JP2006307182A5

JP2006307182A5 -

Info

Publication number: JP2006307182A5
Application number: JP2006086850A
Authority: JP
Filing date: 2006-03-28
Publication date: 2010-07-01
Anticipated expiration: 2026-03-28

Description

（１）励起光源と、該励起光源からの光の少なくとも一部を波長変換する蛍光体とを有する発光装置において、該励起光源が、３００ｎｍ以上、５００ｎｍ以下のピーク発光波長を有する発光ダイオードであり、該蛍光体として、付活元素Ｍ ^１と、２価の金属元素Ｍ ^２と、少なくともＳｉを含む４価の金属元素Ｍ ^４とを含み、かつ、合金を、窒素含有雰囲気下で加熱し、窒化することにより得られた蛍光体（以下、「第１の蛍光体」とする。）を含有することを特徴とする発光装置。
（２）（１）において、前記第１の蛍光体が、２価の金属元素Ｍ ^２としてアルカリ土類金属元素を含むことを特徴とする発光装置。
（３）（１）又は（２）において、前記第１の蛍光体が、さらに３価の金属元素Ｍ ^３を含むことを特徴とする発光装置。
（４）（１）ないし（３）のいずれかにおいて、前記第１の蛍光体が、付活元素Ｍ ^１としてＥｕ及び／又はＣｅを含み、２価の金属元素Ｍ ^２がＣａ及び／又はＳｒを含み、３価の金属元素Ｍ ^３がＡｌを含み、４価の金属元素Ｍ ^４としてＳｉを含むことを特徴とする発光装置。
（５）（１）ないし（４）のいずれかにおいて、前記第１の蛍光体が下記一般式［１］で表されることを特徴とする発光装置。
Ｍ ^１ _ａＭ ^２ _ｂＭ ^３ _ｃＭ ^４ _ｄＮ _ｅＯ _ｆ［１］
（但し、Ｍ ^１は、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、及びＹｂよりなる群から選ばれる１種以上の元素であり、
Ｍ ^２は、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、及びＺｎよりなる群から選ばれる１種以上の元素であり、
Ｍ ^３は、Ａｌ、Ｇａ、Ｉｎ、及びＳｃよりなる群から選ばれる１種以上の元素であり、
Ｍ ^４は、Ｓｉを必須とする、Ｓｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｚｒ、及びＨｆよりなる群から選ばれる１種以上の元素である。
ａ、ｂ、ｃ、ｄ、ｅ、ｆはそれぞれ下記の範囲の値である。
０．００００１≦ａ≦０．１５
ａ＋ｂ＝１
０．５≦ｃ≦１．５
０．５≦ｄ≦１．５
２．５≦ｅ≦３．５
０≦ｆ≦０．５）
（６）（５）において、前記第１の蛍光体が下記一般式［２］で表されることを特徴とする発光装置。
Ｍ ^１’ _ａ’ Ｓｒ _ｂ’ Ｃａ _ｃ’ Ｍ ^２’ _ｄ’ Ａｌ _ｅ’ Ｓｉ _ｆ’ Ｎ _ｇ’ ［２］
（但し、Ｍ ^１’ は、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ及びＹｂからなる群から選ばれる１種以上の元素であり、
Ｍ ^２’ は、Ｍｇ及び／又はＢａである。
ａ’、ｂ’、ｃ’、ｄ’、ｅ’、ｆ’、ｇ’はそれぞれ下記の範囲の値である。
０．００００１≦ａ’≦０．１５
０．１≦ｂ’≦０．９９９９９
０≦ｃ’＜１
０≦ｄ’＜１
ａ’＋ｂ’＋ｃ’＋ｄ’＝１
０．５≦ｅ’≦１．５
０．５≦ｆ’≦１．５
０．８×(２/３＋ｅ’＋４/３×ｆ’)≦ｇ’≦１．２×(２/３＋ｅ’＋４/３×ｆ’))
（７）（６）において、一般式［２］におけるｂ’の値が、０．６≦ｂ’≦０．９９９９９の範囲であり、かつ、ｄ’＝０であることを特徴とする発光装置。
（８）（１）ないし（７）のいずれかにおいて、前記合金が、付活元素Ｍ ^１と、２価の金属元素Ｍ ^２と、少なくともＳｉを含む４価の金属元素Ｍ ^４とを含むことを特徴とする発光装置。
（９）（１）ないし（８）のいずれかにおいて、前記蛍光体として、前記第１の蛍光体とは発光波長の異なる第２の蛍光体を含有することを特徴とする発光装置。
（１０）（９）において、前記第２の蛍光体として、ピーク波長を、４９０ｎｍ以上、５７０ｎｍ以下の波長範囲に有する緑色蛍光体を含有することを特徴とする発光装置。
（１１）（１０）において、前記緑色蛍光体として、(Ｂａ，Ｓｒ，Ｃａ，Ｍｇ) _２ＳｉＯ _４：Ｅｕ、Ｃａ _３ (Ｓｃ，Ｍｇ，Ｎａ，Ｌｉ) _２Ｓｉ _３Ｏ _１２：Ｃｅ、ＣａＳｃ _２Ｏ _４：Ｃｅ、Ｅｕ付活βサイアロン、Ｅｕ付活αサイアロン、及びＢａＭｇＡｌ _１０Ｏ _１７：Ｅｕ，Ｍｎからなる群から選ばれる少なくとも１種以上を含有することを特徴とする発光装置。
（１２）（９）ないし（１１）のいずれかにおいて、前記第２の蛍光体として、ピーク波長を、４２０ｎｍ以上、４８０ｎｍ以下の波長範囲に有する青色蛍光体を含有することを特徴とする発光装置。
（１３）下記一般式［２］で表されることを特徴とする蛍光体。
Ｍ ^１’ _ａ’ Ｓｒ _ｂ’ Ｃａ _ｃ’ Ｍ ^２’ _ｄ’ Ａｌ _ｅ’ Ｓｉ _ｆ’ Ｎ _ｇ’ ［２］
（但し、Ｍ ^１’ は、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ及びＹｂからなる群から選ばれる１種以上の元素であり、
Ｍ ^２’ は、Ｍｇ及び／又はＢａである。
ａ’、ｂ’、ｃ’、ｄ’、ｅ’、ｆ’、ｇ’はそれぞれ下記の範囲の値である。
０．００００１≦ａ’≦０．１５
０．１≦ｂ’≦０．９９９９９
０≦ｃ’＜１
０≦ｄ’＜１
ａ’＋ｂ’＋ｃ’＋ｄ’＝１
０．５≦ｅ’≦１．５
０．５≦ｆ’≦１．５
０．８×(２/３＋ｅ’＋４/３×ｆ’)≦ｇ’≦１．２×(２/３＋ｅ’＋４/３×ｆ’))
（１４）（１３）において、酸素の含有量が５重量％以下であることを特徴とする蛍光体。
（１５）下記一般式［２］で表される蛍光体の製造方法であり、酸素濃度１０００ｐｐｍ以下の窒素含有雰囲気下で、圧力を１０ＭＰａから２００ＭＰａ、温度を８００℃以上、２２００℃以下として、１分以上、２４時間以下加熱することにより、窒化を行うことを特徴とする蛍光体の製造方法。
Ｍ ^１’ _ａ’ Ｓｒ _ｂ’ Ｃａ _ｃ’ Ｍ ^２’ _ｄ’ Ａｌ _ｅ’ Ｓｉ _ｆ’ Ｎ _ｇ’ ［２］
（但し、Ｍ ^１’ は、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ及びＹｂからなる群から選ばれる１種以上の元素であり、
Ｍ ^２’ は、Ｍｇ及び／又はＢａである。
ａ’、ｂ’、ｃ’、ｄ’、ｅ’、ｆ’、ｇ’はそれぞれ下記の範囲の値である。
０．００００１≦ａ’≦０．１５
０．１≦ｂ’≦０．９９９９９
０≦ｃ’＜１
０≦ｄ’＜１
ａ’＋ｂ’＋ｃ’＋ｄ’＝１
０．５≦ｅ’≦１．５
０．５≦ｆ’≦１．５
０．８×(２/３＋ｅ’＋４/３×ｆ’)≦ｇ’≦１．２×(２/３＋ｅ’＋４/３×ｆ’)) (1) In a light emitting device having an excitation light source and a phosphor that converts the wavelength of at least part of light from the excitation light source, the excitation light source is a light emitting diode having a peak emission wavelength of 300 nm to 500 nm. as the phosphor, the activator elements M ^1, divalent metal elements M ^2, and a tetravalent metal elements M ⁴ including at least Si, and the alloy is heated in a nitrogen containing atmosphere, A light emitting device comprising a phosphor obtained by nitriding (hereinafter referred to as “first phosphor”).
(2) In (1), the first phosphor, the light emitting device characterized by comprising an alkaline earth metal element as the divalent metal elements M ^2.
(3) (1) or (2), the first phosphor, further light-emitting device which comprises a trivalent metal element M ^3.
In any one of (4) (1) to (3), wherein the first phosphor comprises a Eu and / or Ce as activator elements ^{M 1,} 2 divalent metal elements ^{M 2} is Ca and / or Sr And a trivalent metal element M ³ containing Al, and a tetravalent metal element M ⁴ containing Si.
(5) In any one of (1) to (4), the first phosphor is represented by the following general formula [1].
^{_{^{_{^{M 1 a M 2 b M 3}}}}} c M 4 d N e O f [1]
(Wherein, ^{M 1} is, Cr, Mn, Fe, Ce , Pr, Nd, Sm, Eu, Tb, Dy, Ho, at least one element selected Er, Tm, and from the group consisting of Yb,
M ² is one or more elements selected from the group consisting of Mg, Ca, Sr, Ba, and Zn,
M ³ is one or more elements selected from the group consisting of Al, Ga, In, and Sc;
M ⁴ is at least one element selected from the group consisting of Si, Ge, Sn, Ti, Zr, and Hf, which essentially requires Si.
a, b, c, d, e, and f are values in the following ranges, respectively.
0.00001 ≦ a ≦ 0.15
a + b = 1
0.5 ≦ c ≦ 1.5
0.5 ≦ d ≦ 1.5
2.5 ≦ e ≦ 3.5
0 ≦ f ≦ 0.5)
(6) The light-emitting device according to ( 5), wherein the first phosphor is represented by the following general formula [2].
M ^{1 ′} _{a ′} Sr _{b ′} Ca _{c ′} M ^{2 ′} _{d ′} Al _{e ′} Sif _′ N _{g ′} [2]
(However, M ^{1 ′} is one or more elements selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb.
M ^{2 ′} is Mg and / or Ba.
a ′, b ′, c ′, d ′, e ′, f ′, and g ′ each have a value within the following range.
0.00001 ≦ a ′ ≦ 0.15
0.1 ≦ b ′ ≦ 0.99999
0 ≦ c ′ <1
0 ≦ d ′ <1
a ′ + b ′ + c ′ + d ′ = 1
0.5 ≦ e ′ ≦ 1.5
0.5 ≦ f ′ ≦ 1.5
0.8 × (2/3 + e ′ + 4/3 × f ′) ≦ g ′ ≦ 1.2 × (2/3 + e ′ + 4/3 × f ′))
(7) In (6), the value of b ′ in the general formula [2] is in the range of 0.6 ≦ b ′ ≦ 0.99999, and d ′ = 0. .
In any one of (8) (1) to (7), wherein the alloy is an activator elements ^{M 1,} divalent metal elements ^{M 2,} include a tetravalent metal elements ^{M 4} including at least Si A light emitting device characterized by the above.
(9) The light emitting device according to any one of (1) to (8), wherein the phosphor includes a second phosphor having a light emission wavelength different from that of the first phosphor.
(10) The light emitting device according to (9), wherein the second phosphor includes a green phosphor having a peak wavelength in a wavelength range of 490 nm or more and 570 nm or less.
(11) In (10), as the green phosphor, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce, CaSc ₂ A light emitting device comprising at least one selected from the group consisting of O ₄ : Ce, Eu activated β sialon, Eu activated α sialon, and BaMgAl ₁₀ O ₁₇ : Eu, Mn.
(12) In any one of (9) to (11), the second phosphor contains a blue phosphor having a peak wavelength in a wavelength range of 420 nm or more and 480 nm or less. .
(13) A phosphor represented by the following general formula [2].
M ^{1 ′} _{a ′} Sr _{b ′} Ca _{c ′} M ^{2 ′} _{d ′} Al _{e ′} Sif _′ N _{g ′} [2]
(However, M ^{1 ′} is one or more elements selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb.
M ^{2 ′} is Mg and / or Ba.
a ′, b ′, c ′, d ′, e ′, f ′, and g ′ each have a value within the following range.
0.00001 ≦ a ′ ≦ 0.15
0.1 ≦ b ′ ≦ 0.99999
0 ≦ c ′ <1
0 ≦ d ′ <1
a ′ + b ′ + c ′ + d ′ = 1
0.5 ≦ e ′ ≦ 1.5
0.5 ≦ f ′ ≦ 1.5
0.8 × (2/3 + e ′ + 4/3 × f ′) ≦ g ′ ≦ 1.2 × (2/3 + e ′ + 4/3 × f ′))
(14) The phosphor according to (13), wherein the oxygen content is 5% by weight or less.
(15) A method for producing a phosphor represented by the following general formula [2], wherein the pressure is 10 MPa to 200 MPa, the temperature is 800 ° C. or more and 2200 ° C. or less in a nitrogen-containing atmosphere having an oxygen concentration of 1000 ppm or less. A method for producing a phosphor, comprising performing nitriding by heating for at least 24 minutes and not longer than 24 minutes.
M ^{1 ′} _{a ′} Sr _{b ′} Ca _{c ′} M ^{2 ′} _{d ′} Al _{e ′} Sif _′ N _{g ′} [2]
(However, M ^{1 ′} is one or more elements selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb.
M ^{2 ′} is Mg and / or Ba.
a ′, b ′, c ′, d ′, e ′, f ′, and g ′ each have a value within the following range.
0.00001 ≦ a ′ ≦ 0.15
0.1 ≦ b ′ ≦ 0.99999
0 ≦ c ′ <1
0 ≦ d ′ <1
a ′ + b ′ + c ′ + d ′ = 1
0.5 ≦ e ′ ≦ 1.5
0.5 ≦ f ′ ≦ 1.5
0.8 × (2/3 + e ′ + 4/3 × f ′) ≦ g ′ ≦ 1.2 × (2/3 + e ′ + 4/3 × f ′) )

Claims

In a light-emitting device having an excitation light source and a phosphor that converts the wavelength of at least part of light from the excitation light source,
The excitation light source is a light emitting diode having a peak emission wavelength of 300 nm or more and 500 nm or less;
As the phosphor comprises the activator elements ^{M 1,} divalent metal elements ^{M 2,} and a tetravalent metal elements ^{M 4} including at least Si, and,
A light emitting device comprising : a phosphor obtained by heating and nitriding an alloy in a nitrogen-containing atmosphere (hereinafter referred to as "first phosphor") .

^{2. The} light emitting device according to claim 1 , wherein the first phosphor includes an alkaline earth metal element as the divalent metal element M2.

According to claim 1 or claim 2, wherein the first phosphor, further light-emitting device which comprises a trivalent metal element M ^3.

In any one of claims 1 to 3, wherein the first phosphor comprises a Eu and / or Ce as activator elements ^{M 1,} 2 divalent metal elements ^{M 2} comprises Ca and / or Sr, A light-emitting device, wherein the trivalent metal element M ³ contains Al and the tetravalent metal element M ⁴ contains Si .

5. The light-emitting device according to claim 1, wherein the first phosphor is represented by the following general formula [1].
M ^１1 _ａa M ^２2 _ｂb M ^３3 _ｃc M ^４4 _ｄd N _ｅe O _ｆf [1]
(However, M ^１1 Is one or more elements selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb,
M ^２2 Is one or more elements selected from the group consisting of Mg, Ca, Sr, Ba, and Zn,
M ^３3 Is one or more elements selected from the group consisting of Al, Ga, In, and Sc,
M ^４4 Is one or more elements selected from the group consisting of Si, Ge, Sn, Ti, Zr, and Hf, which essentially require Si.
a, b, c, d, e, and f are values in the following ranges, respectively.
0.00001 ≦ a ≦ 0.15
a + b = 1
0.5 ≦ c ≦ 1.5
0.5 ≦ d ≦ 1.5
2.5 ≦ e ≦ 3.5
0 ≦ f ≦ 0.5)

6. The light emitting device according to claim 5, wherein the first phosphor is represented by the following general formula [2].
M ^{１’1 ’} _{ａ’a ’} Sr _{ｂ’b ’} Ca _{ｃ’c ’} M ^{２’2 ’} _{ｄ’d ’} Al _{ｅ’e ’} Si _{ｆ’f ’} N _{ｇ’g ’} [2]
(However, M ^{１’1 ’} Is one or more elements selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb,
M ^{２’2 ’} Is Mg and / or Ba.
a ′, b ′, c ′, d ′, e ′, f ′, and g ′ each have a value within the following range.
0.00001 ≦ a ′ ≦ 0.15
0.1 ≦ b ′ ≦ 0.99999
0 ≦ c ′ <1
0 ≦ d ′ <1
a '+ b' + c '+ d' = 1
0.5 ≦ e ′ ≦ 1.5
0.5 ≦ f ′ ≦ 1.5
0.8 × (2/3 + e ′ + 4/3 × f ′) ≦ g ′ ≦ 1.2 × (2/3 + e ′ + 4/3 × f ′))

The light-emitting device according to claim 6, wherein the value of b ′ in the general formula [2] is in a range of 0.6 ≦ b ′ ≦ 0.99999 and d ′ = 0.

The alloy according to any one of claims 1 to 7, wherein the alloy is an activating element M. ^１1 And the divalent metal element M ^２2 And a tetravalent metal element M containing at least Si ^４4 A light-emitting device comprising:

9. The light emitting device according to claim 1, wherein the phosphor includes a second phosphor having a light emission wavelength different from that of the first phosphor. 10.

10. The light emitting device according to claim 9, wherein the second phosphor includes a green phosphor having a peak wavelength in a wavelength range of 490 nm to 570 nm.

In Claim 10, as said green fluorescent substance, (Ba, Sr, Ca, Mg) _２2 SiO _４4 : Eu, Ca _３3 (Sc, Mg, Na, Li) _２2 Si _３3 O _１２12 : Ce, CaSc _２2 O _４4 : Ce, Eu-activated β sialon, Eu-activated α sialon, and BaMgAl _１０10 O _１７17 : A light-emitting device comprising at least one selected from the group consisting of Eu and Mn.

12. The light emitting device according to claim 9, wherein the second phosphor includes a blue phosphor having a peak wavelength in a wavelength range of 420 nm or more and 480 nm or less.

A phosphor represented by the following general formula [2].
M ^{１’1 ’} _{ａ’a ’} Sr _{ｂ’b ’} Ca _{ｃ’c ’} M ^{２’2 ’} _{ｄ’d ’} Al _{ｅ’e ’} Si _{ｆ’f ’} N _{ｇ’g ’} [2]
(However, M ^{１’1 ’} Is one or more elements selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb,
M ^{２’2 ’} Is Mg and / or Ba.
a ′, b ′, c ′, d ′, e ′, f ′, and g ′ each have a value within the following range.
0.00001 ≦ a ′ ≦ 0.15
0.1 ≦ b ′ ≦ 0.99999
0 ≦ c ′ <1
0 ≦ d ′ <1
a '+ b' + c '+ d' = 1
0.5 ≦ e ′ ≦ 1.5
0.5 ≦ f ′ ≦ 1.5
0.8 × (2/3 + e ′ + 4/3 × f ′) ≦ g ′ ≦ 1.2 × (2/3 + e ′ + 4/3 × f ′))

14. The phosphor according to claim 13, wherein the content of oxygen is 5% by weight or less.

A method for producing a phosphor represented by the following general formula [2],
Under a nitrogen-containing atmosphere with an oxygen concentration of 1000 ppm or less,
The pressure is 10 to 200 MPa, the temperature is 800 ° C. or more and 2200 ° C. or less,
A method for producing a phosphor, wherein nitriding is performed by heating for 1 minute to 24 hours.
M ^{1 ′} _{a ′} Sr _{b ′} Ca _{c ′} M ^{2 ′} _{d ′} Al _{e ′} Sif _′ N _{g ′} [2]
(However, M ^{1 ′} is one or more elements selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb.
M ^{2 ′} is Mg and / or Ba.
a ′, b ′, c ′, d ′, e ′, f ′, and g ′ each have a value within the following range.
0.00001 ≦ a ′ ≦ 0.15
0.1 ≦ b ′ ≦ 0.99999
0 ≦ c ′ <1
0 ≦ d ′ <1
a ′ + b ′ + c ′ + d ′ = 1
0.5 ≦ e ′ ≦ 1.5
0.5 ≦ f ′ ≦ 1.5
0.8 × (2/3 + e ′ + 4/3 × f ′) ≦ g ′ ≦ 1.2 × (2/3 + e ′ + 4/3 × f ′) )