for example, a purity of 99% or more, preferably a high purity carbon having an alcohol degree of 99.9% or more.

The amount of the solid carbon added is a stoichiometric reaction ratio required to remove oxygen contained in the phosphor raw material, but the reaction ratio is preferably excessive in order to completely remove the oxygen. If specified by specific numerical values, the excess amount of solid carbon added is preferably not more than 30 atom% required for the above stoichiometric amount.

Further, the solid carbon to be reacted may also serve as a heating element (carbon heater) or as a baking container (carbon crucible or the like). The carbon as the reducing agent may be used in combination with the phosphor raw material, or may be simply contacted.

In addition, the nitriding gas is not particularly limited as long as it is nitriding the alkaline earth metal or the zinc compound which can be reduced by the carbon, and is easy to obtain from a high-purity gas, easy to handle, and expensive. Preferably, it is at least one selected from the group consisting of nitrogen and ammonia, more preferably nitrogen. Further, in order to increase the reducing power of the firing atmosphere, to improve the performance of the phosphor, or to obtain a high-performance phosphor, a nitrogen-hydrogen mixed gas may be used.

The reaction atmosphere containing a nitriding gas is preferably a normal-pressure atmosphere, but it may be a high-pressure atmosphere, a pressurized atmosphere, a reduced-pressure atmosphere, or a vacuum atmosphere. One. In order to improve the performance of the phosphor, the reaction atmosphere is preferably a high-pressure atmosphere, for example, 2 to 100 atmospheres, and if considering the operation of the ambient atmosphere, it is preferably composed of nitrogen gas at a pressure of 5 to 20 atmospheres. The atmosphere of the environment. According to this high-pressure atmosphere, it is possible to prevent or suppress decomposition of the nitride phosphor composition during high-temperature firing, and it is possible to suppress the phosphor composition deviation and to manufacture a high-performance phosphor composition. Further, in order to promote decarburization of the reactant (calcined product), a small amount or a small amount of water vapor may be contained in the reaction atmosphere.

In order to increase the reactivity of the above-mentioned compound raw materials, a flux reaction may be added. The flux can be appropriately selected from an alkali metal compound (Na ₂ CO ₃ , NaCl, LiF) or a halide (SrF ₂ , CaCl ₂ ) or the like.

The greatest feature of the production method 2 of the present invention is that: (1) the raw material of the phosphor composition of the present embodiment does not substantially use an alkaline earth metal or a zinc nitride, an alkaline earth metal or a zinc metal; (2) instead, Using a compound which can form a metal oxide (the aforementioned MO) by heating; (3) reacting the oxygen component contained in the compound with carbon (preferably solid carbon); (4) by nitriding The gas reaction causes the alkaline earth metal compound to be nitrided, and (5) reacts with the telluride and the aluminide to produce the phosphor composition of the present embodiment.

In the above-described production method 2 of the present invention, the reaction temperature is preferably 1300 to 2,000 ° C, and in order to improve the performance of the phosphor, it is preferably 1600 to 2000 ° C, more preferably 1700 to 1900 ° C. If it is a large amount of production, it is preferably 1400 to 1800 ° C, more preferably 1600 to 1700 ° C. . Also, the reaction can be carried out in fractions. In this way, the compound which forms a metal oxide by heating becomes the metal oxide MO, and further reacts with carbon, and the metal oxide is reduced while producing carbon monoxide or carbon dioxide. Further, the reduced metal oxide is nitrided by a nitriding gas to form a nitride, and is simultaneously reacted with another compound such as the above-mentioned telluride or aluminide or a gas or the like. Thereby, the nitride phosphor composition of the present embodiment can be produced.

If the reaction is carried out at a temperature lower than the above temperature range, the above reaction or reduction may be incomplete, and it is difficult to obtain a high-quality nitride phosphor composition, and if it is reacted at a temperature higher than the above temperature range, nitrogen is required. The phosphor composition of the phosphor is decomposed or melted, and it is difficult to obtain a phosphor composition of a desired composition or shape (powder, molded body, etc.). Further, when reacting at a temperature higher than the above temperature range, it is necessary to use a high-priced heat generating body or a high heat-resistant heat insulating material in the manufacturing equipment, and the equipment cost is increased, and it is difficult to provide an inexpensive phosphor composition.

According to the production method 2 of the present invention, it is not necessary to use a high-purity material to obtain an alkaline earth metal or zinc nitride which is difficult to handle in the atmosphere and which is a main raw material of the phosphor. The production method 2 of the present invention is characterized in that a compound containing a compound capable of generating an oxide of the element M by heating, a raw material of a telluride, an aluminide, and a carbon, and a compound containing an element forming an emission center ion are used in a nitriding gas. Reaction in an ambient atmosphere. Since these raw materials are relatively inexpensive and easy to obtain, and are easy to handle in the atmosphere, they are suitable for mass production, and the phosphor of the present embodiment can be produced at low cost. Meanwhile, if the phosphor composition produced by the production method 2 of the present invention is used, the light-emitting device can be made more inexpensive, and an inexpensive light-emitting device can be provided.

Further, it is to be noted that the above-described manufacturing method 2 of the present invention can also be applied to the above-described manufacturing method 1 of the present invention. For example, if at least one of the alkaline earth metal nitride (M ₃ N ₂ ) and the zinc nitride (Zn ₃ N ₂ ) used for forming the phosphor precursor is added to the tantalum nitride (Si ₃ N) ₄ ) When carbon is used as a reducing agent in aluminum nitride (AlN), the impurity oxygen in the firing can be removed as carbon monoxide gas (CO), and the phosphor can be prevented or suppressed. A high-purity nitride phosphor composition can be produced by aeration.

In other words, in the method for producing a nitride phosphor composition comprising at least one nitride selected from the group consisting of alkaline earth metal nitrides and zinc nitrides, at least one phosphor material is added to the phosphor raw material. The method for producing a phosphor composition which is fired after carbon can also be used as a method for producing a phosphor composition of the above other embodiment. In addition, the nitride phosphor composition means a phosphor composition containing nitrogen as a gas element constituting a phosphor precursor, such as a nitride phosphor composition or an oxynitride phosphor composition, in particular, A phosphor composition containing nitrogen as a main gas component element.

Further, in the phosphor composition raw material which is the main component of the phosphor precursor, the composition represented by the above-mentioned MAlSiN ₃ is mixed with some, for example, Si ₃ N ₄ , M ₂ Si ₅ N ₈ , MSiN ₂ , MSi ₇ N ₁₀ When a nitride-based compound is fired, a phosphor composition similar to the light-emitting property of the above-described phosphor composition can be obtained. Therefore, the phosphor composition of the present embodiment may have any one of MAlSiN ₃ ‧ aSi ₃ N ₄ , MAlSiN ₃ ‧ aM ₂ Si ₅ N ₈ , MAlSiN ₃ ‧ aMSiN ₂ , and MAlSiN ₃ ‧ a MSi ₇ N ₁₀ The nitride represented by the formula is a phosphor composition of the phosphor precursor. Wherein M is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and a is a value satisfying 0≦a≦2, preferably 0≦a≦1. Such a phosphor composition is, for example, 2MAlSiN ₃ ‧Si ₃ N ₄ , 4MAlSiN3‧3Si ₃ N ₄ , MAlSiN ₃ ‧Si ₃ N ₄ , MAlSiN ₃ ‧2Si ₃ N ₄ , 2MAlSiN ₃ ‧M ₂ Si ₅ N ₈ MAlSiN ₃ ‧M ₂ Si ₅ N ₈ ,MAlSiN ₃ ‧2M ₂ Si ₅ N ₈ , 2MAlSiN ₃ ‧MSiN ₂ ,MAlSiN ₃ ‧MSiN ₂ ,MAlSiN ₃ ‧2MSiN ₂ ,2MAlSiN ₃ ‧MSi ₇ N ₁₀ ,MAlSiN ₃ ‧ MSi ₇ N _10, the composition represented by the MAlSiN ₃ ‧2MSi ₇ N ₁₀ like a fluorescent emission center ion is added to the composition and the like.

(Embodiment 2)

Hereinafter, an embodiment of the light-emitting device of the present invention will be described. In an example of the light-emitting device of the present invention, the phosphor composition of the first embodiment may be used as the light-emitting source, and the form thereof is not particularly limited. For example, an electromagnetic wave selected from at least one of X-ray, electron beam, ultraviolet ray, near-ultraviolet light, visible light (purple, blue, green light, etc.), near-infrared light, infrared light, or the like can be used as the excitation source of the phosphor. An electric field may be applied to the phosphor of the first embodiment, or an electron or the like may be injected to excite and emit light to serve as a light source.

The light-emitting device of the present embodiment is, for example, a device of the following name.

(1) Fluorescent lamps, (2) plasma displays, (3) inorganic electroluminescent panels, (4) field emission displays, (5) electron tubes, and (6) white LED light sources.

More specifically, the light-emitting device of the present embodiment includes a white LED and various display devices using a white LED (for example, an LED information display terminal, an LED traffic signal, and an LED lamp for an automobile (a vehicle lamp, a direction lamp, a front lamp) Various lighting devices (lighting inside and outside lighting, in-vehicle LED, LED emergency lighting, LED light source, LED decorative light) made of white LEDs, various display devices (tubes, not using white LED lights) There are no electroluminescent panels, plasma display panels, etc.), and various lighting devices (fluorescent lamps, etc.) that do not use white LEDs.

Further, from another viewpoint, the light-emitting device of the present embodiment is, for example, at least an embodiment of an injection-type electroluminescence device (light-emitting diode, semiconductor laser, or organic electroluminescence device) that emits ultraviolet light or blue light. The phosphor composition of 1 is combined into a white light-emitting element or any of various light sources, illumination devices, display devices, and the like. Further, the light-emitting device includes a display device, an illumination device, a light source, and the like which are formed using at least one of the above-described white light-emitting elements.

In the light-emitting device of the present embodiment, it is preferable that a light-emitting light having a luminescence peak in a wavelength region of 580 to 660 nm is emitted, and a nitride-based phosphor composition having a luminescence peak in a wavelength region of 610 to 650 nm is preferable. A light-emitting device comprising a light source, wherein the phosphor composition of the first embodiment is used as the nitride phosphor composition.

Further, the light-emitting device of the present embodiment is, for example, a combination of an emission source that emits primary light of 360 nm or more and less than 560 nm, and a visible light that absorbs primary light of the emission source and is converted to a longer wavelength than the primary light. In the light-emitting device of the light-body composition, the phosphor composition of the first embodiment is used as the phosphor composition, and it is more preferable to use a phosphor composition that emits warm-color light. More specifically, it is an emission source having an emission peak in a wavelength region of 360 nm or more, less than 420 nm, 420 nm or more, less than 500 nm, 500 nm or more, and less than 560 nm, and one time of absorbing the above-mentioned emission source. The light-emitting device in which the light is converted into a phosphor composition having a longer visible light wavelength than the primary light, wherein the phosphor composition is the phosphor composition of the first embodiment.

In the light-emitting device of the present embodiment, an injection-type electroluminescence device can be used as the emission source. Further, the injection type electroluminescence element means a photoelectric conversion element which can convert light into light energy to emit light by applying electric power to inject electrons into the fluorescent substance. Specific examples thereof are as described above.

In the light-emitting device of the present embodiment, a completely novel phosphor that can increase the selectivity of the phosphor material is used as the light-emitting source. Therefore, it is possible to manufacture a light-emitting device comprising a rare and expensive conventional phosphor. Cheap lighting device. Further, since a phosphor that emits warm-colored light, particularly red light, is used as the light-emitting source, the intensity of the light-emitting component of the warm color system is strong, and the light-emitting device having a high number of special color evaluation numbers R9 can be obtained.

Hereinafter, the light-emitting device of the present embodiment will be described with reference to the drawings. The light-emitting device of the present embodiment is not particularly limited as long as it is configured by using the phosphor composition of the first embodiment as a light-emitting source. In a preferred embodiment, in addition to using the phosphor composition of the first embodiment, a light-emitting element is used as a light-emitting source, and the phosphor composition and the light-emitting element are provided so that the phosphor composition covers the light-emitting element. Combined composition.

Fig. 1, Fig. 2, and Fig. 3 are cross-sectional views showing a semiconductor light-emitting device of a representative embodiment of a light-emitting device in which a phosphor composition and a light-emitting device of the first embodiment are combined.

1 shows a semiconductor light-emitting device having at least one light-emitting element 1 mounted on a submount element 4, and comprising at least a phosphor composition of Embodiment 1 and also serving as a phosphor layer The light-emitting element 1 is sealed by encapsulation of a base material of 3 (for example, a transparent resin or a low-melting glass). 2 shows a semiconductor light-emitting device in which at least one light-emitting element 1 is packaged in a cup 6 disposed in a carrier wire of a conductive frame 5, and is provided in the cup body 6 to contain at least the fluorescent light of Embodiment 1. The phosphor layer 3 formed of the base material of the bulk composition 2 is encapsulated in a package such as a resin. Fig. 3 is a view showing a wafer type semiconductor light-emitting device in which at least one light-emitting element 1 is disposed in a casing 8, and at least a base material containing the phosphor composition 2 of the first embodiment is provided in the casing 8. The phosphor layer 3 formed.

In FIGS. 1 to 3, the light-emitting element 1 is a photoelectric conversion element that converts electrical energy into light energy, and specifically, for example, a light-emitting diode, a laser diode, a surface-emitting laser diode, and an inorganic power. A light-emitting element, an organic electroluminescence element, or the like. In particular, from the viewpoint of increasing the output of the semiconductor phosphor composition, a light-emitting diode or a surface-emitting diode is preferable. The wavelength of light emitted from the light-emitting element 1 is not particularly limited as long as it can excite the wavelength range of the phosphor composition of the first embodiment (for example, 250 to 550 nm). However, in order to excite the phosphor composition of the first embodiment with high efficiency to produce a white light-emitting high-luminance semiconductor light-emitting device, the light-emitting element 1 preferably exceeds 340 and 500 nm, and more preferably exceeds 350. The following 420 nm, more preferably more than 420, 500 nm or less, more preferably more than 360, 410 nm or less, and even more preferably in the wavelength range of less than 440, 480 nm, that is, near ultraviolet, purple or blue wavelength regions Luminous peak.

Further, in Fig. 1 to Fig. 3, the phosphor layer 3 contains at least the phosphor composition 2 of the first embodiment. For example, the phosphor composition of the first embodiment can be dispersed in a transparent resin (epoxy resin or anthrone). A transparent base material such as a resin or a low-melting glass is used. The content of the phosphor composition 2 in the transparent base material is, for example, preferably from 5 to 80% by weight, more preferably from 10 to 60% by weight, based on the above transparent resin. The phosphor composition 2 of the first embodiment included in the phosphor layer 3 is a light conversion material, and absorbs part or all of the light emitted from the light-emitting element 1 and converts it into yellow to deep red light. The phosphor composition 2 is excited by the light-emitting element 1 so that the semiconductor light-emitting device can emit a light-emitting component emitted from at least the phosphor composition 2.

Therefore, as described above, when a light-emitting device having the following combined structure is produced, light emitted from the light-emitting element 1 is mixed with light emitted from the phosphor layer, and white light is obtained, which is a white color that can be released. Light semiconductor light emitting element.

(1) emitting near-ultraviolet light (wavelength of 300 or more, less than 380 nm, from the viewpoint of output, preferably 350 or more, less than 380 nm) or violet light (wavelength of 380 or more and less than 420 nm, from the viewpoint of output, preferably The light-emitting element of any of 395 or more and less than 415 nm is combined with a blue phosphor, a green phosphor, and a red phosphor composition of the first embodiment.

(2) A structure in which a light-emitting element that emits light of either near-ultraviolet light or violet light is combined with a blue phosphor, a green phosphor, a yellow phosphor, and a red phosphor composition of the first embodiment .

(3) A structure in which a light-emitting element of either near-ultraviolet light or violet light is combined with a blue phosphor, a yellow phosphor, and a red phosphor composition of the first embodiment.

(4) A light-emitting element that emits blue light (having a wavelength of 420 or more and less than 480 nm, preferably 450 or more and less than 480 nm from the viewpoint of output), a green phosphor, a yellow phosphor, and the red of the first embodiment A structure in which a phosphor composition is combined.

(5) A structure in which a blue light emitting element is combined with a blue phosphor, a yellow phosphor, and a red phosphor composition of the first embodiment.

(6) A structure in which a blue light emitting element is combined with a green phosphor and the red phosphor composition of the first embodiment.

(7) A structure in which a light-emitting element of blue-green light (wavelength: 480 nm or more and less than 510 nm) is combined with the red phosphor composition of the first embodiment.

Since the phosphor composition of the first embodiment which emits red light can be excited by green light having a wavelength of 510 nm or more and less than 560 nm or yellow light having a wavelength of 560 nm or more and less than 590 nm, the green light can be emitted. The light-emitting element of either the yellow light or the red phosphor composition of the first embodiment is combined to manufacture a semiconductor light-emitting device.

Further, since the phosphor composition of the first embodiment can emit yellow light, the yellow phosphor can also be used as the yellow phosphor composition of the first embodiment. Further, in this case, the red phosphor composition may be used as a red phosphor other than the phosphor composition of the first embodiment. Further, white light can be obtained by combining the light-emitting element that emits blue light with the yellow phosphor composition of the first embodiment.

Further, the blue phosphor, the green phosphor, the yellow phosphor, and the red phosphor other than the phosphor composition of the first embodiment may be activated by Eu ²⁺ -activated aluminate Body, Eu ²⁺ activated halophosphate-based phosphor, Eu ²⁺ activated phosphate-based phosphor, Eu ²⁺ activated citrate-based phosphor, Ce ³⁺ activated garnet-based phosphor (especially , YAG (钇 铝 aluminum garnet): Ce-based phosphor), Tb ³⁺ activated citrate-based phosphor, Eu ²⁺ activated thiophthalate, Eu ²⁺ activated nitride-based phosphor (particularly, SiAlON phosphor), Eu ²⁺ activated alkaline earth metal sulfide phosphor, Eu ³⁺ activated acid sulfide phosphor, and the like, more specifically, For example, (Ba,Sr)MgAl ₁₀ O ₁₇ :Eu ²⁺ blue phosphor, (Sr,Ca,Ba,Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ :Eu ²⁺ blue phosphor, (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ green phosphor, BaMgAl ₁₀ O ₁₇ :Eu ²⁺ , Mn ²⁺ green phosphor, Y ₃ Al ₅ O ₁₂ :Ce ³⁺ green phosphor, BaY ₂ SiAl ₄ O ₁₂ :Ce ³⁺ green phosphor, Ca ₃ Sc ₂ Si ₃ O ₁₂ :Ce ³⁺ green phosphor, Y ₂ SiO ₅ :Ce ³⁺ , Tb ^{3 +} Green phosphor, BaSiN ₂ :Eu ²⁺ green phosphor, SrGa ₂ S ₄ :Eu ²⁺ green phosphor, (Y,Gd) ₃ Al ₅ O ₁₂ :Ce ³⁺ yellow phosphor, Y ₃ Al ₅ O ₁₂ :Ce ³⁺ ,Pr ³⁺ yellow phosphor, (Sr,Ba) ₂ SiO ₄ :Eu ²⁺ yellow phosphor, CaGa ₂ S ₄ :Eu ²⁺ yellow phosphor, 0.75CaO ‧2.25AlN‧3.25Si ₃ N ₄ :Eu ²⁺ yellow phosphor, CaS:Eu ²⁺ red phosphor, SrS:Eu ²⁺ red phosphor, La ₂ O ₂ S:Eu ³⁺ red fluorescent Body, Y ₂ O ₂ S: Eu ³⁺ red phosphor, and the like.

Further, conventionally, an excitation source using a blue LED as a phosphor has been known, and the phosphor layer contains, for example, a Sr ₂ Si ₅ N ₈ :Eu ²⁺ nitride red phosphor, and the above YAG:Ce a yellow phosphor, or a green phosphor, and a high-color white LED, and the phosphor composition of the first embodiment and the above-mentioned Sr ₂ Si ₅ N ₈ :Eu ²⁺ nitride red Since the phosphor can exhibit similar light-emitting characteristics, the blue LED is used as an excitation source of the phosphor, and the red phosphor composition of the first embodiment is combined with the YAG:Ce-based yellow phosphor. The light-emitting device can also be a white LED that emits a strong light beam and a high-color white light, which is equivalent to a conventional light-emitting device.

The semiconductor light-emitting device of the present embodiment can be excited by near-ultraviolet to blue light, is easy to manufacture, has high luminous intensity, and is chemically stable, and is configured by using a phosphor composition of the first embodiment having a large red light-emitting component. It can be a light-emitting device which is more resistant to light emission than the red light-emitting component of the conventional light-emitting device, has good reliability, and can be manufactured at low cost.

(Embodiment 3)

4 and 5 are schematic diagrams showing the configuration of an illumination and display device as an example of a light-emitting device of the present invention. Fig. 4 shows an illumination and display device comprising at least one semiconductor light-emitting device 9 which is a combination of the phosphor composition of the above-described first embodiment and a light-emitting device. An example. Fig. 5 shows an illumination and display device in which at least one light-emitting element 1 is combined with a phosphor layer 3 containing at least the phosphor composition 2 of the first embodiment. The light-emitting element 1 and the phosphor layer 3 can be the same as those of the semiconductor light-emitting device of the second embodiment described above. Moreover, the action and effect of the illumination and display device of this configuration are also the same as those of the semiconductor light-emitting device of the second embodiment. Further, in Fig. 4 and Fig. 5, 10 is output light.

6 to 12 show a specific example of an illumination device which is combined with the illumination and display device of the embodiment schematically shown in Figs. 4 and 5 described above. FIG. 6 shows a perspective view of the illumination module 12 having the integrated light-emitting portion 11. FIG. 7 shows a perspective view of the illumination module 12 having a plurality of light-emitting portions 11. Fig. 8 is a perspective view showing a table type illumination device having a light-emitting portion 11 and capable of controlling ON-OFF or controllable light amount with a switch 13. Fig. 9 is a side view of a lighting device using a lighting module having a screw-in base 14, a reflecting plate 15, and a plurality of light-emitting portions 11 to constitute a light source. 10 is a bottom view of the lighting device of FIG. 9. FIG. 11 is a perspective view of a flat-panel image display device having a light-emitting portion 11. Fig. 12 is a perspective view of a line segment type digital display device having a light emitting portion.

The illumination and display device of the present embodiment are easy to manufacture, have high luminous intensity, are chemically stable, and can use a phosphor composition or a red light-emitting component of the first embodiment having a large red light-emitting component, and have high luminous intensity and good reliability. Since the semiconductor light-emitting device of the second embodiment can be manufactured at a low cost, it is possible to provide an illumination display device which is more excellent in luminous intensity of a red light-emitting component than a conventional illumination display device, and which is excellent in reliability and can be manufactured at low cost.

(Embodiment 4)

Fig. 13 is a partial perspective view showing an end portion of a fluorescent lamp using an example of a light-emitting device of the phosphor composition of the first embodiment. In Fig. 13, the glass tube 16 is sealed by the electron tube 17, and the inside is sealed with a rare gas such as helium, argon or helium, and mercury. The phosphor composition 18 of the first embodiment is applied to the inner surface of the glass tube 16. The electron tube 17 mounts the filament electrode 20 by two wires 19. Both ends of the glass tube 16 are followed by a cap 22 having an electrode terminal 21, and the electrode terminal 21 is connected to the wire 19.

The shape, size, wattage of the fluorescent lamp of the present embodiment, and the color and color rendering properties of the light emitted by the fluorescent lamp are not particularly limited. The shape is not limited to the straight tube of the present embodiment, and may be, for example, a circular shape, a double ring shape, a double subtype, a small shape, a U shape, a light bulb shape, or the like, and may include a thin tube for liquid crystal backlight or the like. The size is, for example, a shape of 4 to 110. The wattage is, for example, several watts to hundreds of watts, which is appropriately determined depending on the intended use. The light color is, for example, a matte color, a white color, a white color, a warm white color, or the like.

Since the fluorescent lamp of the present embodiment is composed of the phosphor composition of the first embodiment which is easy to manufacture, has high luminous intensity, is chemically stable, and can use many red light-emitting components, it is compatible with a conventional fluorescent lamp. Compared with the red luminescent component, the illuminating intensity is stronger, and the fluorescent lamp can be manufactured at low cost.

(Embodiment 5)

Fig. 14 is a cross-sectional view showing a double-insulation structure thin film electroluminescent panel using an example of a light-emitting device of the phosphor composition of the first embodiment. In FIG. 14, the back substrate 23 is a substrate for holding a thin film EL panel, and is made of metal, glass, ceramics or the like. The lower electrode 24 is an electrode for applying an alternating current voltage of about 100 to 300 V to the laminated structure of the thick film dielectric 25 / the thin film phosphor 26 / the thin film dielectric 27, for example, a metal formed by a printing technique or the like. Electrode or In-Sn-O transparent electrode, etc. The thick film dielectric body 25 is used to limit the amount of charge flowing through the thin film phosphor 26 in addition to the film forming substrate of the thin film phosphor 26, and may be, for example, a thickness of 10 μm to several cm. A ceramic material such as BaTiO _{3 is} formed. Further, the thin film phosphor 26 is composed of an electroluminescent material which can generate high-intensity fluorescence by flowing a charge through the phosphor layer, and is formed, for example, by a thin film technique such as electron beam evaporation or sputtering. Thioaluminate phosphor (blue luminescence BaAl ₂ S ₄ :Eu ²⁺ , blue luminescence (Ba,Mg)Al ₂ S ₄ :Eu ^{2+ ,} etc.) or thioantimonate phosphor ( Blue luminescence CaGa ₂ S ₄ : Ce ^3+, etc.). In addition to limiting the amount of charge flowing through the thin film phosphor 26, the thin film dielectric body 27 can prevent the thin film phosphor 26 from deteriorating by reaction with water vapor or the like in the atmosphere, for example, by chemical vapor deposition or sputtering. A light-transmissive dielectric such as cerium oxide or aluminum oxide formed by a thin film forming technique. Further, the electrode 28 is paired with the lower electrode 24, and is an electrode that applies an alternating current voltage of about 100 to 300 V to the laminated structure of the thick film dielectric 25/thin film phosphor 26/thin film dielectric 27, for example, by vacuum. A film forming technique such as a vapor deposition method or a sputtering method forms a transparent electrode made of In-Sn-O or the like on the upper surface of the thin film dielectric body 27. The light wavelength conversion layer 29 converts light emitted from the thin film phosphor 26 and transmitted through the thin film dielectric body 27 and the upper electrode 28 (for example, blue light) into wavelengths such as green light or yellow light or red light. Further, the optical wavelength conversion layer 29 may be provided in a plurality of types. The surface glass 30 is used to protect the double-insulation structural film EL panel constructed as above.

If an alternating voltage of about 100 to 300 V is applied between the lower electrode 24 of the thin film EL panel and the upper electrode 28, the laminated structure of the thick film dielectric 25 / the thin film phosphor 26 / the thin film dielectric 27 is applied. An alternating voltage of about 100 to 300 V causes a charge to flow through the thin film phosphor 26 and emit light. This light is transmitted through the light transmissive thin film dielectric body 27 and the upper electrode 28, and the light wavelength conversion layer 29 is excited to become wavelength-converted light. The wavelength converted light is emitted through the surface glass 30 toward the outside of the panel and can be viewed from outside the panel.

In an embodiment of the light-emitting device using the phosphor composition of the first embodiment, at least one of the light wavelength conversion layers 29 is composed of the phosphor composition of the first embodiment, in particular, a phosphor composition that emits red light. . Further, in a preferred embodiment, a blue-light thin film blue phosphor is used as the thin film phosphor 26, and the optical wavelength conversion layer 29 is excited by a blue-emitting green light-emitting material (for example, SrGa ₂ S ₄ :Eu ² a wavelength conversion layer 31 of green light composed of a ⁺ fluorescent body or the like, and a wavelength conversion layer 32 which is a phosphor composition of the first embodiment which emits red light as a red light wavelength conversion layer, and further, As shown in FIG. 14, a portion of the blue light emitted by the thin film blue phosphor does not excite the light wavelength conversion layer 29 but is emitted toward the outside of the panel. Further, the electrodes are configured to be lattice-driven in a matrix form.

As described above, if the light-emitting device emits the blue light 33 emitted from the thin film phosphor 26, the wavelength is converted into the green light 34 by the light wavelength conversion layer 29 (31), and the wavelength is converted by the wavelength conversion layer 29 (32). When it is red light 35, the light-emitting device can emit three primary colors of light such as blue, green, and red. Furthermore, since the lighting of each pixel emitting blue, green, and red light can be separately controlled, a display device capable of full color display can be provided.

According to a preferred embodiment of the phosphor composition of the first embodiment, the red phosphor composition of the first embodiment is used (it is easy to manufacture, chemically stable, and can be excited by blue light to emit red with good color purity) Since light constituting a part of the light wavelength conversion layer 29, it is possible to provide the above-described light-emitting device having high red light-emitting characteristics and high reliability.

As described above, the present invention can provide a phosphor composition containing a composition represented by the above structural formula of aM ₃ N ₂ ‧bAlN‧cSi ₃ N ₄ as a host of a phosphor precursor, which can emit completely novel Warm color (especially red). Further, the present invention provides a method for producing a nitride phosphor composition which is suitable for mass production and which can inexpensively produce the nitride phosphor composition of the present invention. Further, by using a highly efficient novel nitride phosphor composition, it is possible to provide a light-emitting device which is excellent in luminous intensity of a warm-colored light-emitting component (particularly red) and which is inexpensive and uses a novel material.

Hereinafter, the present invention will be specifically described based on examples.

(Example 1)

As the nitride phosphor composition of the present invention, a phosphor composition having a composition of Sr _{o. 98} Eu _{o. 02} AlSiN _{3 was} produced by the following method.

The phosphor composition in this example used the following compounds.

(1) Cerium nitride powder (Sr ₃ N ₂ : purity 99.5%): 25.00 g

(2) Cerium oxide powder (Eu ₂ O ₃ : purity 99.9%): 0.93 g

(3) Cerium nitride powder (Si ₃ N ₄ : purity 99%): 13.00 g

(4) Aluminum nitride powder (AlN: purity 99.9%): 10.78g

The phosphor materials were weighed in a nitrogen atmosphere using a glove box and thoroughly mixed in a mortar. Thereafter, the mixed powder was placed in an aluminum crucible, placed in a predetermined position in an ambient atmosphere furnace, and heated in a nitrogen-hydrogen mixed gas (97% nitrogen 3% hydrogen) atmosphere at 1600 ° C for 2 hours. For simplification, post-treatment such as pulverization, classification, and cleaning is omitted.

Hereinafter, the properties of the fired product (SrAlSiN ₃ :Eu ²⁺ phosphor composition) obtained by the above production method will be described.

The above phosphor composition is bright orange. Fig. 15 is a view showing an emission spectrum (254 nm excitation) 37 and an excitation spectrum 36 of the phosphor composition of the present embodiment obtained by the above production method. Fig. 15 is a red phosphor having a luminescent peak at a wavelength of 635 nm in the above-mentioned fired product, and can be light in a wide wavelength range of 220 to 600 nm, that is, ultraviolet to near ultraviolet to purple to green to green to yellow to orange. Excited. Further, the chromaticity (x, y) of the luminescence in the CIE chromaticity coordinates is x=0.612 and y=0.379.

As a result of semi-quantitative analysis and evaluation of the constituent metal elements of the fired product by the fluorescent X-ray analysis method, the fired product is a compound mainly composed of Sr, Eu, Al, and Si.

These results show that the composition represented by (Sr _0.98 Eu _0.02 )AlSiN ₃ can be produced by the production method of the present embodiment, and the SrAlSiN ₃ :Eu ²⁺ phosphor can be produced. .

For ease of reference, Fig. 16 shows an X-ray diffraction pattern of the phosphor composition of the present embodiment. As shown in FIG. 16, in the diffraction evaluation of the phosphor composition of the present embodiment by the X-ray diffraction method using at least the Cu-Kα line at normal temperature and pressure, the diffraction angle (2θ) is 28 In the vicinity of ~37 ⁰ , it is different from the diffraction peak of an alkaline earth metal oxide or a phosphorous material such as tantalum nitride or aluminum nitride or a conventional Sr ₂ Si ₅ N ₈ compound, and is a crystal having a complex strong diffraction peak. A fluorescent substance.

Further, this example is considered to be a composition represented by a chemical formula (Sr _0.98 Eu _0.02 )AlSiN ₃ or a structural formula represented by (Sr _0.98 Eu _0.02 )AlSiN ₃ or a similar structural formula according to the following chemical reaction formula. Things.

(Chemical reaction formula 1)

1.96Sr ₃ N ₂ +0.06Eu ₂ O ₃ +2Si ₃ N ₄ +6AlN+0.04N ₂ +0.18H ₂ →6Sr _0.98 Eu _0.02 AlSiN ₃ +0.18H ₂ O↑

As described above, by using the production method of the present embodiment, the SrAlSiN ₃ :Eu ²⁺ phosphor can be produced even if Sr ₃ N ₂ which is difficult to operate in the atmosphere and which is expensive in chemical atmosphere is used.

Further, in the present embodiment, a case is described in which a nitride phosphor composition containing Eu ²⁺ ions as a luminescent center ion is described. However, a luminescent center ion other than Eu ²⁺ ions (for example, Ce ³⁾ can be produced in the same manner. ⁺ ion) phosphor composition.

(Example 2)

As the nitride phosphor composition of the present invention, a phosphor composition having a composition of Sr _{o. 98} Eu _0.02 AlSiN ₃ was produced by the following production method different from that of Example 1.

The following compounds were used as the phosphor raw material in this example.

(1) Barium carbonate powder (Sr ₃ CO ₃ : purity 99.9%): 2.894 g

(2) Cerium oxide powder (Eu ₂ O ₃ : purity 99.9%): 0.070 g

(3) Cerium nitride powder (Si ₃ N ₄ : purity 99%): 0.988 g

(4) Aluminum nitride powder (AlN: purity 99.9%): 0.820g

Further, the following solid carbon was used as the reducing agent (adding reducing agent) of the above-mentioned cerium carbonate and the above cerium oxide.

(5) Carbon (graphite) powder (C: purity 99.9%): 0.240 g

First, the phosphor raw materials and the added reducing agent are thoroughly mixed in an automatic mortar. Thereafter, the mixed powder was placed in an aluminum crucible, placed in a predetermined position in an ambient atmosphere furnace, and heated in a nitrogen-hydrogen mixed gas (97% nitrogen 3% hydrogen) atmosphere at 1600 ° C for 2 hours. For the sake of simplicity, post-treatment such as pulverization, classification, and washing is omitted.

Hereinafter, the properties of the fired product (SrAlSiN ₃ :Eu ²⁺ phosphor composition) obtained by the above production method will be described.

The above phosphor composition is orange. Fig. 17 is a view showing an emission spectrum (254 nm excitation) 37 and an excitation spectrum 36 of the phosphor composition of the present embodiment obtained by the above production method. Fig. 17 is a red phosphor having a luminescence peak in the vicinity of a wavelength of 640 nm, which can be light in a wide wavelength range of 220 to 600 nm, that is, ultraviolet to near ultraviolet to purple to green to green to yellow to orange. Excited.

In addition, as a result of semi-quantitative analysis of the constituent metal elements of the fired product by a fluorescent X-ray analysis method, the fired product is a compound mainly composed of Sr, Eu, Al, and Si.

These results show that the composition represented by (Sr _0.98 Eu _0.02 )AlSiN ₃ can be produced by the production method of the present embodiment, and the SrAlSiN ₃ :Eu ²⁺ phosphor can be produced.

For ease of reference, Fig. 18 shows an X-ray diffraction pattern of the phosphor composition of this embodiment. As shown in FIG. 18, in the diffraction evaluation of the phosphor composition of the present embodiment by using the Cu-Kα line at normal temperature and normal pressure by the X-ray diffraction method, the diffraction angle (2θ) is 30 In the vicinity of ~37 ⁰ , it is different from the diffracting peak of an alkaline earth metal oxide or a phosphoric acid material such as tantalum nitride or aluminum nitride or a conventional Sr ₂ Si ₅ N ₈ compound, and is a crystal having a complex strong diffraction peak. Fluorescent body.

Further, in the present embodiment, it is considered that the alkaline earth metal oxide SrO and the lanthanide oxide EuO are substantially reduced by carbon C according to the following chemical reaction formula, and are reacted with nitrogen and tantalum nitride to form a chemical formula (Sr _0.98). compound Eu _0.02) AlSiN ₃ indicates, the compositions or in a (Sr _0.98 Eu _0.02) AlSiN represented by formula ₃ of the formula or similar.

(Chemical reaction formula 2)

0.98SrCO ₃ +0.01Eu ₂ O ₃ +(1/3)Si ₃ N ₄ +AlN+C+(1/3)N ₂ +0.01H ₂ →Sr _0.98 Eu _0.02 AlSiN ₃ +0.98CO ₂ ↑+CO↑+ 0.01H ₂ O↑

Thus, by using the production method of the present embodiment, it is possible to use a commercially inexpensive and inexpensive strontium carbonate as a supply source of an alkaline earth metal without using a Sr metal or Sr ₃ N ₂ which is difficult to operate in the atmosphere and which is difficult to operate in the atmosphere. To produce SrAlSiN ₃ :Eu ²⁺ phosphor.

In the SrAlSiN ₃ :Eu ²⁺ phosphor composition of Example 2, the characteristics when the Eu substitution ratio of Sr (Eu substitution amount: Eu / (Sr + Eu) × 100 (atomic %)) is changed.

Figure 19 is a luminescence spectrum of a different Eu substitution amount of SrAlSiN ³ :Eu ²⁺ phosphor under ultraviolet excitation of 254 nm. As can be understood from Fig. 19, the luminescence peak wavelength is gradually shifted from about 615 nm (Eu substitution amount: 100 atom%) to about 750 nm on the long wavelength side (Eu substitution amount: 100 atom%) as the Eu substitution amount increases. range. Further, as the Eu substitution amount increases, the intensity of the luminescence peak gradually becomes stronger, and the Eu substitution amount exhibits a maximum value in the vicinity of 1 to 3 atom%, and then gradually decreases. Moreover, even if excited by ultraviolet to near ultraviolet to purple to blue to green light in the wavelength range of 250 to 550 nm, the peak position of the emission spectrum hardly changes.

Fig. 20 is a graph showing the relationship between the Eu substitution amount of the SrAlSiN ₃ :Eu ²⁺ phosphor composition to the alkaline earth metal element (Sr) and the luminescence peak wavelength. If the wavelength of the illuminating peak suitable as the illuminating device is 610-660 nm, preferably 620-650 nm, it can be understood from the figure that the preferred Eu substitution amount of the red phosphor used as the illuminating device is 0.1 or more, less than 7 atom%.

21 is a graph showing the relationship between the amount of Eu substitution of the alkaline earth metal element (Sr) and the luminescence peak height (luminescence intensity) of the SrAlSiN ₃ :Eu ²⁺ phosphor composition. Further, even if the peak wavelength of the excitation light source changes between the wavelength range of 250 to 500 nm, the same tendency is exhibited. As is clear from Fig. 21, in terms of luminescent color, the Eu substitution amount is preferably 0.3 atom% or more, less than 6 atom%, more preferably 1 atom% or more, and less than 4 atom%.

That is, as can be understood from Fig. 20 and Fig. 21, the Eu substitution amount of the red phosphor used as the light-emitting device is 0.1 or more, less than 7 atom%, more preferably 1 atom% or more, and less than 4 atoms. %.

Further, in the present embodiment, a case of a nitride phosphor composition containing Eu ²⁺ ions as a luminescent center ion is described. However, a phosphor containing luminescent center ions other than Eu ²⁺ ions may be produced in the same manner. Composition.

(Example 3)

As the nitride phosphor composition of the present invention, a phosphor composition having a substantial composition of Sr _0.98 Ce _0.02 AlSiN _{3 was} produced by the following method.

The following compounds were used as the phosphor raw material in this example.

(1) Barium carbonate powder (Sr ₃ CO ₃ : purity 99.9%): 2.894 g

(2) Cerium oxide powder (CeO ₂ : purity 99.99%): 0.069 g

(3) Cerium nitride powder (Si ₃ N ₄ : purity 99%): 0.988 g

(4) Aluminum nitride powder (AlN: purity 99.9%): 0.820g

Further, the following solid carbon was used as the reducing agent for the above-mentioned cerium carbonate and the above cerium oxide.

(5) Carbon (graphite) powder (C: purity 99.9%): 0.240 g

The phosphor composition was produced in the same manner and in the same manner as in Example 2 using these phosphor materials.

Hereinafter, the properties of the fired product (SrAlSiN ₃ :Ce ³⁺ phosphor composition) obtained by the above production method will be described.

The above phosphor composition is white with a blue-green color. Fig. 22 is a view showing an emission spectrum (254 nm excitation) 37 and an excitation spectrum 36 of the phosphor composition of the present embodiment obtained by the above production method. Fig. 22 shows a blue-green phosphor having a luminescent peak in the vicinity of a wavelength of 504 nm, which can be excited by light of a wide wavelength range of 220 to 450 nm, that is, ultraviolet to near ultraviolet to violet to blue.

These results show that the manufacturing method of the present embodiment can produce a composition represented by SrAlSiN ₃ :Ce ³⁺ .

Further, this example is considered to be the same chemical reaction formula as in Example 2, and substantially reduces the alkaline earth metal oxide SrO and the lanthanide oxide CeO ₂ by carbon C, and reacts with nitrogen and tantalum nitride to A composition represented by a structural formula close to the chemical formula (Sr _0.98 Ce _0.02 ) AlSiN ₃ was produced.

As described above, by using the production method of the present embodiment, it is possible to use a commercially inexpensive and inexpensive strontium carbonate as an alkaline earth metal supply without using a Sr metal or Sr ₃ N ₂ which is chemically unstable and difficult to operate in the atmosphere. Source to make a SrAlSiN ₃ :Ce ³⁺ phosphor composition.

(Example 4)

As the nitride phosphor composition of the present invention, a phosphor composition having a composition of Ca _0.98 Eu _0.02 AlSiN _{3 was} produced by the following method.

In the present embodiment, a phosphor composition was produced in the same manner as in Example 2 except that the following materials were used as the phosphor raw material and the reducing agent (carbon powder) was added.

(1) Calcium carbonate powder (CaCO ₃ : purity 99.9%): 1.962 g

(2) Cerium oxide powder (Eu ₂ O ₃ : purity 99.9%): 0.070 g

(3) Cerium nitride powder (Si ₃ N ₄ : purity 99%): 0.988 g

(4) Aluminum nitride powder (A1N: purity 99.9%): 0.820g

(5) Carbon (graphite) powder (C: purity 99.9%): 0.240 g

Hereinafter, the properties of the fired product (CaAlSiN ₃ :Eu ²⁺ phosphor composition) obtained by the above production method will be described.

The above phosphor composition is orange. Fig. 23 is a view showing an emission spectrum (254 nm excitation) 37 and an excitation spectrum 36 of the phosphor composition of the present embodiment obtained by the above production method. Fig. 23 shows that the above-mentioned fired product is a red-orange phosphor having an emission peak at a wavelength of around 600 nm, and can be excited by light of a wide wavelength range of 220 to 550 nm, that is, ultraviolet to near ultraviolet to purple to green to green. Further, the illuminance chromaticity (x, y) in the CIE chromaticity coordinates is x = 0.496 and y = 0.471.

In addition, as a result of semi-quantitative analysis of the constituent metal elements of the fired product by a fluorescent X-ray analysis method, the fired product is a compound mainly composed of Ca, Eu, Al, and Si.

These results show that the manufacturing method of the present embodiment can produce a composition represented by (Ca _0.98 Eu _0.02 )AlSiN ₃ and can produce a CaAlSiN ₃ :Eu ²⁺ phosphor.

Further, in the present embodiment, it is considered that the alkaline earth metal oxide CaO and the lanthanide oxide EuO are substantially reduced by carbon C according to the following chemical reaction formula, and are reacted with nitrogen and cerium nitride to form a near chemical formula (Ca _0.98). Ce _0.02 ) A composition represented by the structural formula of AlSiN ₃ or a composition represented by a structural formula of (Ca _0.98 Ce _0.02 )AlSiN ₃ .

(Chemical reaction formula 3)

0.98CaCO ₃ +0.01Eu ₂ O ₃ +(1/3)Si ₃ N ₄ +AlN+C+(1/3)N ₂ +0.01H ₂ →Ca _0.98 Eu _0.02 AlSiN ₃ +0.98CO ₂ ↑+CO↑+ 0.01H ₂ O↑

Thus, by using the production method of the present embodiment, calcium metal or Ca ₃ N ₂ which is difficult to operate in the atmosphere and which is difficult to operate in the atmosphere can be used at all, and calcium carbonate which is easy to handle and inexpensive is used as a supply source of the alkaline earth metal. To produce a CaAlSiN ₃ :Eu ²⁺ phosphor.

In the present embodiment, a case is described in which a nitride phosphor composition containing Eu ²⁺ ions as a luminescent center ion is described. However, a luminescent center ion other than Eu ²⁺ ions may be produced in the same manner (for example, Ce ^3+). ) a phosphor composition.

Further, this embodiment describes the use of carbon powder as a method of producing a reducing agent, but a phosphor material such as a nitride (Ca ₃ N ₂ ) using an alkaline earth metal element (calcium) or cerium nitride (Si ₃ N ₄ ). Aluminum aluminum nitride (AlN), Eu raw material (Eu ₂ O ₃ ) or tantalum nitride (EuN) or metal Eu, etc., can be produced in the same manner as in Example 1 without using a reducing agent. ₃ : Eu ²⁺ phosphor.

Further, by appropriately selecting the amount of Eu ²⁺ added or the production conditions, red light having a luminescence peak in a wavelength region of 610 nm or more and less than 650 nm can be obtained from the CaAlSiN ₃ :Eu ²⁺ phosphor, and CaAlSiN ₃ :Eu ²⁺ The light body can also be a red phosphor.

(Examples 5 to 8)

As a phosphor composition of Examples 5 to 8 of the present invention, a phosphor composition represented by a structural formula having a substantial composition of SrAlSiN ₃ ‧a'Si ₃ N ₄ as a phosphor precursor was produced by the following method. .

Hereinafter, as an example, a phosphor composition having a value of a' of 0.5, 0.75, and 1.2, that is, 2SrAlSiN ₃ ‧Si ₃ N ₄ , 4SrAlSiN ₃ ‧3Si ₃ N ₄ , SrAlSiN ₃ ‧Si ₃ N ₄ A method for producing a phosphor composition in which each composition of SrAlSiN ₃ ‧2Si ₃ N ₄ is used as a phosphor precursor and in which 2 atom% of Sr is substituted with Eu is described.

At the time of manufacture, the same phosphor raw materials and addition reducing agents as described in Example 2 were used. The phosphor composition was produced and evaluated in the same manner and under the same conditions as in Example 2 except that the mixing ratio was changed to the weight ratio shown in Table 1.

The characteristics of the obtained phosphor composition will be described below.

The above phosphor compositions are all orange. 24 to 27 are representative examples showing the luminescence spectrum (254 nm excitation) 37 and the excitation spectrum 36 of the phosphor compositions of Examples 5 to 8 obtained by the above production method. 24 to 27 show that the above-mentioned burned materials are red phosphors having an emission peak near a wavelength of 640 nm, and can be light of a wide wavelength range of 220 to 600 nm, that is, ultraviolet to near ultraviolet to purple to blue to green to yellow. ~ Orange light is excited.

Further, the detailed data is omitted. As described in the fifth to eighth embodiments, not only the phosphor composition in which the Eu ²⁺ ion is added to the composition of Si ₃ N ₄ in the excessive addition of SrAlSiN ₃ , but SrAlSiN ₃ is excessively added to the SrAlSiN ₃ . A composition of Eu ²⁺ ions is added to the composition of ₂ Si ₅ N ₈ , SrSiN ₂ , and SrSi ₇ N ₁₀ , that is, the substantial composition is SrAlSiN ₃ ‧a'Sr2Si ₅ N ₈ , SrAlSiN ₃ ‧a'SrSiN _{2 ,} etc. The composition represented by the structural formula is a main body of the phosphor precursor, and a nitride-based phosphor composition in which Eu ²⁺ ions are added as an illuminating center is added, and Eu ² is added to the composition in which the Si ₃ N _{4 is} excessively added. The phosphor composition of the ⁺ ion has the same luminescent properties. Wherein, the above a' may be a value satisfying 0≦a'≦2, preferably 0≦a'≦1, specifically, including 0, being 0.25, 0.33, 0.5, 0.67, 0.75, 1, 1.15, 2 equal values. Further, the above a' may be a value satisfying 0.25 ≦ a' ≦ 2, preferably 0.25 ≦ a' ≦ 1.

Excess addition of Si ₃ N ₄ , Sr ₂ Si ₅ N ₈ , SrSi ₇ N ₁₀ in these phosphor composition systems coexisting with the above-mentioned SrAlSiN 3 or forming a novel compound, for example, Sr ₂ Al ₂ Si ₅ N ₁₀ , Sr ₄ Al ₄ Si ₁₃ N ₂₄ , SrAlSi ₄ N ₇ , SrAlSi ₇ N ₁₁ , Sr ₄ Al ₂ Si ₇ N ₁₄ , Sr ₃ AlSi ₆ N ₁₁ , Sr ₅ AlSi ₁₁ N ₁₉ , Sr ₃ Al ₂ Si ₃ N ₈ , Sr ₂ AlSi ₂ N ₅ , Sr ₃ AlSi ₃ N ₇ , Sr ₃ Al ₂ Si ₉ N ₁₆ , Sr ₂ AlSi ₈ N ₁₃ , Sr ₃ AlSi ₁₅ N _23, etc., whether the novel compound has a fluorescent precursor The function has not been confirmed, and it is necessary to examine it in a variety of crystal structure analysis methods in the future, but both have great possibilities.

(Examples 9 to 25)

As a phosphor composition of Examples 9 to 25 of the present invention, a phosphor represented by a structural formula having a substantial composition of aSr ₃ N ₂ ‧bAlN‧cSi ₃ N ₄ as a phosphor precursor was produced by the following method. Composition.

Hereinafter, as an example, the values of a, b, and c are each a value shown in Table 2, and the phosphor composition in which 2 atom% of Sr is replaced with Eu is shown in Table 2, Table 3, and Table 6, and Manufacturing methods and characteristics. The phosphor compositions of Tables 2, 3, and 6 have slightly different expression methods, but each represents a phosphor composition having the same composition ratio.

Further, as Comparative Examples 1 to 5, the numerical values of a, b, and c are the values shown in Table 4, and the phosphor compositions in which 2 atom% of Sr is replaced with Eu are shown in Table 4, Table 5, and Table 6. And produced and evaluated in the same manner as above. The phosphor compositions of Tables 4, 5, and 6 are slightly different in expression, but each represents a phosphor composition having the same composition ratio.

In the production of these, the same phosphor raw materials and addition reducing agents as described in Example 2 were used. The phosphor composition was produced and evaluated in the same manner and under the same conditions as in Example 2 except that the mixing weight ratio was changed to the weight ratio shown in Table 6.

Hereinafter, the characteristics of the obtained phosphor composition will be briefly described.

The phosphor compositions of the above examples were all orange. The luminescence spectrum and the excitation spectrum are omitted, but any of the phosphor compositions of Examples 9 to 25 is the same as the phosphor of Example 1 or Example 2 shown in Fig. 15 or Fig. 17 at a wavelength of 620 to 640 nm. A red phosphor with a luminescent peak nearby can be excited by a wide wavelength range of 220 to 600 nm, that is, ultraviolet to near ultraviolet to purple to green to green to yellow to orange.

For convenience of reference, the relative values of the luminescence peak wavelength and the luminescence peak height of the phosphor compositions of Examples 9 to 25 and Comparative Examples 1 to 5 were summarized in Table 7.

Further, Fig. 28 is a ternary composition diagram showing the composition range of the phosphor composition of the present invention. In Fig. 28, among the luminescent colors of the phosphor compositions of Examples 1, 2, 5, and 5 to 25 and the phosphor compositions of Comparative Examples 1 to 5, red is represented by ●, and colors other than red are represented by Δ. .

○ in Fig. 28 shows a conventional red light-emitting Sr ₂ Si ₅ N ₈ :Eu ²⁺ nitride tellurite phosphor. Further, Fig. 28 shows a composition of Sr ₃ Al ₂ N ₅ :Eu ²⁺ phosphor which is not stable in the atmosphere and which is not capable of performing evaluation of luminescent properties. Further, when the production conditions of the second embodiment are used, the composition having a high ratio of Sr ₃ N ₂ in the ternary composition diagram of Fig. 28 is melted to make production difficult, and there is a tendency for chemical instability in the atmosphere.

28 and Table 7, it can be understood that the present invention is a phosphor composition different from a conventional nitride phthalate phosphor (for example, Sr ₃ Al ₂ N ₅ :Eu ²⁺ ), and the present invention The phosphor composition is a composition represented by the structural formula of aSr ₃ N ₂ ‧bAlN‧cSi ₃ N ₄ as the main body of the phosphor precursor, and Eu ²⁺ ions are used as an activator, and a, b, and c respectively In order to satisfy the values of 0.2≦a/(a+b)≦0.95, 0.05≦b/(b+c)≦0.8, 0.4≦c/(c+a)≦0.95, it becomes a red phosphor.

Further, in comparison with the conventional nitride phthalate phosphor, the composition of the phosphor represented by the composition is such that a, b, and c satisfy 0.2 ± a / (a + b) ≦ 0.6, 0.3, respectively. ≦b/(b+c)≦0.8, 0.4≦c/(c+a)≦0.8, especially, a, b, and c respectively satisfy 0.2≦a/(a+b)≦0.3, 0.6≦b /(b+c) is a value of 0.8, 0.4≦c/(c ⁺ a)≦0.6, and is a phosphor composition represented by the SrAlSiN ₃ structural formula containing Eu ²⁺ as an activator.

Further, in the examples 9 to 25, the case where the phosphor composition is produced in the same manner as the production method of the second embodiment will be described. However, the same method as the production method in which the nitride raw materials are directly reacted with each other as shown in the first embodiment can be obtained. the result of.

Further, in Examples 9 to 25, the case where the element M is Sr is described, but the same result can be obtained when M is Ca or Ca or Sr is the main body of M and a part of the above M is substituted with Ba, Mg or Zn. .

Hereinafter, other embodiments of the present invention will be described.

The characteristics of the phosphor activated by Eu ^{2+ were} examined in detail, and it was found that the phosphors shown in the following (1) to (3) were excited not only by the violet light-emitting elements having a luminescence peak in the near-ultraviolet-violet region of wavelengths above 360 nm and below 420 nm. The internal quantum efficiency is high, and the internal quantum efficiency is high and good at the wavelength of 420 nm or more and less than 500 nm, especially in the blue region having a wavelength of 440 nm or more and less than 500 nm. The efficiency is 90~100%.

(1) Alkaline earth metal orthosilicate type, thiophthalate type, aluminate type and nitride type (nitride 活化 activated by Eu ²⁺ and having a luminescence peak in a wavelength range of 500 nm to less than 560 nm a green phosphor such as an acid salt or a sialon, for example, (Ba, Sr) ₂ SiO ₄ :Eu ²⁺ , SrGa ₂ S ₄ :Eu ²⁺ , SrAl ₂ O ₄ :Eu ²⁺ , BaSiN ₂ : phosphors such as Eu ²⁺ , Sr _1.5 Al ₃ Si ₉ N ₁₆ :Eu ²⁺ .

(2) Alkaline earth metal orthosilicates, thiosilicates and nitrides (nitride tellurite or sialon) which have Eu ²⁺ activation and have luminescence peaks in the wavelength range from 560 nm to less than 600 nm. a yellow phosphor such as (Sr, Ba) ₂ SiO ₄ :Eu ²⁺ , CaGa ₂ S ₄ :Eu ²⁺ , 0.75 (Ca _0.9 Eu _0.1 )O ̇2.25AlN ̇3.25Si ₃ N ₄ :Eu ²⁺ , Ca _1.5 Al ₃ Si ₉ N ₁₆ :Eu ²⁺ , (Sr,Ca) ₂ SiO ₄ :Eu ²⁺ , CaSiAl ₂ O ₃ N ₂ :Eu ²⁺ , CaSi ₆ AlON ₉ :Eu ²⁺ Fluorescent body.

(3) A red phosphor which is activated by Eu ²⁺ and has a luminescence peak (nitride bismuth hydride or nitrite bismuth citrate) in a wavelength region of from 600 nm to less than 660 nm, for example, A phosphor such as Sr ₂ Si ₅ N ₃ :Eu ²⁺ , SrSiN ₂ :Eu ²⁺ , SrAlSiN ₃ :Eu ²⁺ , CaAlSiN ₃ :Eu ²⁺ , Sr ₂ Si ₄ AlON ₇ :Eu ²⁺ .

The excitation spectrum of the phosphors is in a region shorter than the wavelength of the light emitted by the blue light-emitting element, and the ultraviolet-violet region having a wavelength of 360 nm or more and less than 420 nm has an excitation spectrum, so the blue light is emitted. The external quantum efficiency under excitation of the component is not necessarily high. The internal quantum efficiency is unexpectedly higher than the excitation spectrum, which is 70% or more, and particularly good is 90 to 100%.

As an example, FIG. 29 shows the internal quantum efficiency 40, the external quantum efficiency, and the excitation spectrum 42 of the SrSiN ₂ :Eu ²⁺ red phosphor, and also shows the luminescence spectrum 43 of the phosphor for convenience of reference. In Fig. 30 to Fig. 35, SrAlSiN ₃ :Eu ²⁺ red phosphor (Fig. 30), Sr ₂ lSi ₅ N ₈ :Eu ²⁺ red phosphor (Fig. 31), (Ba, Sr) ₂ SiO ₄ : Eu ²⁺ green phosphor (Fig. 32), (Sr, Ba) ₂ SiO ₄ : Eu ²⁺ yellow phosphor (Fig. 33), (Sr, Ca) ₂ SiO ₄ : Eu ²⁺ yellow phosphor ( Fig. 34), 0.75 (Ca _0.9 Eu _0.1 )O‧2.25AlN‧3.25Si ₃ N ₄ :Eu ² + yellow phosphor (Fig. 35), which is shown in the same manner as Fig. 29. For example, as shown, the original Eu ²⁺ activated silicate phosphor of alkaline earth metal _{(S r, Ba) 2 SiO} 4 33: Eu ²⁺ Yellow external quantum efficiency of the phosphor at a wavelength of 440nm The blue light-emitting element is about 75% excited, about 67% at a wavelength of 460 nm, and about 60% at a wavelength of 470 nm. Further, in the blue region having a wavelength of 440 nm or more and less than 500 nm, the internal quantum efficiency is preferably 85% or more higher than the excitation spectrum, and particularly preferably about 94%.

Further, in addition to the above-described phosphor, the phosphor activated by Eu ²⁺ or Ce ³⁺ may have the same characteristics. As an example, in FIGS. 36 to 39, (Y, Gd) ₃ Al ₅ Ol ₂ : Ce ^{3 +} yellow phosphor ( FIG. 36 ), BaMgAl ₁₀ O ₁₇ : Eu ²⁺ blue phosphor ( FIG. 37 ) , Sr ₄ Al ₁₄ O ₂₅ :Eu ²⁺ blue-green phosphor (Fig. 38), (Sr, Ba) ₁₀ (PO ₄ ) ₆ C ₁₂ :Eu ²⁺ blue phosphor (Fig. 39), also Figure 29 is shown in the same manner.

As can be seen from FIG. 29 to FIG. 36, the dependence of the external quantum efficiency of each phosphor on the excitation wavelength is similar to the shape of the excitation spectrum, and when the peak of the excitation spectrum is excited by light of a long wavelength, for example, the blue light is emitted. Under the excitation of the element, the external quantum efficiency is not necessarily high, but the internal quantum efficiency exhibits a high value under the excitation of the blue light-emitting element. Further, as can be seen from FIGS. 29 to 35 and FIGS. 37 to 39, the internal quantum efficiency of each of the phosphors excited by the ultraviolet light-emitting element was high, and was 90 to 100%.

As a result of further investigation, it was found that the phosphors other than the above (1) to (3) have the internal quantum efficiency high under the excitation of the purple light-emitting device described below (4) and (5).

(4) A cyan or green phosphor which is activated by Eu ²⁺ or Ce ³⁺ and has a luminescence peak (nitride citrate system, sialon system, etc.) in a wavelength region of 490 nm to 550 nm, for example , a phosphor such as Sr ₂ Si ₅ N ₈ :Ce ³⁺ , SrSiAl ₂ O ₃ N ₂ :Eu ²⁺ , Ca _1.5 Al ₃ Si ₉ N ₁₆ :Ce ³⁺ .

(5) Eu ²⁺ activated, and at more than 420nm, less than 500nm region having an emission peak wavelength of the primary alkaline earth metal silicate-based, blue-green or blue of the halophosphate-based phosphor, e.g., Ba ₃ A phosphor such as MgSi ₂ O ₈ :Eu ²⁺ , (Sr,Ca) ₁₀ (PO ₄ ) ₆ Cl ₂ :Eu ²⁺ .

Since the excitation spectrum of the phosphors has an excitation peak in a near-ultraviolet to violet region having a wavelength of 360 nm or more and less than 420 nm, the external quantum efficiency is not high when the violet light-emitting element is excited.

As an example, the internal quantum efficiency 40, the external quantum efficiency 41, and the excitation spectrum 42 of the La ₂ O 2 _s :Eu ³⁺ red phosphor commonly used in combination with the above-described purple light-emitting element are shown in FIG. 40 for convenience of reference. The luminescence spectrum 43 of the phosphor is also shown together. As can be seen from FIG. 40, the internal quantum efficiency and external quantum of the La ₂ O 2 _s :Eu ³⁺ red phosphor are obtained in the ultraviolet region of the excitation spectrum of 380 nm or more, the ultraviolet region of less than 420 nm, and the excitation wavelength of about 360 to 380 nm. The efficiency drops rapidly as the excitation wavelength increases. For example, in a purple region having an excitation wavelength of 380 nm or more and less than 420 nm, when the excitation wavelength is sequentially increased, the internal quantum efficiency is about 80% (380 nm), about 62% (400 nm), and about 25% (420 nm). Drastically lower.

Moreover, although the data is omitted, the internal quantum efficiency, external quantum efficiency, and excitation spectrum of the Y ₂ O ₂ S:Eu ³⁺ red phosphor, and the internal quantum efficiency of the above La ₂ O 2 _S :Eu ³⁺ red phosphor are The external quantum efficiency and excitation characteristics are shifted by 10 to 50 nm toward the short wavelength side.

That is, it is commonly used in combination with the above-mentioned purple light-emitting elements, La ₂ O 2 _S :Eu ³⁺ red phosphor and Y ₂ O ₂ S:Eu ³⁺ red phosphor, although high conversion efficiency will be at the wavelength The light emitted from the light-emitting element having a luminescence peak of 360 nm or more and less than 420 nm (especially the purple region having a wavelength of 380 nm or more and less than 420 nm) is converted into a red light wavelength, but is difficult to be processed in terms of material properties. Light body.

Further, the reason why the above-mentioned La ₂ O ₂ S:Eu ³⁺ red phosphor and Y ₂ O ₂ S:Eu ³⁺ red phosphor exhibit the excitation wavelength dependence of the internal quantum efficiency is as Eu ³⁺ When the charge transfer state (CTS: charge transfer state) is used as the excited state, when the excitation energy is relaxed and illuminates through the 4f energy level of Eu ³⁺ of the CTS, the light is emitted with high efficiency, and without the CTS by Eu ^{3 +} When the light is directly excited, it cannot be illuminated with high efficiency. The above CTS is a state in which one electron moves from the surrounding anion (O or S) to Eu ³⁺ . Therefore, due to the above mechanism, it is difficult for the above-mentioned acid sulfide-based red phosphor and the light-emitting element, particularly the ultraviolet light-emitting element, to obtain a light-emitting device of a strong light beam.

Further, when a plurality of phosphors are excited by a purple light-emitting element to constitute a white light-emitting device, in order to consider the hue balance, the intensity of the output light is correlated with the internal quantum efficiency of the phosphor having the lowest internal quantum efficiency. In other words, in the phosphor constituting the light-emitting device, if there is one phosphor having a low internal quantum efficiency, the intensity of the output light is also lowered, and the white light of the strong light beam cannot be obtained.

Here, the internal quantum efficiency refers to the ratio of the quantum number of light emitted from the phosphor to the quantum number of the excitation light absorbed by the phosphor, and the external quantum efficiency is the excitation of the quantum number of the light emitted by the phosphor to the phosphor. The quantum number of light. That is, high quantum efficiency means that the excitation light is efficiently subjected to light conversion. The method of measuring quantum efficiency has been established and is detailed in the aforementioned Lighting Society.

Light emitted by a light-emitting element that is absorbed by a phosphor having a high internal quantum efficiency is efficiently emitted after light conversion. On the other hand, light emitted from a light-emitting element that is not absorbed by the phosphor is directly discharged. Therefore, a light-emitting element including a light-emitting peak in the above-described wavelength region, and a light-emitting device having a high internal quantum efficiency phosphor excited by the light-emitting element can effectively use light energy. Therefore, by combining at least the phosphors of the above (1) to (5) and the above-mentioned light-emitting elements, a light beam having a strong light beam and a high color rendering can be obtained.

On the other hand, a light-emitting device having a light-emitting element having a light-emitting peak in the wavelength region and a phosphor having a low internal quantum efficiency at the time of excitation of light emitted from the light-emitting element is not effective in light energy emitted from the light-emitting element. The ground is changed, and a low beam illumination device is used.

Further, a light-emitting device having a light-emitting peak in a near-ultraviolet to purple region of 360 nm to less than 420 nm and a phosphor having a low internal quantum efficiency under excitation by light emitted from the light-emitting element have low visibility The light in the near-ultraviolet-purple region is almost independent of the enhanced beam, so if the thickness of the phosphor layer is not increased, the concentration of the phosphor in the phosphor layer is increased, so that the light emitted by the light-emitting element is multiplied by the phosphor. When absorbed, it becomes a low-beam illumination device.

Hereinafter, other embodiments of the light-emitting device of the present invention will be described.

(Embodiment 6)

An example of the light-emitting device of the present invention includes a phosphor layer containing a nitride phosphor and a light-emitting element. In the light-emitting device, the light-emitting element has an emission peak in a wavelength region of 360 nm or more and less than 500 nm, and the nitride phosphor is excited by light emitted from the light-emitting element to emit light, and the nitride phosphor emits light. The composition is used as the output light. Further, the nitride fluorescent system is activated by Eu ²⁺ and is a phosphor represented by a structural formula (Ml-xEux)AlSiN3, wherein the M is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn. The above x is a value satisfying 0.005 ≦ x ≦ 0.3.

The light-emitting element is a photoelectric conversion element that converts electric energy into light, and may be emitted at 360 nm or more, less than 420 nm or 420 nm or more, less than 500 nm, more preferably 380 nm or more, less than 420 nm or 440 nm or more, and less than 500 nm. The light-emitting region has a light-emitting peak, and is not particularly limited. For example, a light-emitting diode (LED), a laser diode (LD), a surface light-emitting LD, an inorganic electroluminescence (EL) element, an organic EL element, or the like can be used. .

When an LED or LD having a GaN-based compound as a light-emitting layer is used for a light-emitting element, it is preferable to emit purple light having a light-emitting peak at 380 nm or more, less than 420 nm, and more preferably 395 nm to 415 nm from the viewpoint of obtaining a high output. The element is preferably a blue light-emitting element having a light-emitting peak in a wavelength region of 440 nm or more, less than 500 nm, and more preferably 450 to 480 nm.

Preferably, the output light includes a light-emitting component that is emitted by the light-emitting element. In particular, when the light-emitting element has a light-emitting peak in the blue region, if the output light contains the light-emitting component and the output light emitted by the nitride phosphor, white light having higher color rendering property can be obtained.

The nitride phosphor is a warm-colored light having an emission peak in a wavelength region of 600 nm or more and less than 660 nm, and preferably emits red light having a light-emitting peak in a wavelength region of 610 nm to 650 nm, and has the above structural formula (M _{1 -x} Eu _x )AlSiN ₃ represents a nitride phosphor having high internal quantum efficiency under excitation light in a wavelength region of 360 nm or more and less than 500 nm, for example, SrAlSiN ₃ :Eu ²⁺ red as shown in FIG. A phosphor or a CaAlSiN ₃ :Eu ²⁺ red phosphor or the like.

A phosphor layer having at least a nitride phosphor having a high internal quantum efficiency and a light-emitting device having the above-described light-emitting element can efficiently output light energy. The light-emitting device having the above configuration is a device having a strong warm-based light-emitting component and a high specific color evaluation number R9. These can be compared to the conventional light-emitting device using La2O2S:Eu ³⁺ phosphor, or a combination of Sr ₂ Si ₅ N ₈ :Eu ²⁺ phosphor and YAG (钇·aluminum ‧ garnet): Ce-based phosphor A conventional light-emitting device having a strong light beam and high color rendering.

The light-emitting device of the present embodiment is not particularly limited as long as it has at least a phosphor layer containing the nitride phosphor and the light-emitting element, and may be, for example, a semiconductor light-emitting device, a white LED, or a display device using a white LED. Use a white LED lighting device, etc. More specifically, display devices using white LEDs include, for example, LED information display terminals, LED traffic signals, LED bulbs for automobiles, and the like. Lighting devices using white LEDs include, for example, LED indoor and outdoor lighting, interior LED lights, LED emergency lights, LED decorative lights, and the like.

Among them, the above LED is particularly preferable. In general, a conventional LED is a light-emitting element that emits a monochromatic light source of a specific wavelength by the principle of its light emission. That is to say, the conventional LED cannot obtain a light-emitting element that emits white light. On the other hand, in the white LED of the present embodiment, white fluorescence can be obtained by, for example, a combination of a conventional LED and a phosphor.

In the present embodiment, in the nitride phosphor, when the main component of the element M is Sr or Ca, a good color tone and a strong light-emitting intensity can be obtained, which is preferable. Further, the main component is Sr or Ca, meaning that 50 atom% of the element M is Ca or Sr. Further, it is more preferable that 80 atom% or more of the element M is Sr or Ca, and it is more preferable that all atoms of the element M are Sr or Ca.

Further, it is preferable that the light-emitting element uses the injection-type electroluminescent element to emit strong output light. If an LED or LED containing a GaN-based semiconductor in the active layer is used, a strong and stable output light can be obtained, which is more preferable.

(Embodiment 7)

In another example of the light-emitting device of the present invention, the phosphor layer of the sixth embodiment may further contain a green phosphor which is activated by Eu ²⁺ or Ce ³⁺ and has an emission peak in a wavelength region of 500 nm or more and less than 560 nm. . The phosphor may be excited by light emitted from the light-emitting element described in the sixth embodiment, and may be emitted in a wavelength region of 550 nm or more and less than 560 nm (preferably, a wavelength region of 510 nm to 550 nm, more preferably The phosphor having a luminescence peak in the wavelength region of 525 to 550 nm is not particularly limited.

For example, when a blue light-emitting element is used, the excitation peak at the longest wavelength side of the excitation spectrum is not a green phosphor in a wavelength region of 420 nm or more and less than 500 nm, that is, it may be the longest wavelength side of the excitation spectrum. The excitation peak is a green phosphor having a wavelength region of less than 420 nm.

The green phosphor is a phosphor having a high internal quantum efficiency at excitation light having a wavelength of 360 nm or more and less than 500 nm, for example, as shown in Fig. 32, (Ba, Sr) ₂ SiO ₄ :Eu ²⁺ green Fluorescent body. It is preferable that the light-emitting device including the phosphor layer containing the phosphor and the light-emitting element can efficiently output light energy. In the light-emitting device, the green light intensity of the output light is increased, and the color rendering property is improved. Moreover, the green light has high visibility and a strong light beam. In particular, by combining with the phosphor contained in the phosphor layer, it is possible to obtain an output light having a high color rendering property with an average color rendering number (Ra) of 90 or more.

If the green phosphor is a nitride phosphor or an oxynitride phosphor activated by Eu ²⁺ , such as BaSiN ₂ :Eu ²⁺ , Sr _1.5 Al ₃ Si ₉ N ₁₆ :Eu ²⁺ , Ca _1.5 Al ₃ Si ₉ N ₁₆ :Eu ²⁺ , CaSiAl ₂ O ₃ N ₂ :Eu ²⁺ , SrSiAl ₂ O ₃ N ₂ :Eu ²⁺ , CaSi ₂ O ₂ N ₂ :Eu ²⁺ , SrSi ₂ O ₂ N ₂ : Eu ²⁺ , BaSi ₂ O ₂ N ₂ :Eu ^{2+ ,} etc.; alkaline earth metal orthosilicate phosphor activated by Eu, such as (Ba, Sr) ₂ SiO ₄ :Eu ²⁺ , (Ba, Ca) ₂ SiO ₄ :Eu ²⁺ or the like; a thiophthalate phosphor activated with Eu, for example, SrGa ₂ S ₄ :Eu ²⁺ or the like; an aluminate phosphor activated with Eu, for example, SrAl ₂ O ₄ : Eu ²⁺ or the like; aluminate phosphor co-activated with Eu ²⁺ and Mn ²⁺ , for example, BaMgAl ₁₀ O ₁₇ :Eu ²⁺ , Mn ^{2+ ,} etc.; nitride activated by Ce ³⁺ a phosphor or an oxynitride phosphor, for example, Sr ₂ Si ₅ N ₈ :Ce ₃₊ , Ca ₁₅ Al ₃ Si ₉ N ₁₆ :Ce ³⁺ , Ca ₂ Si ₅ N ₈ :Ce ^{3+ ,} etc.; A garnet-structured phosphor activated by Ce ³⁺ , such as Y ₃ (Al,Ga) ₅ O ₁₂ :Ce ³⁺ , Y ₃ Al ₅ O ₁₂ :Ce ³⁺ , BaY ₂ SiAl ₄ O _12: Ce ³⁺ , Ca ₃ Sc ₂ Si ₃ O ₁₂ :Ce ^3+, etc. Under the excitation of the component, the internal quantum efficiency will be improved, which is better.

As described above, the light-emitting device of the present embodiment includes the phosphor layer including at least the nitride phosphor of the sixth embodiment and the green phosphor, and the light-emitting element of the sixth embodiment, and the output light contains the nitride. The red component emitted by the phosphor and the green component emitted by the green phosphor.

(Embodiment 8)

In another embodiment of the light-emitting device of the present invention, the phosphor layer of the above-described Embodiment 6 or Embodiment 7 may further include a light-emitting region which is activated by Eu ²⁺ or Ce ³⁺ and has a light-emitting region of 560 nm or more and less than 600 nm. The yellow phosphor of the peak. The yellow phosphor may be excited by light emitted from the light-emitting element described in the sixth embodiment, and may be emitted in a wavelength region of 560 nm or more and less than 600 nm, preferably a wavelength region of 565 nm to 580 nm, more preferably The phosphor having a luminescence peak in a wavelength region of 525 to 550 nm is not particularly limited.

For example, when a blue light-emitting element is used, the excitation peak at the longest wavelength side of the excitation spectrum may not be a yellow phosphor in a wavelength region of 420 nm or more and less than 500 nm, that is, the longest wavelength side of the excitation spectrum. The excitation peak is a yellow phosphor having a wavelength region of less than 420 nm.

The yellow phosphor is a phosphor having a high internal quantum efficiency at excitation light having a wavelength of 360 nm or more and less than 500 nm, and is, for example, (Sr, Ba) ₂ SiO ₄ :Eu ²⁺ yellow as shown in FIG. Phosphor, (Sr, Ca) ₂ SiO ₄ :Eu ²⁺ yellow phosphor shown in Fig. 34, 0.75CaO‧2.25AlN‧3.25Si ₃ N ₄ :Eu ²⁺ yellow phosphor shown in Fig. 35 And a phosphor having high internal quantum efficiency under excitation light of a wavelength region of 420 nm or more and less than 500 nm, for example, (Y, Gd) ₃ Al ₅ Ol ₂ : Ce ^{3 +} yellow phosphor shown in FIG. Wait. It is preferable that the light-emitting device including the phosphor layer containing the phosphor and the light-emitting element can efficiently output light energy. In the light-emitting device, the yellow light-emitting intensity of the output light is increased, and the color rendering property is improved, and in particular, a light-emitting device that emits a warm color system or a warm color light can be provided. Moreover, the yellow light has high visibility and a strong beam. In particular, by the material design of the phosphor material, it is possible to obtain an output light having a high color rendering property with Ra of 90 or more.

If the above-mentioned yellow phosphor, is in the E _u ²⁺ activated nitride phosphor or an oxynitride phosphor, e.g. ^{_{0.75CaO‧2.25AlN‧3.25Si 3 N 4: Eu 2+,}} Ca 1.5 Al 3 Si ₉ N ₁₆ :Eu ²⁺ , CaSiAl ₂ O ₃ N ₂ :Eu ²⁺ , CaSi ₆ AlON ₉ :Eu ^{2+ ,} etc.; alkaline earth metal orthosilicate phosphor activated by Eu ²⁺ , for example, (Sr _{, Ba) 2 SiO 4: Eu} 2+, (Sr, Ca) 2 SiO 4: Eu 2+ and the like; to activation of the E _u ²⁺ phosphor thio gallate, e.g. CaGa ^₂ S _4: E _{u 2} ^+, etc.; and a garnet-structured phosphor activated by Ce ³⁺ , such as (Y, Gd) ₃ Al ₅ O ₁₂ : Ce ^3+, etc., the internal quantum efficiency is increased by excitation of the above-mentioned light-emitting element , for better.

As described above, the light-emitting device of the present embodiment includes the phosphor layer including at least the nitride phosphor of the sixth embodiment and the yellow phosphor, and the light-emitting element of the sixth embodiment, and the output light contains the nitride. The red component emitted by the phosphor and the yellow component emitted by the yellow phosphor.

(Embodiment 9)

In another aspect of the light-emitting device of the present invention, the phosphor layer according to any one of the above-mentioned Embodiments 6 to 8 may further include an luminescence peak which is activated by Eu ²⁺ and has a luminescence peak in a wavelength region of 420 nm or more and less than 500 nm. Blue phosphor. The blue phosphor can be excited by light emitted from the light-emitting element described in the sixth embodiment, and is in a wavelength region of 420 nm or more and less than 500 nm (preferably from 380 to 480 nm from the viewpoint of color rendering and output). The region may be a phosphor having a luminescence peak, and is not particularly limited. In this case, the light-emitting element is not particularly limited as long as it is a light-emitting element described in the embodiment, and it is preferable to use a purple light-emitting element because the selectivity of the phosphor material can be broadened, and not only the design light can be made. The light color emitted by the device is easy, and even if the wavelength position emitted by the light-emitting element fluctuates due to driving conditions such as the input power of the light-emitting element, the influence on the output light is not large.

The blue phosphor is a phosphor having a high internal quantum efficiency in excitation light in a wavelength region of 360 nm or more and less than 500 nm (preferably 360 nm or more and less than 420 nm), for example, as shown in FIG. BaMgAl ₁₀ O ₁₇ :Eu ²⁺ blue phosphor, Sr ₄ Al ₁₄ O ₂₅ :Eu ²⁺ blue phosphor shown in FIG. 38, (Sr,Ba) ₁₀ (PO ₄ ) shown in FIG. ₆ C ₁₂ : Eu ²⁺ blue phosphor, etc. It is preferable that the light-emitting device including the phosphor layer containing the phosphor and the light-emitting element can efficiently output light energy. In the light-emitting device, the blue light-emitting intensity of the output light is increased, the color rendering property is improved, and the light beam is improved. In particular, by designing the material of the phosphor material, it is possible to obtain an output light having a high color rendering property of Ra of 90 or more, and all the special color rendering numbers of R1 to R15 are 80 or more, and preferably 85 or more. More preferably, a white output light of 90 or more close to sunlight can be obtained. For example, by using BaMgAl ₁₀ O ₁₇ :Eu ²⁺ , (Sr,Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ :Eu ²⁺ , Ba ₃ MgSi ₂ O ₈ :Eu ²⁺ , SrMgAl ₁₀ O ₁₇ :Eu ^{2 +} , (Sr, Ca) ₁₀ (PO ₄ )Cl ₂ :Eu ²⁺ , Ba ₅ SiO ₄ Cl ₆ :Eu ²⁺ , BaAl ₈ O ₁ . ₅ :Eu ²⁺ , Sr ₁₀ (PO ₄ )Cl ₂ : A yellow phosphor such as Eu ²⁺ can obtain an output light having the above-described high color rendering property and special color rendering number.

Further, the blue phosphor is a nitride phosphor or an oxynitride phosphor activated by Eu ²⁺ , for example, SrSiAl ₂ O ₃ N ₂ :Eu ²⁺ or the like; an alkaline earth activated with Eu ²⁺ Metal-like orthosilicate phosphors, such as Ba ₃ MgSi ₂ O ₈ :Eu ²⁺ , Sr ₃ MgSi ₂ O ₈ :Eu ^{2+ ,} etc.; aluminate phosphors activated by Eu ²⁺ , such as BaMgAl ₁₀ O ₁₇ :Eu ²⁺ , BaAl ₈ O ₁₃ :Eu ²⁺ , Sr ₄ Al ₁₄ O ₂₅ :Eu ^{2+ ,} etc.; and a halophosphoric acid phosphor activated with Eu ²⁺ , for example, Sr ₁₀ (PO ₄ ) ₆ Cl ₂ :Eu ²⁺ , (Sr,Ca) ₁₀ (PO ₄ ) ₆ Cl ₂ :Eu ²⁺ , (Ba,Ca,Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ :Eu ^{2+ ,} etc. Under the excitation of the component, the internal quantum efficiency is improved, so it is better.

In the sixth to ninth embodiments, in order to obtain a strong light beam, the phosphor contained in the phosphor layer preferably contains substantially no phosphor other than the phosphor activated by Eu ²⁺ or Ce ³⁺ , and is substantially It is preferable that the inorganic phosphor other than the nitride phosphor or the oxynitride phosphor is contained. The phosphor body does not substantially contain a fluorescent system other than the phosphor activated by Eu ²⁺ or Ce ³⁺ , and the phosphor layer contains 90% by weight or more, preferably 95% by weight or more, more preferably 95% by weight or more. Preferably, 98% by weight or more is a phosphor activated with Eu ²⁺ or Ce ³⁺ . The inorganic phosphor other than the nitride phosphor or the oxynitride phosphor is substantially 90% by weight or more, preferably 95% by weight or more, more preferably 95% by weight or more. 98% by weight or more is a nitride phosphor or an oxynitride phosphor. The nitride phosphor and the oxynitride phosphor can maintain a high internal quantum efficiency even at an operating temperature of 100 to 150 ° C and an ambient temperature, and the wavelength peak of the luminescence spectrum does not resemble the alkaline earth. The metal-like orthosilicate phosphor or the phosphor having the garnet structure is shifted toward the short wavelength side. Therefore, in the fluorescent device having the above configuration, even if the input electric power is increased and the excitation light intensity is increased, or the use is performed in a high-temperature atmosphere, the fluctuation of the luminescent color is small, and stable output light can be obtained.

Further, in order to obtain a light-emitting device that emits a strong light beam, the internal quantum efficiency (absolute value) of the phosphor having the lowest internal quantum efficiency excited by the light emitted from the light-emitting element among the phosphors substantially contained in the phosphor layer is More than 80%, preferably more than 85%, more preferably more than 90%.

(Embodiment 10)

Another example of the light-emitting device of the present invention includes a phosphor-containing phosphor layer and a light-emitting element, and the light-emitting element has an emission peak in a wavelength region of 360 nm or more and less than 500 nm, and the phosphor is emitted by the light-emitting element. The light is excited to emit light, and the output light contains at least the luminescent component emitted by the phosphor. And the phosphor comprises Eu ²⁺ can be activated to the above and of 600 nm, of less than 660nm wavelength region having an emission peak of the nitride phosphor or an oxynitride phosphor, and a Eu ²⁺ activated and the above 500nm An alkaline earth metal orthosilicate phosphor having a light-emitting peak in a wavelength region of less than 600 nm is excited by light emitted from the light-emitting element, and the internal quantum efficiency of the phosphor is 80% or more.

The light-emitting element described above can be used in the same manner as the light-emitting element described in the sixth embodiment.

Preferably, the output light contains a luminescent component emitted by the luminescent element. In particular, when the light-emitting element has a light-emitting peak in the blue-wavelength region, the output light contains the light-emitting component emitted by the phosphor and the light-emitting component emitted by the light-emitting element, thereby obtaining white having higher color rendering properties. Light, for better.

The above-mentioned Eu ²⁺ -activated nitride phosphor or oxynitride phosphor is a warm-colored light having a luminescence peak in a wavelength region of 600 nm or more and less than 660 nm, preferably in a wavelength region of 610 to 650 nm. A phosphor having a red-based light having a luminescence peak and a phosphor having a high internal quantum efficiency under excitation light in a wavelength region of 360 nm or more and less than 500 nm. More specifically, it is a nitride aluminosilicate phosphor represented by the structural formula (M _1-x Eu _x )AlSiN ₃ , for example, SrAlSiN ₃ :Eu ²⁺ red phosphor or CaAlSiN ₃ shown in FIG. :Eu ²⁺ red phosphor or the like; a nitride silicate phosphor represented by a structural formula (M _1-x Eu _x )SiN ₂ , for example, SrSiN ₂ :Eu ²⁺ red phosphor shown in FIG. Or a CaSiN ₂ :Eu ²⁺ red phosphor or the like; a nitride silicate phosphor represented by the structural formula (M _1-x Eu _x )Si ₅ N ₈ , for example, Sr ₂ Si ₅ N shown in FIG. ₈ : Eu ²⁺ red phosphor or Ca ₂ Si ₅ N ₈ : E _u ²⁺ red phosphor or Ba ₂ Si ₅ N ₈ :Eu ²⁺ red phosphor; etc.; structural formula (M _1-x Eu _x ) Si ₄ A ₁₀ N ₇ represents an oxynitride aluminosilicate phosphor, for example, Sr ₂ Si ₄ A ₁₀ N ₇ :E _u ²⁺ red phosphor. Wherein M of the above structural formula is an element selected from at least one of Mg, Ca, Sr, Ba, and Zn, and x is a value satisfying 0.005 ≦ x ≦ 0.3.

The alkaline earth metal orthosilicate phosphor is a phosphor which is activated by Eu ²⁺ and has an emission peak in a wavelength region of 500 nm or more and less than 600 nm, preferably 525 nm or more and less than 600 nm, and more specifically a green phosphor having a light-emitting peak in a wavelength region of 525 nm or more and less than 560 nm, preferably in a wavelength region of 530 nm to 550 nm, for example, (Ba, Sr) ₂ SiO ₄ : Eu ²⁺ green as shown in FIG. a phosphor; or a yellow phosphor having an emission peak in a wavelength region of 560 nm or more and less than 600 nm, for example, (Sr, Ba) ₂ SiO ₄ :Eu ²⁺ yellow phosphor shown in FIG. 33, as shown in FIG. Sr, Ca) ₂ SiO ₄ :Eu ²⁺ yellow phosphor or the like, and the internal quantum efficiency is high under excitation light having a wavelength region of 360 nm or more and less than 500 nm.

The phosphor is internally excited by light emitted from the light-emitting element to have an internal quantum efficiency of 80% or more, preferably 85% or more, more preferably 90% or more. A light-emitting device having at least a phosphor layer containing a phosphor having a high internal quantum efficiency as described above and the above-described light-emitting element can efficiently output light energy. Further, in the light-emitting device comprising the above-described nitride phosphor or oxynitride phosphor, the intensity of the warm-colored light-emitting component is strong, and the value of the special color rendering number R9 is large.

Further, the light-emitting device having the above configuration does not use a sulfide-based phosphor having a problematic reliability, and only a red phosphor using a high-priced nitride phosphor or an oxynitride phosphor is used, so that a strong light beam can be provided. The high-color white light source can reduce the cost of light-emitting devices such as white light sources.

The light emitting device according to the present embodiment, at least as long as the above-containing nitride phosphor or an oxynitride phosphor of the Eu ²⁺ -activated red-emitting, and the alkaline earth metal to the Eu ²⁺ -activated silicate of the original The phosphor layer of the salt phosphor and the light-emitting element are not particularly limited, and for example, the white LED.

In the present embodiment, the nitride phosphor or the oxynitride phosphor represented by the above structural formula is more preferably a good color tone and a strong luminescent intensity when the main component of the element M is Sr or Ca. Further, the main component is Sr or Ca, which means that 50 atom% or more of the element M is any element of Sr or Ca. Preferably, 80 atom% or more of the element M is any element of Sr or Ca, and more preferably all of the elements M are either Sr or Ca.

Further, when the light-emitting element uses the injection-type electroluminescent element, it is possible to emit strong output light, which is more preferable.

The alkaline earth metal orthosilicate phosphor is preferably activated by EU ²⁺ and is in a wavelength region of 500 nm or more and less than 560 nm, preferably 525 or more and less than 560 nm, more preferably 530~. A green phosphor having a light-emitting peak in a wavelength region of 550 nm or less, for example, (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ , (Ba,Ca) ₂ SiO ₄ :Eu ^{2+ can be used} . In the light-emitting device using a green phosphor, the green light contained in the output light has high luminous intensity and high color rendering property. Moreover, the green light has high visibility and a stronger beam. In particular, high color rendering output light with Ra of 90 or more can be obtained depending on the combination of phosphors in different phosphor layers.

Further, the alkaline earth metal orthosilicate phosphor is preferably a yellow phosphor having an emission peak in a wavelength region of 560 nm or more and less than 600 nm, preferably in a wavelength range of 565 to 580 nm, which is activated by EU ²⁺ . For example, (Sr,Ba) ₂ SiO ₄ :Eu ²⁺ can be used. According to the light-emitting device of the yellow phosphor, the yellow light-emitting intensity of the output light is increased, and the color rendering property is improved, and in particular, a light-emitting device that emits warm color or warm color light can be provided. Moreover, the yellow light has a higher visibility and the light beam also becomes stronger. In particular, according to the design of the phosphor layer material, high color rendering output light with Ra of 90 or more can be obtained. Further, it is preferable to use (Sr, Ca) ₂ SiO ₄ :Eu ²⁺ yellow phosphor which emits fluorescence close to the yellow phosphor.

In the present embodiment, it is preferable that the phosphor other than the red phosphor contained in the phosphor layer contains substantially no nitride phosphor or oxynitride phosphor. Thereby, the amount of use of the nitride phosphor or the oxynitride phosphor used in the light-emitting device can be minimized, and the manufacturing cost of the light-emitting device can be reduced. Preferably, the phosphor other than the red phosphor contained in the phosphor layer is substantially free of sulfide phosphor. Thereby, the reliability of the light-emitting device can be improved, and for example, a light-emitting device having little change with time such as deterioration can be provided.

Further, in the tenth embodiment, the phosphor contained in the phosphor layer is a strong light beam, and is preferably a phosphor other than the phosphor which is substantially free of Eu ²⁺ or Ce ³⁺ activation. Further, in the phosphor substantially contained in the phosphor layer, it is preferable that the internal quantum efficiency of the phosphor having the lowest internal quantum efficiency is 80% or more under excitation of light emitted from the light-emitting element.

Hereinafter, the light-emitting devices of Embodiments 6 to 10 will be described using Figs. 1 to 12 described above.

1, 2 and 3 are cross-sectional views showing a semiconductor light-emitting device which is an example of a light-emitting device of the present invention.

Fig. 1 shows a semiconductor light-emitting device in which at least one light-emitting element 1 is mounted on a base member 4 and sealed with a base material containing a phosphor composition 2 and also serving as a phosphor layer 3. 2 shows a semiconductor light-emitting device which is attached to the cup body 6 provided on the carrier wire of the lead frame 5, and has at least one light-emitting element 1 disposed therein, and is provided with a phosphor body in the cup body 6. The phosphor layer 3 of the object 2 has a structure in which the sealing material 7 such as a resin is sealed as a whole. Fig. 3 shows a wafer type semiconductor light-emitting device in which at least one light-emitting element 1 is mounted in a casing 8, and a phosphor layer 3 containing a phosphor composition is provided.

In FIGS. 1 to 3, the light-emitting element 1 is a photoelectric conversion element capable of converting electric energy into light energy, and is preferably 360 nm or more and less than 500 nm, preferably 380 nm or more, less than 420 nm, or 440 nm or more and less than 500 nm. More preferably, it is not particularly limited as long as it has a light-emitting peak in a wavelength region of 395 to 415 nm or 450 to 480 nm, and for example, an LED, an LD, a surface-emitting LED, an inorganic EL element, an organic EL element, or the like can be used. In particular, in order to increase the output of the semiconductor light-emitting element, it is preferable to use an LED or a surface-emitting LED.

In FIGS. 1 to 3, the phosphor composition 2 in the phosphor layer 3 is a nitride phosphor represented by a structural formula (M _1-x Eu _x )AlSiN ₃ , which disperses the phosphor. to make. M is an element selected from at least one of Mg, Ca, Sr, Ba, and Zn, and x is a value satisfying 0.005 ≦ x ≦ 0.3.

The material used for the base material of the phosphor layer 3 is not particularly limited, and generally, a transparent resin such as an epoxy resin or an anthrone resin or a low-melting glass may be used. In order to provide a light-emitting device in which the luminous intensity decreases with a decrease in the operation time, the base material is preferably a light-transmitting inorganic material such as an fluorenone resin or a low-melting glass, and more preferably a light-transmitting inorganic material. For example, when the base material of the phosphor 3 is made of the above transparent resin, the content of the nitride phosphor is preferably from 5 to 80% by weight, more preferably from 10 to 60% by weight. The nitride phosphor contained in the phosphor layer 3 can absorb a part or all of the light emitted by the light-emitting element to be converted into red light, so that the output light of the semiconductor light-emitting device contains at least the light emitted by the nitride phosphor. ingredient.

Further, when the phosphor composition 2 contains at least a nitride phosphor represented by a structural formula (M _1-x Eu _x )AlSiN ₃ , the phosphor layer 3 may further contain a nitride other than the nitride phosphor. The phosphor can also be included. For example, if the above-mentioned high alkaline earth metal orthosilicate phosphor, nitride having high internal quantum efficiency, for example, activated by Eu ²⁺ or Ce ³⁺ and excited in a wavelength region of 360 nm or more and less than 500 nm is used. Phosphors, oxynitride phosphors, aluminate phosphors, halophosphate phosphors, thiophthalate phosphors, etc., will illuminate according to the combination of (1) to (6) shown below. The element 1 is formed as a violet light-emitting element having a light-emitting peak in a wavelength region of 360 nm or more and less than 420 nm, and the light emitted from the light-emitting element 1 can efficiently excite the phosphor and emit light by the plurality of phosphors. The color mixture is mixed, and is, for example, a semiconductor light-emitting element that emits white light.

(1) A phosphor layer comprising: a blue phosphor which emits light having a luminescence peak in a wavelength region of 420 nm or more and less than 500 nm, preferably 440 nm or more and less than 500 nm; and a green phosphor emitted at 500 nm Above, below 560 nm, preferably in the wavelength region of 510 nm to 550 nm, having a luminescence peak; the yellow phosphor emitting light having a luminescence peak in a wavelength region of 560 nm or more, less than 600 nm, preferably 565 nm to 580 nm; Nitride phosphor.

(2) A phosphor layer comprising: a blue phosphor which emits light having a luminescence peak in a wavelength region of 420 nm or more and less than 500 nm, preferably 440 nm or more and less than 500 nm; and a green phosphor emitted at 500 nm The light having a luminescence peak in a wavelength region of less than 560 nm, preferably 510 nm to 550 nm; and the above-described nitride phosphor.

(3) A phosphor layer comprising: a blue phosphor which emits light having a luminescence peak in a wavelength region of 420 nm or more and less than 500 nm, preferably 440 nm or more and less than 500 nm; and a yellow phosphor emitted at 560 nm The light having a luminescence peak in a wavelength region of less than 600 nm, preferably 565 nm to 580 nm; and the above-described nitride phosphor.

(4) A phosphor layer comprising: a green phosphor which emits light having a luminescence peak in a wavelength region of 500 nm or more, less than 560 nm, preferably 510 nm to 550 nm; and a yellow phosphor which emits at 560 nm or more. Light having a luminescence peak in a wavelength region of 600 nm, preferably 565 nm to 580 nm; and the above-described nitride phosphor.

(5) A phosphor layer comprising the yellow phosphor and the nitride phosphor.

(6) A phosphor layer comprising the green phosphor and the nitride phosphor.

Further, when the phosphor combination of (7) to (9) is used as follows, the light-emitting element 1 is formed as a blue light-emitting element having a light-emitting peak in a wavelength range of 420 nm to less than 500 nm, and is emitted from the light-emitting element 1. When the light is mixed with the light emitted by the phosphor, it can be a semiconductor light-emitting device that emits white light.

(7) A phosphor layer comprising: a green phosphor which emits light having a luminescence peak in a wavelength region of 500 nm or more and less than 560 nm, preferably 525 nm or more and less than 560 nm; and a yellow phosphor which emits at 560 nm. The light having a luminescence peak in a wavelength region of less than 600 nm, preferably 565 nm to 580 nm; and the above-described nitride phosphor.

(8) A phosphor layer comprising the yellow phosphor and the nitride phosphor.

(9) A phosphor layer comprising the green phosphor and the nitride phosphor.

If the light emitting element is a blue light emitting element, the green phosphor, the yellow phosphor in addition to the above-described alkali earth metal atom silicate phosphor of the Eu ²⁺ activator, Eu ²⁺ activated nitride phosphor of Alternatively, in addition to the oxynitride phosphor, a phosphor having a Ce ³⁺ -activated garnet structure (in particular, a YAG:Ce-based phosphor) and Eu ²⁺ -activated thioantate fluorite may be used. Light body, etc. More specifically, for example, SrGa ₂ S4:Eu ²⁺ green phosphor, Y ₃ (Al,Ga) ₅ O ₁₂ :Ce ³⁺ green phosphor, Y ₃ Al ₅ O ₁₂ :Ce ³⁺ green can be used. Phosphor, BaY ₂ SiAl ₄ O ₁₂ :Ce ³⁺ green phosphor, Ca ₃ Sc ₂ Si ₃ O ₁₂ :Ce ³⁺ green phosphor, (Y,Gd) ₃ Al ₅ O ₁₂ :Ce ³⁺ Yellow phosphor, Y ₃ Al ₅ O ₁₂ :Ce ³⁺ , Pr ³⁺ yellow phosphor, CaGa ₂ S ₄ :Eu ²⁺ yellow phosphor, and the like.

Alternatively, the phosphor composition 2 of the phosphor layer 3 in FIGS. 1 to 3 may be a red-emitting photo-nitride phosphor or an oxynitride phosphor which is activated by at least Eu ²⁺ , and Eu ^{2+ is} activated by dispersing an alkaline earth metal orthosilicate phosphor having an emission peak in any wavelength region of 500 nm or more, less than 560 nm or 560 nm or more and less than 600 nm.

As the phosphor layer 3, the base material of the above-described phosphor layer 3 can be used. Further, the phosphor composition 2 contained in the phosphor layer 3 can absorb a part or all of the light emitted from the light-emitting element 1 and convert it into light, so that the output light of the semiconductor light-emitting device contains at least a nitride phosphor or The luminescent component emitted by the oxynitride phosphor and the luminescent component emitted by the alkaline earth metal orthosilicate phosphor.

Further, phosphor composition 2, lines containing the Eu ²⁺ activated nitride red light emitting phosphor or an oxynitride phosphor, and the Eu ²⁺ activated and the above 500 nm, less than 560nm or more than 560nm In the case of an alkaline earth metal orthosilicate phosphor having a luminescence peak in any wavelength region of less than 600 nm, the phosphor layer 3 may further contain the above-mentioned nitride phosphor or oxynitride phosphor and alkaline earth metal precursor. Phosphors other than acid sulfates, but they are not included.

In order to reduce the amount of use of the nitride phosphor or the oxynitride phosphor or the sulfide-based phosphor, it is preferred to contain no nitride phosphor or oxynitride phosphor or sulfide other than the above. A fluorescent body.

For example, the aluminate phosphor, the halophosphate phosphor, etc., which are activated by Eu ²⁺ or Ce ³⁺ and excited in a wavelength region of 360 nm or more and less than 500 nm, and the above (1) When the phosphors of the (6) are combined, the light emitted from the light-emitting element 1 can efficiently excite the phosphor, and the light emitted by the plurality of phosphors is mixed to become a semiconductor light-emitting device that emits white light. Further, when the phosphors shown in the above (7) to (9) are combined, the light emitted from the light-emitting element 1 is mixed with the light emitted from the phosphor, and becomes a semiconductor light-emitting device that emits white light.

In the semiconductor light-emitting device of the present embodiment, since the phosphor having a high external quantum efficiency and high internal quantum efficiency is excited by the blue light-emitting element, for example, the light emitted by the blue light-emitting element and the fluorescent light are used. When the light emitted by the light body is mixed to obtain the desired white light, a large amount of phosphor is required. Therefore, in order to obtain desired white light, it is necessary to increase the thickness of the phosphor layer, and if the thickness of the phosphor layer is increased, it becomes a light-emitting device having a small amount of white light, which is an advantage.

When the phosphor layer 3 has a complex or multilayer structure and a part of the layer is a phosphor layer containing the nitride phosphor or the oxynitride phosphor, the luminescent color spot of the semiconductor light-emitting device of the embodiment can be suppressed. Or it is better to output spots.

Further, since the nitride phosphor or the oxynitride phosphor having Eu ²⁺ as the luminescent center ion can absorb blue, green, and yellow visible light and convert it into red light, if the above-mentioned nitride phosphor or oxygen is contained, The phosphor layer of the nitride phosphor is formed by mixing a phosphor of any of a blue phosphor, a green phosphor, and a yellow phosphor with the nitride phosphor or the oxynitride phosphor. The light emission of the blue, green, and yellow phosphors is also absorbed, and the nitride phosphor or the oxynitride phosphor emits red light. Therefore, the illuminating color control of the illuminating device becomes difficult due to the process of the phosphor layer. In order to prevent this problem, it is preferable that the phosphor layer 3 has a plurality of layers or a multilayer structure, and the layer closest to the main light output surface of the light-emitting element 1 is a red-emitting nitride phosphor or oxynitride phosphor. The body is made less susceptible to the luminescence of the blue, green, and yellow phosphors described above. Further, since the yellow phosphor activated by Eu ²⁺ or Ce ³⁺ is excited by blue light or green light, the green phosphor activated by Eu ²⁺ or Ce ³⁺ is blue light. Excited, the same problem as described above occurs when a plurality of phosphors having different luminescent colors are mixed to form the phosphor layer 3. In order to solve this problem, in the semiconductor light-emitting device of the present embodiment, the phosphor layer 3 is preferably a multi-layer or multi-layer structure, and the layer away from the main light output surface of the light-emitting element 1 is a phosphor containing a short-wavelength light. Floor.

The semiconductor light-emitting device of the present embodiment includes the above-described light-emitting element and a nitride phosphor or oxynitride phosphor which has high internal quantum efficiency and can efficiently convert excitation light into red light under excitation of the light-emitting element. Since the phosphor layer has at least the red light-emitting component emitted by the nitride phosphor or the oxynitride phosphor, the output light of the light-emitting device has both a strong light beam and high color rendering properties, and in particular, a warm color is emitted. It is white light. Further, when the light-emitting element is a blue light-emitting element, the output light further includes a light-emitting component emitted by the light-emitting element.

4 and 5 are schematic views showing the configuration of an illumination and display device which is an example of a light-emitting device of the present invention. 4 shows an illumination display device including at least one semiconductor light-emitting device 9 (a phosphor layer 3 including the above-described phosphor composition 2 and a light-emitting element 1) and an output light 10 thereof. Fig. 5 shows an illumination display device including at least one light-emitting element 1 combined with a phosphor layer 3 of the above-described phosphor composition 2, and an output light 10 thereof. The phosphor layer 3 of the light-emitting element 1 can be the same as the semiconductor light-emitting device described above. Further, the action or effect of the illumination display device of this configuration is also the same as that of the semiconductor light-emitting device described above.

6 to 12 are specific examples of the illumination display device of the embodiment of the light-emitting device of the present invention schematically shown in Figs. 4 and 5 described above. FIG. 6 shows a perspective view of a lighting module 12 having integrally formed light-emitting portions 11. FIG. 7 shows a perspective view of the illumination module 12 having a plurality of light-emitting portions 11. Fig. 8 shows a perspective view of a table lamp type illumination device having a light-emitting portion 11 and capable of controlling the opening and closing or the amount of light by the switch 11. FIG. 9 shows a side view of a lighting device comprising a light source 12 having a screw-in base 14, a reflector 15 and a plurality of light-emitting portions 11. 10 is a bottom view of the lighting device of FIG. 9. FIG. 11 is a perspective view of a flat-panel image display device having a light-emitting portion 11. Fig. 12 is a perspective view of a segmented digital display device having a light-emitting portion 11.

The illumination and display device of the present embodiment is configured to use a phosphor having a high internal quantum efficiency under excitation by the above-described light-emitting element, and in particular, a red light-emitting component having a strong light-emitting component and excellent color rendering properties is used. It has good characteristics equal to or higher than that of the conventional illumination display device, and has high color rendering properties of strong light beams and particularly red-based light-emitting components.

As described above, according to the present invention, by combining at least the nitride phosphor represented by the above structural formula (M _1-x Eu _x )AlSiN ₃ and the above-mentioned light-emitting element, it is possible to obtain a light beam having both a strong light beam and high color rendering properties. The device, in particular, a light-emitting device that emits warm white light.

Further, according to the present invention, at least a nitride phosphor or an oxynitride phosphor having an emission peak in a wavelength region of 600 nm or more and less than 660 nm is combined, and the above-mentioned wavelength region of 500 nm or more and less than 600 nm has a light-emitting peak. The alkaline earth metal orthosilicate phosphor and the light-emitting element can provide a light-emitting device having both a strong light beam and high color rendering properties, and in particular, a light-emitting device that emits white light of a warm color.

Hereinafter, the light-emitting device of the present invention will be described in more detail by way of examples.

(Example 26)

In this embodiment, a light-emitting device of the card-type illumination module light source shown in Fig. 41 is produced, and the light-emitting characteristics are evaluated. Figure 42 is a partial cross-sectional view of Figure 41.

First, a method of manufacturing the semiconductor light-emitting device 44 will be described. On each of the pair of n-electrodes 46 and p-electrodes 47 of the Si diode element (base element) 45 formed in an array on the n-type Si wafer, GaInN is used as a microbump structure. A blue LED wafer 49 having a light-emitting peak at about 470 nm is emitted from the light-emitting layer.

Further, since the blue LED chips 49 are mounted on the respective Si diode elements 45 formed in a matrix, the blue LED chips 49 are also arranged in a matrix.

Next, after the n-electrode 46 and the p-electrode 47 are connected to the n-electrode and the p-electrode of each of the blue LED chips 49, a phosphor layer 3 containing a phosphor composition is formed on the peripheral portion of the blue LED chip 49 by a printing technique. . The upper surface of the phosphor layer 3 is ground and flattened, and then cut into semiconductor light-emitting devices 44 by using a diamond knife.

Next, a first insulator thick film 51 (thickness: 75 μm), a copper electrode 52 (thickness: about 10 μm, width: 0.5 mm), and a second insulator thick film 53 are sequentially laminated on the aluminum metal substrate 50 (size: 3 cm × 3 cm, thickness: 1 mm). (thickness: 30 μm), electrode pads 54a and 54b (thickness: about 10 μm, total of 64 pairs) to form a heat-dissipating multilayer substrate 55. The first insulator thick film 51 and the second insulator thick film 53 are made of an alumina-dispersed epoxy resin formed by thermocompression bonding. Further, the copper electrode 52 is patterned by an etching technique, and the electrode pads 54a and 54b are formed by a etching technique to form a negative electrode and a positive electrode for power supply. Further, a contact hole is provided in one of the second film thickness films 53 so that the electrode pads 54a and 54b can be supplied with power through the copper electrode 52.

Next, the semiconductor light-emitting device 44 is placed on a predetermined position on the heat-dissipating multilayer substrate 55. At this time, the inner electrode (n electrode) 56 of the Si diode element 45 is fixedly connected to the electrode pad 54a by using an Ag paste, and the bonding pad portion 58 on the p electrode 47 is connected to the bonding pad 58 by using the Au wire 57. The electrode pad 54b allows power to the semiconductor light emitting device.

Next, an aluminum metal reflecting plate 59 having an inverted conical cylindrical grinding hole is adhered to the heat dissipation multilayer substrate 55 by using an adhesive. At this time, the semiconductor light-emitting device 44 on the heat-dissipating multilayer substrate 55 can be wrapped in the polishing hole portion of the aluminum metal reflector 59. Then, the semiconductor light-emitting device 44 and the entire polishing hole portion were wrapped with an epoxy resin to form a dome-shaped crucible 60, and the light-emitting device of Example 26 was obtained.

Figure 41 is a perspective view of a light-emitting device of Embodiment 26. In Example 26, a card type illumination module light source was produced using 64 semiconductor light-emitting devices 44, and the light-emitting characteristics were evaluated.

In the twenty-sixth embodiment, a semiconductor current light-emitting device group in which 32 copper electrodes 52 are connected in series is used, and a current of about 80 mA is applied to a total of about 80 mA to drive the semiconductor light-emitting device 44 to obtain output light. The output light is a mixed light of light emitted from the blue LED chip 49 and light emitted from a phosphor contained in the phosphor layer 3 that is excited by the light. The output light can obtain arbitrary white light by appropriately selecting the type and amount of the LED chip and the phosphor.

The phosphor layer 3 will be described in detail below.

The phosphor layer 3 is formed by drying and solidifying an epoxy resin to which a phosphor is added. In Example 26, two kinds of phosphors were used, one was SrAlSiN ₃ :Eu ²⁺ red phosphor having a luminescence peak at a wavelength of 625 nm (center particle diameter: 2.2 μm, maximum internal quantum efficiency '60%), and the other For the (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ green phosphor (center particle diameter: 12.7 μm, maximum internal quantum efficiency: 91%) having an emission peak near the 555 nm wavelength, the epoxy resin uses a two-liquid mixed type ring The main component of the oxygen resin is an epoxy resin containing a bisphenol A type liquid resin as a main component, and the hardener is an epoxy resin containing an alicyclic acid anhydride as a main component. The weight mixing ratio of the SrAlSiN ₃ :Eu ²⁺ red phosphor to the (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ green phosphor is about 1:10. The weight ratio of the mixed phosphor to the epoxy resin was about 1:3 (phosphor concentration = 25% by weight).

(Comparative Example 6)

Two kinds of phosphors were used, one was Sr ₂ Si ₅ N ₈ :Eu ²⁺ red phosphor having a luminescent peak near the wavelength of 625 nm (center particle diameter: 1.8 μm, maximum internal quantum efficiency: 62%), and the other was A Y ₃ Al ₅ O ₁₂ :Ce ³⁺ yellow phosphor having a luminescence peak near the wavelength of 560 nm (central particle diameter: 17.6 μm, maximum internal quantum efficiency: 98%), and a card type illumination mode was produced in the same manner as in Example 26. Group light source. In the phosphor layer 3, the mixing ratio of the Sr ₂ Si ₅ N ₈ :Eu ²⁺ red phosphor to the Y ₃ Al ₅ O ₁₂ :Ce ³⁺ yellow phosphor is about 1:6, and the mixed phosphor is The weight mixing ratio of the epoxy resin was about 1:14 (phosphor concentration = 6.7% by weight). Then, as in the embodiment, the output light was obtained by flowing a current through the semiconductor light-emitting device, and the light-emitting characteristics were evaluated.

Regarding the thickness of the phosphor layer 3, in order to obtain white light of a homochromatic color (correlation color temperature of about 3800 K, duv, chromaticity), the thickness in Example 26 was about 500 μm, and the thickness of Comparative Example 6 was about 100 μm. Further, the luminescent characteristics of the SrAlSiN ₃ :Eu ²⁺ red phosphor of Example 26 and the Sr ₂ Si ₅ N ₈ :Eu ²⁺ red phosphor of Comparative Example 6 were similar. Therefore, in order to increase the comparison accuracy as much as possible, the fluorescent system of Example 26 was selected as much as possible from the green phosphor of Comparative Example 6. Of Example 26 _{(Ba, Sr) 2 SiO 4} : Eu 2+ Green phosphor of FIG. 32 _{(Ba, Sr) 2 SiO 4} : Sr and Ba, Eu ²⁺ Green phosphor although the atomic ratio Different, however, the excitation wavelength dependence of internal quantum efficiency and external quantum efficiency is similar.

Hereinafter, the light-emitting characteristics of the light-emitting devices of Example 26 and Comparative Example 6 will be described.

Fig. 43 and Fig. 44 show the luminescence spectra of Example 26 and Comparative Example 6, respectively. As can be seen from FIG. 43 and FIG. 44, the light-emitting devices of Example 26 and Comparative Example 6 have very similar luminescence spectra, and all emit white light having a luminescence peak near 470 nm and around 600 nm, that is, blue light and yellow light are emitted. It is a white light that is mixed with light.

Table 8 shows the characteristics of the light-emitting devices of Example 26 and Comparative Example 6.

The duv of Table 8 is an index showing the deviation of white light from the black body emission trajectory. Ra is the average color rendering number, R9 is the red special color evaluation number, and the color seen by the reference light is 100, which indicates the degree to which the test light faithfully reproduces the test color.

In the case of about the same light color (correlated color temperature, duv and chromaticity), Example 26 used a (Ba, Sr) ₂ SiO ₄ :Eu ²⁺ green phosphor having a low luminescence intensity under 470 nm light irradiation, but Ra, R9, and the light beam which are substantially equal to Comparative Example 6 are still displayed. That is to say, Example 26 has equivalent luminescent properties as compared with a conventional illuminating device having both high color rendering and strong light beam. The reason for this is presumably that the quantum efficiency of the phosphor used in Example 26 is high under the illumination of the blue LED, and the light emitted by the blue LED absorbed by the phosphor can be efficiently wavelength-converted. It emits light and efficiently outputs light emitted by the unabsorbed blue LED.

Further, the correlated color temperature of the light-emitting device can be arbitrarily adjusted by changing the phosphor concentration or the thickness of the phosphor layer, and at least one type of phosphor having a predetermined spectral distribution and a predetermined internal quantum efficiency, and a transmittance are used. A base material of 100% (for example, a resin) constitutes a phosphor layer, and a light-emitting device is constructed using a fixed output light-emitting element having a predetermined spectral distribution, and the number of color evaluations when the correlated color temperature of the output light is changed can be evaluated by simulation. Light-emitting characteristics such as light beams. Among them, the color evaluation number may not require an internal quantum efficiency value, and may be simulated only from the spectral distribution of the phosphor and the light-emitting element. Therefore, in order to examine the light color of the light-emitting device which has both high color rendering properties and strong light beams, when the duv of the white light emitted by the light-emitting devices of Example 26 and Comparative Example 6 is changed to 0 and the correlated color temperature is changed, the simulation is performed on Ra. Evaluate with the behavior of the relative beam.

Fig. 45 is a view showing the influence of the white light emitted from the light-emitting devices of Example 26 and Comparative Example 6 on the relative light beam when the correlation color temperature was changed by the simulation evaluation. As can be seen from FIG. 45, Example 26 and Comparative Example 6 show the same fluctuation. When the color temperature of the white light is 3,000 to 6000 K, preferably 3500 to 5000 K, when the correlated color temperature is 3797 K, Example 26 For the light source of Comparative Example 6, 95 to 100% is a strong beam. Further, the light beam when the correlated color temperature of Comparative Example 6 is controlled to 3797 K is indicated by a solid line in Fig. 45.

Fig. 46 is a graph showing the influence of white light emitted from the light-emitting devices of Example 26 and Comparative Example 6 on Ra when the correlation color temperature was changed by a simulation evaluation. When the color temperature of the white light is 2000 to 5000 K, preferably 2500 to 4000 K, the Ra of Example 26 and Comparative Example 6 is a higher value of 80 or more.

As can be seen from FIG. 45 and FIG. 46, when the color temperature of the white light is 3,000 to 5,000 K, preferably 3,000 to 4,500 K, more preferably 3,500 to 4,000 K, the embodiment 26 and the comparative example 6 can be obtained. A light-emitting device with a strong beam and high Ra.

(Example 27)

The (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ green phosphor of Example 26 was changed from a phosphor having an emission peak at a wavelength of 555 nm to a phosphor having an emission peak at a wavelength of 535 nm, and a duv was prepared to be 0. A light-emitting device that changes the correlated color temperature.

Fig. 47 shows the results of evaluation of the Ra of the white light emitted in Example 27 by simulation. As can be seen from Fig. 47, when the light-emitting device of the white light having a higher correlated color temperature and a correlated color temperature of 2000 to 5000 K is produced, Ra is 80 or more, and when the correlated color temperature is 3000 K or less, Ra is 90 or more.

Fig. 48 shows the results of evaluation of the R9 of the white light emitted in Example 27 by simulation. As can be seen from Fig. 48, when a light-emitting device that emits white light having a color temperature of 2000 to 8000 K is produced, R9 is a high value of 40 or more, and when the correlated color temperature is 2500 to 6500 K, Ra is as high as about 80 or more.

Fig. 49 shows the results of evaluation of the relative light beams when the correlated color temperature of the white light emitted in Example 27 was changed. In Fig. 49, when the color temperature of the white light of Example 27 is 2500~8000K, preferably 3000~5000R, more preferably 3500~4500K, Example 27 is shown as related in Comparative Example 6. A light beam with a color temperature of 82 to 85% of the beam at 3797K. Further, the light beam when the correlated color temperature of Comparative Example 6 is 3797 is shown by the solid line in Fig. 49.

In Figs. 47 to 49, when the color temperature of the light-emitting device of Example 27 is 3,000 to 5,000 K, Ra and R9 are 80 or more, and a strong light beam is obtained and high color rendering output light is emitted. When the correlated color temperature is 3500~4500K, Ra and R9 are 82 or more, and a strong beam is obtained and a higher color rendering output light is emitted. In particular, when the correlated color temperature is about 4000K, Ra and R9 are 85 or more, and a stronger beam is obtained and a higher color rendering output light is emitted.

Fig. 50 is a view showing simulation data of an emission spectrum of the light-emitting device of Example 27 which emits a warm white color light of a correlated color temperature of 4000 K (duv = 0). In the luminescence spectrum, the chromaticity (x, y) was (0.3805, 0.3768), Ra was 86, and R9 was 95. The shape of the luminescence spectrum is emitted from 520 to 550 nm of the green phosphor of Example 27 emitted from the blue LED by the luminescence peak of the wavelength region of 460 to 480 nm and by the 5d-4f electron transfer of the rare earth ion. The intensity ratio of the luminescence peak at 610 to 640 nm emitted by the red phosphor of Example 27, which is emitted by the 5d-4f electron transfer of the rare earth ions, is 460 to 480 nm: 520 to 550 nm: 610 to 640 nm is 24 ~28, 12~15:16~20. One of the preferred embodiments of the present invention is a light-emitting device characterized by warm-white light having a light-emitting spectrum shape having an emission peak of the above ratio. Further, the phosphor which emits light by the 5d-4f electron transfer of the rare earth ions is a phosphor which mainly contains a rare earth ion such as Eu ²⁺ or Ce ³⁺ as a luminescent center ion. When the wavelength of the luminescence peak is the same, the phosphor forms a similar luminescence spectrum shape regardless of the type of the phosphor precursor.

Further, if the green phosphor of Example 26 is changed to a (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ green phosphor having a light-emitting peak in the wavelength range of 520 to 550 nm, and is added in the wavelength range of 560 to 580 nm to emit light. In the case of the peak (Sr, Ba) SiO ₄ :Eu ²⁺ yellow phosphor, a high color rendering light-emitting device can be obtained from the simulation. For example, in the output light having a relative color temperature of 3800K, duv=0, and chromaticity (0.3897, 0.3823), Ra is 88, R9 is 72, and the relative beam is 93%.

When the phosphor of Example 26 is changed to a shorter (B, Sr) ₂ SiO ₄ :Eu ²⁺ green phosphor having a luminescence peak in a wavelength region of 520 nm, for example, under the light color condition of duv=0, The relationship between the correlated color temperature and Ra, R9 and the relative beam is evaluated by simulation. As a result, it was found that the shorter the wavelength of the luminescence peak of the green phosphor, the lower the values of Ra, R9 and the relative beam, and the lower the performance of the illuminating device. For example, when used for a green phosphor having a luminescence peak at a wavelength of 520 nm, when the correlated color temperature is 3800 K, duv = 0, and chromaticity (0.3897, 0.3823), Ra is 80, R9 is 71, and the relative beam is 85%. From the above, it is preferable to use a green phosphor having a light-emitting peak wavelength of 525 nm or more.

Further, the SrAlSiN ₃ :Eu ²⁺ red phosphor used in Example 26 and Example 27 is a red phosphor represented by the structural formula (M _1-x Eu _x )AlSiN ₃ and M is selected from Mg. And at least one element of Ca, Sr, Ba, and Zn, and x satisfies 0.005 ≦ x ≦ 0.3, and is not particularly limited. For example, the CaAlSiN ₃ :Eu ²⁺ red phosphor can also achieve the same effect.

Further, in place of the SrAlSiN ₃ :Eu ²⁺ red phosphor, for example, a well-known nitride phosphor or an oxynitride phosphor exhibiting similar luminescent properties, for example, a structural formula (M _1-x Eu _x )SiN ₂ or a nitride silicate phosphor represented by the structural formula (M _1-x Eu _x ) ₂ Si ₅ N ₈ or the like or an oxonitrogen represented by the structural formula (M _1-x Eu _x ) ₂ Si ₄ A _1O N ₇ The same effect can be obtained when the aluminosilicate phosphor is used. Wherein M is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and x satisfies 0.005 ≦ x ≦ 0.3.

In addition, the green phosphor and the yellow phosphor are not limited to those of the above-described embodiments, and may be a phosphor having a light-emitting peak in a wavelength region of 525 nm or more and less than 600 nm, for example, may be used for underfill. A phosphor having an excitation peak on the longest wavelength side of the excitation spectrum of the wavelength region of 420 nm. Further, a white LED is a YAG:Ce-based phosphor known as a phosphor, for example, (Y ₃ (Al, Ga) ₅ Ol2: Ce ^{3 +} green phosphor, Y ₃ Al ₅ O ₁₂ : Ce ³⁺ green phosphor, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce ^{3 +} yellow phosphor, Y ₃ Al ₅ O ₁₂ : Ce ³⁺ , Pr ^{3 +} yellow phosphor, etc. as the above green fluorescent The same effect can be obtained when a body or a yellow phosphor is used.

(Embodiment 28)

In this embodiment, the card type lighting module light source shown in FIG. 41 and FIG. 42 is produced and the light-emitting characteristics are evaluated. The blue LED chip 49 described in the embodiment 26 or the embodiment 27 is modified to be decorated with GaInN. The layer will emit a purple LED wafer with a luminescent peak near 405 nm. The output light of the present embodiment is excited by at least the light emitted by the purple LED chip to emit light, and is a mixed color light mainly composed of light emitted from the phosphor contained in the phosphor layer 3. Further, by appropriately selecting the type and amount of the phosphor, the output light can be made to be arbitrary white light.

Hereinafter, the phosphor layer 3 of the present embodiment will be described in detail.

The phosphor layer 3 is formed by drying and solidifying an epoxy resin to which a phosphor is added. The phosphor in the present embodiment uses three kinds of phosphors: SrAlSiN ₃ :Eu ²⁺ red phosphor having an emission peak at a wavelength of 625 nm (central particle diameter: 2.2 μm, maximum internal quantum efficiency: 60%, at 402 nm) Internal quantum efficiency under excitation: about 60%), (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ green phosphor with luminescence peak around 535 nm (central particle size: 15.2 μm, maximum internal quantum efficiency: 97%) , internal quantum efficiency at 405 nm excitation: about 97%) and BaMgAl ₁₀ O ₁₇ :Eu ²⁺ blue phosphor with luminescence peak near wavelength 405 nm (center particle diameter: 8.5 μm, maximum internal quantum efficiency: about 100 %, internal quantum efficiency at 405 nm excitation: about 100%), while epoxy resin is a two-liquid mixed epoxy resin, and epoxy resin based on bisphenol A liquid epoxy resin is the main component. And an epoxy resin containing an alicyclic anhydride as a main component is a hardener. Further, since the SrAlSiN ₃ :Eu ²⁺ red phosphor is not optimized as a manufacturing condition, the internal quantum efficiency is low. However, in the future, the internal quantum efficiency can be improved to 1.5 times or more by optimizing the production conditions. SrAlSiN ₃ :Eu ²⁺ red phosphor, (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ green phosphor and BaMgAl ₁₀ O ₁₇ :Eu ²⁺ blue phosphor weight mixing ratio is about 6:11: 30. The mixing ratio of the mixed phosphor to the epoxy resin is about 1:3 (fluorescence concentration = 25% by weight).

(Comparative Example 7)

A card type illumination module light source was produced in the same manner as in Example 28 using three types of phosphors: La ₂ O ₂ S:Eu ³⁺ red phosphor having an emission peak near a wavelength of 626 nm. (Center particle size: 9.3 μm, maximum internal quantum efficiency: 84%, internal quantum efficiency at 402 nm excitation: about 50%), and luminescence peak near the wavelength of 535 nm (Ba, Sr) ₂ SiO ₄ : Eu ²⁺ green Phosphor (center particle size: 15.2 μm, maximum internal quantum efficiency: 97%, internal quantum efficiency at 405 nm excitation: about 97%), and BaMgAl ₁₀ O ₁₇ :Eu ²⁺ blue with luminescence peak around 405 nm Color phosphor (center particle size: 8.5 μm, maximum internal quantum efficiency: about 100%, internal quantum efficiency at 405 nm excitation: about 100%). Phosphor layer 3, which is La ₂ O ₂ S:Eu ³⁺ red phosphor, (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ green phosphor and BaMgAl ₁₀ O ₁₇ :Eu ²⁺ blue fluorescent The mixture was mixed at a weight mixing ratio of about 155:20:33, and the mixing ratio of the mixed phosphor to the epoxy resin was about 1:3 (fluorescence concentration = 25% by weight). In the same manner as in the embodiment 28, the output light was obtained by flowing a current through the semiconductor light-emitting device, and the light-emitting characteristics of the output light were evaluated.

In order to obtain white light of a homochromatic color (correlation color temperature of about 3800 K, duv, chromaticity), the thickness of the phosphor layer 3 was formed to have a thickness of about 500 μm in the same manner as in Example 28 and Comparative Example 7.

Hereinafter, the light-emitting characteristics of the light-emitting devices of Example 28 and Comparative Example 7 will be described.

The luminescence spectra of Example 28 and Comparative Example 7 are shown in Figs. 51 and 52. As can be seen from FIG. 51 and FIG. 52, the light-emitting devices of Example 28 and Comparative Example 7 emit white light having a luminescence peak near 405 nm, around 450 nm, around 535 nm, and around 625 nm, that is, purple light is emitted. White light mixed with blue light, green light and red light. Further, the luminescence peak near 405 nm is the light leakage of the purple light-emitting element, and the luminescence peak near 450 nm, around 535 nm, and around 625 nm is a light-converted light of the violet light wavelength by a phosphor.

Table 9 shows the light-emitting characteristics of the light-emitting devices of Example 28 and Comparative Example 7.

The duv of Table 9 is an index indicating that white light is deviated from the black body emission locus. Ra is the average color rendering number, and R1 to R15 are the special color evaluation numbers, which indicates the degree to which the test light faithfully reproduces the test color when the reference light observation color is set to 100. In particular, R9 is a special color evaluation number of red.

Although a red phosphor having a production condition of a phosphor that has not been optimized, a maximum internal quantum efficiency of 60%, and low performance is used, Example 28 is under the condition of approximately equivalent light color (correlated color temperature, duv, and chromaticity). It is possible to emit white light which is 17% higher than the relative light beam of Comparative Example 7. In Comparative Example 7, the maximum internal quantum efficiency of the red phosphor was 83%, and the output efficiency of the light-emitting device was improved by about 20%. However, the maximum internal quantum efficiency of the red phosphor used in Example 28 was 60%. The white output of the illuminating device can be improved by about 60% or more. That is, in theory, in the end, the material of the light-emitting device of Embodiment 28 constitutes a white light that can emit a strong light beam.

Further, in the light-emitting device of Example 28, when white light having a correlated color temperature of 3800 K was emitted in combination with at least the above-mentioned phosphor, a larger Ra ratio than Comparative Example 7 was exhibited. Further, not only the special color evaluation numbers of all of R9 and R1 to R15 can be obtained as large as Comparative Example 7. This indicates that Example 28 can emit white light having excellent color rendering properties.

Further, in the light-emitting device of the twenty-seventh embodiment, it is possible to emit high-color rendering white light having a special color rendering number of R1 to R15 of 80 or more, and to display light which is close to sunlight. Such a light-emitting device is particularly suitable for medical use, for example, it can be provided as an LED light source that can be applied to an endoscope or the like, and can be diagnosed in an excellent endoscope system under the light of sunlight.

Hereinafter, in order to examine the light color of the light-emitting device having high color rendering property and strong light beam, the duv of the white light emitted by the light-emitting devices of Example 28 and Comparative Example 7 is 0, and the influence of Ra and the relative light beam when the correlated color temperature is changed. , evaluate by simulation, and explain the results.

Fig. 53 is a view showing the relative light beams obtained by changing the correlated color temperatures of the white light emitted from the light-emitting devices of Example 28 and Comparative Example 7, and the results of the evaluation were carried out using simulation. As can be seen from Fig. 53, the light-emitting device of Example 28 can emit white light of about 10 to 20% higher than that of Comparative Example 7 in the wide range of correlated color temperatures of 2000 to 12000K. Further, when the light-emitting device of the embodiment 28 is configured to output light having a correlated color temperature of 2500 to 12000 K, preferably 3500 to 7000 K, it is about 110 to 115% of the light beam of Comparative Example 7 at a correlated color temperature of 3792 K, which is strong. beam. Further, the solid line in Fig. 53 indicates the light beam when the correlated color temperature of Comparative Example 7 is 3792K.

Hereinafter, it is assumed that the production conditions of the respective phosphors used in Example 28 and Comparative Example 7 have been optimized, and a phosphor having a maximum internal quantum efficiency of 100% is obtained, and the result of the simulation of the beam with the ideal phosphor is obtained. . In the simulation, the internal internal quantum efficiencies of the respective phosphors excited at 405 nm in FIGS. 30, 32, 37, and 40 were estimated and evaluated as shown in Table 10 below.

Fig. 54 shows the results of evaluating the influence of the correlated color temperature of the white light emitted from the light-emitting device of Example 28 and Comparative Example 7 on the relative light beam when the ideal phosphor was used. As can be seen from Fig. 54, in the light-emitting device of the twenty-eighth embodiment, when an ideal phosphor is used, the wide range of correlated color temperatures of 2000 to 12000 K can be about 45 to 65% higher than that of the light beam of Comparative Example 7. . Further, when a light-emitting device having a white light-related color temperature of 2500 to 12000 K, preferably 3500 to 6000 K, is produced, it is a strong light beam of a light beam having a correlated color temperature of 3792 K in Comparative Example 7 of 150 to 160%. Further, the light beam when the correlated color temperature of Comparative Example 7 is 3792 K is indicated by the solid line in Fig. 54.

In other words, it is presumed that in the future, the SrAlSiN ₃ :Eu ²⁺ red phosphor can be obtained by a high performance, and a light-emitting device having a light beam emission of about 45 to 65% higher than that of the comparative example 7 can be obtained under the same correlated color temperature evaluation.

Further, Fig. 55 shows the results of the evaluation of the influence on the average color rendering number (Ra) when the correlated color temperature of the white light emitted from the light-emitting devices of Example 28 and Comparative Example 7 was changed. The illuminating device of the illuminating device of Example 28 exhibits a high Ra of 90 or more in a wide range of color temperatures of 2000 to 12000 K, and preferably exhibits a very high Ra of 95 or more when the illuminating device of 3000 to 12000 K is produced.

Fig. 56 is a graph showing the results of the evaluation of the influence on the number of special color evaluations (R9) of red when the correlated color temperature of the white light emitted from the light-emitting devices of Example 28 and Comparative Example 7 was changed. The R9 of the light-emitting device of Example 28 having a correlated color temperature of 2500 to 12000 K was larger than Comparative Example 7. Further, the light-emitting device of the embodiment 28 exhibits a high R9 of 30 or more in a wide color temperature range of 2000 to 12000 K in white light, 70 or more in 3000 to 12000 K, and 80 or more in 3500 to 12000 K, in 5000 to 12000 K. A high-level R9 of 90 or more is a preferred light-emitting device for emitting white light of a high red color appearance number. In addition, the maximum R9 value (96~98) can be obtained in the correlated color temperature range of 6000~8000K.

As can be seen from FIGS. 53 to 55, the light-emitting device of Example 28 can emit a white light having a strong light beam and a high Ra ratio in Comparative Example 7 over a wide range of correlated color temperatures of 2000 to 12000K. When the color temperature of the white light is 2500~12000K, preferably 3500~7000K, and more preferably 4000~5000K, it can have both a strong beam and a high Ra.

As can be seen from FIGS. 56 to 58, the light-emitting device of Example 28 can emit a strong light beam and a high R9 white light in Comparative Example 7 over a wide range of correlated color temperatures of 2500 to 12000K. When the color temperature of the white light is 3000~12000K, preferably 3500~12000K, more preferably 5000~12000K, especially when the light emitting device is 6000~8000k, it can have both a strong beam and a high R9.

Fig. 57 is a view showing the luminescence spectrum simulation data of the illuminating device of Example 28, which emits a light beam and Ra warm color light having a correlated color temperature of 4500K (duv = 0). In the luminescence spectrum, the chromaticity (x, y) is (0.3608, 0.3635), Ra is 96, R1 is 96, R2 and R6 to R8 are 97, R3, R10 and R11 are 91, and R4 and R14 are 94, R5. R13 and R15 are 99, and R9 and R12 are 88. From the above, it can be seen that a light-emitting device can be provided which can emit white light having good color rendering properties of all the special color rendering numbers of R1 to R15 of 85 or more. The shape of the luminescence spectrum is RGB phosphor of Example 28, which emits light having a luminescence peak in a wavelength range of 400 to 410 nm in the wavelength range of 400 to 410 nm and emits light by 5d-4f electron transfer from the rare earth ion at 440 to 460 nm. The luminescence peaks in the wavelength range of 520~540nm and 610~640nm have an intensity ratio of 400~410nm: 440~460nm: 520~540nm: 610~640nm is 8~10:12~14:15~17:16~18. One of the preferred embodiments of the present light-emitting device is a light-emitting device characterized in that it emits warm-white light having a light-emitting spectrum shape having an emission peak of the above ratio. Further, the phosphor in which the 5d-4f electron of the rare earth ion migrates and emits light refers to a phosphor mainly containing a rare earth ion of Eu ²⁺ or Ce ³⁺ as a luminescent center ion. When the wavelength of the luminescence peak is the same, the luminescence spectrum shape of the phosphor is similar regardless of the type of the phosphor precursor.

Fig. 58 is a view showing luminescence spectrum simulation data of the illuminating device of Example 28, which emits a light beam and a white light having a correlated color temperature of 5500 K (duv = 0). In the luminescence spectrum, the chromaticity (x, y) is (0.3324, 0.3410), Ra is 96, R1 and R13 are 98, R2 and R8 and R15 are 97, R3 and R12 are 90, R4 is 92, and R5 is 99. R6 is 96, R7 is 95, R9 and R14 are 94, and R10 and R11 are 91. That is to say, according to the present invention, it is possible to provide a light-emitting device which can emit white light of all the special color rendering numbers of R1 to R15 which are suitable for medical use and which are close to sunlight of 90 or more. Further, regarding the shape of the luminescence spectrum, the ultraviolet ray LED emits light having a luminescence peak in a wavelength range of 400 to 410 nm, and the RGB phosphor of Example 28 which emits light by electron transfer from 5d-4f of rare earth ions at 440~ The intensity ratio of the luminescence peaks in the wavelength regions of 460 nm, 520 to 540 nm, and 610 to 640 nm is 400 to 410 nm: 440 to 460 nm: 520 to 540 nm: 610 to 640 nm is 4 to 6: 9 to 11: 8 to 10: 7 to 9. One of the preferred embodiments of the light of the present invention is a light-emitting device characterized by emitting white light having an emission spectrum shape having an emission peak of the above ratio.

Embodiment 28 illustrates a case where three kinds of phosphors of a combination of a purple LED and red, green and blue (RGB) are combined, and SrAlSiN ₃ :Eu ^{2+ is} used as a red phosphor, but at least the above-mentioned purple LED and SrAlSiN ₃ :Eu ²⁺ or CaAlSiN ₃ :Eu ²⁺ or the like (M _1-x Eu _x )AlSiN ₃ is a combination of phosphors represented by the structural formula, and the phosphor is composed of four kinds of red, yellow, green and blue (RYGB) or reddish yellow The same effect and effect can be obtained when three kinds of blue (RYB) are used.

In the embodiment 28, the case where SrAlSiN ₃ :Eu ^{2+ is} used as the red phosphor is described, but the phosphor is represented by the structural formula of the structural formula (M _1-x Eu _x )AlSiN ₃ and M is selected. The element of at least one of Mg, Ca, Sr, Ba, and Zn and x are values of 0.005 ≦ x ≦ 0.3, and are not particularly limited. In addition, the green phosphor is not limited to the green phosphor used in the above-described embodiment, and may be a green phosphor having a light-emitting peak in a wavelength region of 560 nm or more and less than 600 nm. The green phosphor may be a yellow phosphor that emits light having a luminescence peak of 560 nm or more and less than 600 nm. Further, the light output of the green or yellow phosphor is preferably a phosphor activated by Eu ²⁺ or Ce ³⁺ .

Due to the characteristics of the SrAlSiN ₃ :Eu ²⁺ red phosphor and the conventional red phosphor, for example, SrSiN ₂ :Eu ²⁺ , Sr ₂ Si ₅ N ₈ :Eu ²⁺ , Sr ₂ Si ₄ A _1O N ₇ : nitride phosphors such as Eu ²⁺ or oxynitride phosphors are similar, so if SrAlSiN ₃ :Eu ²⁺ red phosphors are used in the above-mentioned conventional nitride phosphors or oxygen nitrogen in Examples 27 and 28 The same effect can be obtained by replacing the phosphor with a phosphor.

Hereinafter, in the above phosphor, SrAlSiN ₃ :Eu ²⁺ , Sr ₂ Si ₅ N ₈ :Eu ²⁺ , SrSiN ₂ :Eu ²⁺ , (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ (light-emitting peak: 555 nm), (Ba, Sr) ₂ SiO ₄ : Eu ²⁺ (luminescence peak: 535 nm), (Ba, Sr) ₂ SiO ₄ : Eu ²⁺ (luminescence peak: 520 nm), (Sr, Ba) ₂ SiO ₄ : A method for producing Eu ²⁺ (luminescence peak: 570 nm) is for reference. Further, a commercially available product was used for the Y ₃ Al ₅ O ₁₂ :Ce ₃₊ yellow phosphor, the La ₂ O ₂ S:Eu ³⁺ red phosphor, and the BaMgAl ₁₀ O ₁₇ :Eu ²⁺ blue fluorescent system.

Tables 11 and 12 show the mass of the raw material compound used in the production of each phosphor.

The method for producing the three red phosphors shown in Table 11 will be described below. First, the predetermined compounds shown in Table 11 were mixed in a dry nitrogen atmosphere using a handle box and a mortar to obtain a mixed powder. At this time, no reaction accelerator (flux) is used. Next, the mixed powder is placed in an aluminum crucible, and temporarily calcined in a nitrogen atmosphere at a temperature of 800 to 1400 ° C for 2 to 4 hours, and then subjected to a nitrogen atmosphere at a temperature of 1600 to 1800 ° C and a hydrogen atmosphere of 3% in an atmosphere of 3%. The hour is burned to synthesize a red phosphor. The phosphor powder after the firing is orange. After the firing, a predetermined post-treatment such as pulverization, classification, washing, and drying is applied to obtain a red phosphor.

Next, a method of manufacturing the four kinds of green phosphors and yellow phosphors shown in Fig. 12 will be described. First, the predetermined compounds shown in Table 12 were mixed in the atmosphere using a mortar to obtain a mixed powder. Next, the mixed powder is placed in an aluminum crucible, and is temporarily calcined in an atmosphere at a temperature of 950 to 1000 ° C for 2 to 4 hours until the powder is temporarily calcined. To the temporarily calcined powder, 3.620 g of calcium chloride (CaCl ₂ ) powder was added as a flux, and the mixture was fired at a temperature of 1200 to 1300 ° C in a nitrogen atmosphere of 97% and a hydrogen atmosphere at 3% for 4 hours to synthesize green. Phosphor and yellow phosphor. The phosphor powder after the firing is green to yellow. After the firing, a predetermined post-treatment such as pulverization, classification, washing, and drying is performed to obtain a green phosphor and a yellow phosphor.

The present invention can be carried out in other forms than those described above without departing from the spirit of the invention. The embodiment disclosed in the present application is merely an example and is not limited thereto. The scope of the invention is defined by the scope of the claims, and all modifications within the scope of the invention are included in the scope of the claims.

The composition of the present invention is a composition represented by a structural formula represented by aM ₃ N ₂ ‧bAlN‧cSi ₃ N ₄ as a main body of a phosphor precursor. In the above structural formula, M is selected from the group consisting of Mg, Ca, and Sr. The element, a, b, and c of at least one of Ba and Zn satisfy 0.2≦a/(a+b)≦0.95, 0.05≦b/(b+c)≦0.8, 0.4≦c/(c+a)≦ 0.95; in particular, the composition represented by the structural formula of MAlSiN3 is the main body of the phosphor precursor, which can be excited by ultraviolet to near ultraviolet ~ violet ~ blue ~ green ~ yellow ~ orange light, especially the warm color red A novel fluorescent light that is light.

Moreover, the method for producing a phosphor composition of the present invention is a compound containing a compound which forms an oxide of the element M by heating, a ruthenium compound, an aluminum compound, a compound containing an element forming a luminescent center ion, and a raw material of carbon. By reacting in a nitriding gas atmosphere to produce a phosphor composition, it is easy to handle and inexpensive to use without using a nitride or alkaline earth metal of a high-priced alkaline earth metal which is chemically unstable and difficult to handle in the atmosphere. Raw material to produce the phosphor assembly of the present invention. Therefore, it is possible to industrially produce a novel nitride phosphor composition having good material properties at low cost.

Further, the light-emitting device of the present invention is composed of the above-described phosphor composition of the present invention which emits warm color light, particularly red light, which is novel, high-performance and inexpensive, and thus can provide a strong red light-emitting component. A high-performance, low-cost, and novel light-emitting device (LED light source, etc.).

Furthermore, according to the present invention, it is possible to provide a light-emitting device which combines high color rendering properties and a strong light beam and emits white light. In particular, it is possible to provide a light-emitting device such as an LED light source that emits warm white light and has a strong red light-emitting component.

1. . . Light-emitting element

2. . . Phosphor composition

3. . . Phosphor layer

4. . . Base element

5. . . Lead frame

6. . . Cup

7. . . Sealing material

8. . . framework

9. . . Semiconductor light emitting device

10. . . Output light

11. . . Light department

12. . . Lighting module

13. . . switch

14. . . Lamp head

15. . . Reflective plate

16. . . Glass tube

17. . . Electronic tube

18. . . Phosphor composition

19. . . wire

20. . . Filament electrode

twenty one. . . Electrode terminal

twenty two. . . Lamp head

twenty three. . . Back substrate

twenty four. . . Lower electrode

25. . . Thick film dielectric

26. . . Thin film phosphor

27. . . Thin film dielectric

28. . . Upper electrode

29. . . Optical wavelength conversion layer

30. . . Surface glass

31. . . Wavelength conversion layer

32. . . Wavelength conversion layer

33. . . Blue light

34. . . Green light

35. . . Red light

36. . . Excitation spectrum of phosphor composition

37. . . Luminescence spectrum of phosphor composition

40. . . Internal quantum efficiency of phosphor

41. . . External quantum efficiency of the phosphor

42. . . Internal quantum efficiency of phosphor

43. . . External quantum efficiency of the phosphor

44. . . Semiconductor light emitting device

45. . . Si diode

46. . . N electrode

47. . . P electrode

48. . . Micro-bump

49. . . Blue LED chip

50. . . Aluminum metal substrate

51. . . 1st source thick film

52. . . Copper electrode

53. . . 2nd insulator thick film

54a, 54b. . . Electrode pad

55. . . Heat dissipation multilayer substrate

56. . . Inner electrode

57. . . Au line

58. . . Combined pad

59. . . Aluminum metal reflector

60‧‧‧稜鏡

Fig. 1 is a cross-sectional view showing a semiconductor light emitting device according to an embodiment of the present invention.

Fig. 2 is a cross-sectional view showing a semiconductor light emitting device according to an embodiment of the present invention.

Fig. 3 is a cross-sectional view showing a semiconductor light emitting device according to an embodiment of the present invention.

Fig. 4 is a schematic view showing the configuration of an illumination and display device according to an embodiment of the present invention.

Fig. 5 is a schematic view showing the configuration of an illumination and display device according to an embodiment of the present invention.

Figure 6 is a perspective view of a lighting module in accordance with an embodiment of the present invention.

Fig. 7 is a perspective view of a lighting module in accordance with an embodiment of the present invention.

Fig. 8 is a perspective view of the lighting device in the embodiment of the present invention.

Fig. 9 is a side view of the lighting device in the embodiment of the present invention.

Figure 10 is a bottom plan view of the lighting device of Figure 9.

Figure 11 is a perspective view of a video display device in accordance with an embodiment of the present invention.

Figure 12 is a perspective view of a digital display device in accordance with an embodiment of the present invention.

Figure 13 is a partial perspective view of an end portion of a fluorescent lamp in an embodiment of the present invention.

Figure 14 is a cross-sectional view showing an EL panel in an embodiment of the present invention.

Fig. 15 is a view showing an emission spectrum and an excitation spectrum of a phosphor composition in Example 1 of the present invention.

Fig. 16 is a view showing an X-ray diffraction pattern of a phosphor composition in Example 1 of the present invention.

Fig. 17 is a view showing an emission spectrum and an excitation spectrum of a phosphor composition in Example 2 of the present invention.

Fig. 18 is a view showing an X-ray diffraction pattern of a phosphor composition in Example 2 of the present invention.

Fig. 19 is a view showing the luminescence spectrum of the phosphor composition according to Example 2 of the present invention.

Fig. 20 is a graph showing the relationship between the Eu substitution amount and the luminescence peak wavelength of the phosphor composition according to Example 2 of the present invention.

Fig. 21 is a graph showing the relationship between the Eu substitution amount and the luminescence intensity of the phosphor composition according to Example 2 of the present invention.

Fig. 22 is a view showing an emission spectrum and an excitation spectrum of a phosphor composition in Example 3 of the present invention.

Fig. 23 is a view showing an emission spectrum and an excitation spectrum of a phosphor composition in Example 4 of the present invention.

Fig. 24 is a view showing an emission spectrum and an excitation spectrum of a phosphor composition in Example 5 of the present invention.

Fig. 25 is a view showing an emission spectrum and an excitation spectrum of a phosphor composition in Example 6 of the present invention. ;

Fig. 26 is a view showing an emission spectrum and an excitation spectrum of a phosphor composition in Example 7 of the present invention.

Fig. 27 is a view showing an emission spectrum and an excitation spectrum of a phosphor composition in Example 8 of the present invention.

Fig. 28 is a view showing the ternary composition of the composition range of the phosphor composition of the present invention.

Fig. 29 is a graph showing the luminescence characteristics of a SrSiN ₂ :Eu ²⁺ red phosphor.

Fig. 30 is a graph showing the luminescence characteristics of a SrAlSiN ₃ :Eu ²⁺ red phosphor.

Fig. 31 is a graph showing the luminescence characteristics of a Si ₂ Si ₅ N ₈ :Eu ²⁺ red phosphor.

Fig. 32 is a graph showing the luminescence characteristics of a (Ba, Sr) ₂ SiO ₄ :Eu ²⁺ green phosphor.

Fig. 33 is a graph showing the luminescence characteristics of (Sr,Ba) ₂ SiO ₄ :Eu ²⁺ yellow phosphor.

Fig. 34 is a view showing the illuminance of (Sr, Ca) ₂ SiO ₄ :Eu ²⁺ yellow phosphor.

Fig. 35 is a graph showing the luminescence characteristics of a 0.75CaO ₂ .25AlN ₃ .25Si ₃ N ₄ :Eu ²⁺ yellow phosphor.

Fig. 36 is a graph showing the luminescence characteristics of (Y, Gd) ₃ Al ₅ O ₁₂ : Ce ^{3 +} yellow phosphor.

Fig. 37 is a graph showing the luminescence characteristics of a BaMgAl ₁₀ O ₁₇ :Eu ²⁺ blue phosphor.

Fig. 38 is a graph showing the luminescence characteristics of a Sr ₄ Al ₁₄ O ₂₅ :Eu ²⁺ blue-green phosphor.

Fig. 39 is a graph showing the luminescence characteristics of (Sr,Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ :Eu ²⁺ blue phosphor.

Fig. 40 is a graph showing the luminescence characteristics of La ₂ O ₂ S:Eu ³⁺ red phosphor.

Figure 41 is a perspective view of a light-emitting device of Embodiment 26 of the present invention.

Figure 42 is a partial cross-sectional view showing a light-emitting device of Embodiment 26 of the present invention.

Figure 43 is a graph showing the luminescence spectrum of a light-emitting device of Example 26 of the present invention.

Fig. 44 is a chart showing the luminescence spectrum of the light-emitting device of Comparative Example 6 of the present invention.

Fig. 45 is a graph showing the results of simulating the relationship between the correlated color temperature and the relative light beam in Example 26 and Comparative Example 6 of the present invention.

Fig. 46 is a graph showing the results of simulating the relationship between the correlated color temperature and Ra in Example 26 and Comparative Example 6 of the present invention.

Fig. 47 is a view showing the result of simulating the relationship between the correlated color temperature and Ra in the twenty-seventh embodiment of the present invention.

Fig. 48 is a view showing the result of simulating the relationship between the correlated color temperature and R9 in the twenty-seventh embodiment of the present invention.

Fig. 49 is a view showing the result of simulating the relationship between the correlated color temperature and the relative light beam in the twenty-seventh embodiment of the present invention.

Figure 50 is a graph showing the luminescence spectrum of a light-emitting device in Example 27 of the present invention.

Figure 51 is a graph showing the luminescence spectrum of a light-emitting device in Example 28 of the present invention.

Figure 52 is a graph showing the luminescence spectrum of a light-emitting device of Comparative Example 7 of the present invention.

Figure 53 is a graph showing the results of simulations of the relationship between the correlated color temperature and the relative beam in Example 28 and Comparative Example 7 of the present invention.

Fig. 54 is a view showing simulation results of the relationship between the correlated color temperature and the relative light beam of the light-emitting device using the ideal phosphor in Example 28 and Comparative Example 7 of the present invention.

Fig. 55 is a graph showing the results of simulation of the relationship between the correlated color temperature and Ra in Example 28 and Comparative Example 7 of the present invention.

Fig. 56 is a graph showing the results of simulation of the relationship between the correlated color temperature and R9 in Example 28 and Comparative Example 7 of the present invention.

Fig. 57 is a view showing a simulation result of an emission spectrum of a light-emitting device of a warm-color white light having a light-emission-related color temperature of 4500 K (duv = 0) in Example 28 of the present invention.

Fig. 58 is a view showing a simulation result of an emission spectrum of a light-emitting device of a warm-color white light having an emission-related color temperature of 5,500 K (duv = 0) in Example 28 of the present invention.

1. . . Light-emitting element

2. . . Phosphor composition

3. . . Phosphor layer

4. . . Base element

Claims (16)

A phosphor composition comprising MAlSiN ₃ . a'Si ₃ N ₄ , MAlSiN ₃ . a'M ₂ Si ₅ N ₈ , MAlSiN ₃ . a'MSiN ₂ or MAlSiN ₃ . The nitride represented by any one of the structural formulas of a'MSi ₇ N ₁₀ is a main body of the phosphor precursor, and contains a metal ion selected from the group consisting of rare earth ions and transition metal ions as a luminescent center ion, characterized in that the structural formula In the above, M is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and a' is a value satisfying 0.25 ≦ a' ≦ 2 . The phosphor composition according to claim 1, wherein the phosphor precursor system is a composition represented by a structural formula of MAlSi ₄ N ₇ . The phosphor composition according to claim 1, wherein one of the elements Al is substituted with an element which is trivalent, and the substitution amount is less than 30 atom% with respect to the element A1. A phosphor composition according to claim 1 which contains a metal element in an amount of less than 10 atomic % corresponding to at least one of the elements M, Al or Si. A phosphor composition according to claim 1 which contains oxygen in an amount corresponding to less than 10 atomic % of the element N. The phosphor composition of claim 1, which contains a metal element in an amount of less than 10 atomic % corresponding to at least one of the elements M, Al, or Si, and contains a lower equivalent of the element N. Oxygen in an amount of 10 atom%. The phosphor composition according to claim 1, wherein the luminescent center ion is an ion selected from at least one of Ce ³⁺ and Eu ²⁺ . The phosphor composition according to claim 7, wherein the amount of the luminescent center ion added is 0.5 atom% or more and 10 atom% or less based on the element M. The phosphor composition according to claim 1, wherein the main component of the element M is at least one element selected from the group consisting of Ca and Sr. The phosphor composition of claim 1, wherein the main component of the element M is Sr. The phosphor composition according to claim 7, wherein the luminescent center ion is Eu ²⁺ , and the phosphor composition has an illuminating peak in a wavelength region of 580 nm or more and less than 660 nm. A light-emitting device comprising the phosphor composition of claim 1 of the patent application as a light-emitting source. The illuminating device of claim 12, further comprising an emission source capable of emitting primary light of 360 nm or more and less than 560 nm, wherein the phosphor composition absorbs the primary light emitted by the emission source and emits a wavelength More than the secondary light of the primary light. The illuminating device of claim 13, wherein the emitting source is an injection type electroluminescent element. A light-emitting device according to claim 14, which is a white light-emitting element. The light-emitting device of claim 14, which is a display device including a white light-emitting element, a light source including a white light-emitting element, or an illumination device including a white light-emitting element.