JP6130808B2 - Phosphor and light emitting device - Google Patents
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- JP6130808B2 JP6130808B2 JP2014084522A JP2014084522A JP6130808B2 JP 6130808 B2 JP6130808 B2 JP 6130808B2 JP 2014084522 A JP2014084522 A JP 2014084522A JP 2014084522 A JP2014084522 A JP 2014084522A JP 6130808 B2 JP6130808 B2 JP 6130808B2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 238000010306 acid treatment Methods 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 230000005284 excitation Effects 0.000 description 9
- 238000012423 maintenance Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229920000995 Spectralon Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Description
本発明は、ＬＥＤ（Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ）又はＬＤ（Ｌａｓｅｒ Ｄｉｏｄｅ）用の蛍光体の製造方法に関する。
The present invention relates to a method for manufacturing a phosphor for LED (Light Emitting Diode) or LD (Laser Diode).
従来の蛍光体としては、例えば特許文献１、２に開示されている蛍光体が挙げられるが、発光素子を作製した際、長期使用による蛍光体の酸化や加水分解による劣化に由来した発光不良が生じていた。 Examples of conventional phosphors include phosphors disclosed in Patent Documents 1 and 2. However, when a light emitting device is manufactured, a light emission failure caused by deterioration due to oxidation or hydrolysis of the phosphor due to long-term use. It was happening.
特許文献２の実施例、比較例の蛍光体を用いた発光装置では、更なる高出力化に伴い、温度上昇によって、蛍光体の劣化による発光不良が見受けられた。この蛍光体の比表面積は、１．６ｍ２／ｇ以上５．０ｍ２／ｇ以下であった。 In the light emitting devices using the phosphors of the examples and comparative examples of Patent Document 2, a light emission failure due to deterioration of the phosphors was observed due to a temperature rise as the output was further increased. The specific surface area of this phosphor was 1.6 m 2 / g or more and 5.0 m 2 / g or less.
本発明の目的は、高出力のＬＥＤに長時間の使用があっても発光不良の少ない蛍光体の製造方法を提供することにある。
当該蛍光体を用いた用途としては、発光装置、照明装置、バックライト装置、画像表示装置及び交通標識としての信号機がある。
An object of the present invention is to provide a method for producing a phosphor with little light emission failure even when a high-power LED is used for a long time.
Applications using the phosphor include a light emitting device, a lighting device, a backlight device, an image display device, and a traffic signal as a traffic sign.
本発明は、一般式：Ｍ１ａＭ２ｂＭ３ｃＭ４ｄＮｅＯｆで表され、Ｍ１はＥｕ又はＣｅのいずれか一方又は双方、Ｍ２はＭｇ、Ｃａ、Ｓｒ、Ｂａ及びＺｎのうち１種以上の元素、Ｍ３はＡｌ、Ｇａ、Ｉｎ及びＳｃのうち１種以上の元素、Ｍ４はＳｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｚｒ及びＨｆのうち１種以上の元素であると共にＳｉを必須とし、Ｎは窒素、Ｏは酸素、ａ乃至ｆは、０．００００１≦ａ≦０．１５、ａ＋ｂ＝１、０．５≦ｃ≦１．５、０．５≦ｄ≦１．５、ｃ＋ｄ＝２、２．５≦ｅ≦３．０、０≦ｆ≦０．５、ｅ＋ｆ＝３であり、比表面積が６．０ｍ２／ｇ以上１０．０ｍ２／ｇ以下の、酸処理工程の処理物である蛍光体の製造方法である。なお、前記酸処理工程時の塩酸溶液濃度は４．５質量％以上６．０質量％以下、温度は７０℃であることが好ましい。 The present invention has the general formula: M1 is represented by a M2 b M3 c M4 d N e O f, either or both of Eu or Ce M1, M2 is Mg, Ca, Sr, 1 kind of Ba and Zn M3 is one or more elements of Al, Ga, In, and Sc, M4 is one or more elements of Si, Ge, Sn, Ti, Zr, and Hf, and Si is essential, N Is nitrogen, O is oxygen, a to f are 0.00001 ≦ a ≦ 0.15, a + b = 1, 0.5 ≦ c ≦ 1.5, 0.5 ≦ d ≦ 1.5, c + d = 2, 2.5 ≦ e ≦ 3.0, 0 ≦ f ≦ 0.5, e + f = 3, and a processed product of the acid treatment step having a specific surface area of 6.0 m 2 / g or more and 10.0 m 2 / g or less. It is a manufacturing method of a certain phosphor. In addition, it is preferable that the hydrochloric acid solution density | concentration at the time of the said acid treatment process is 4.5 mass% or more and 6.0 mass% or less, and temperature is 70 degreeC.
本発明は、Ｍ１がＥｕであり、Ｍ２がＣａ及びＳｒであり、Ｍ３はＡｌであり、Ｍ４はＳｉであることが好ましい。 In the present invention, it is preferable that M1 is Eu, M2 is Ca and Sr, M3 is Al, and M4 is Si.
本発明の蛍光体の製造方法で得られた蛍光体と、発光素子を有する発光装置を提供することができる。 A phosphor obtained by the phosphor production method of the present invention and a light emitting device having a light emitting element can be provided .
本発明によれば、長期信頼性に優れる、すなわち発光効率の低下が少なく、長時間の使用があっても発光不良の少ない蛍光体を提供することができ、同様な効果を発揮する発光装置を提供することができる。発光装置としては、具体的には、照明装置、バックライト装置、画像表示装置及び交通標識としての信号機がある。 According to the present invention, it is possible to provide a phosphor that is excellent in long-term reliability, i.e., has little decrease in light emission efficiency, and has few light emission defects even when used for a long time. Can be provided. Specific examples of the light emitting device include a lighting device, a backlight device, an image display device, and a traffic signal as a traffic sign.
本発明の実施の形態について説明する。
本発明は、一般式：Ｍ１ａＭ２ｂＭ３ｃＭ４ｄＮｅＯｆで表され、Ｍ１はＥｕ又はＣｅのいずれか一方又は双方、Ｍ２はＭｇ、Ｃａ、Ｓｒ、Ｂａ及びＺｎのうち１種以上の元素、Ｍ３はＡｌ、Ｇａ、Ｉｎ及びＳｃのうち１種以上の元素、Ｍ４はＳｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｚｒ及びＨｆのうち１種以上の元素であると共にＳｉを必須とし、Ｎは窒素、Ｏは酸素、ａ乃至ｆは、０．００００１≦ａ≦０．１５、ａ＋ｂ＝１、０．５≦ｃ≦１．５、０．５≦ｄ≦１．５、ｃ＋ｄ＝２、２．５≦ｅ≦３．０、０≦ｆ≦０．５、ｅ＋ｆ＝３であり、比表面積が６．０〜１０．０ｍ２／ｇの、酸処理工程の処理物である蛍光体の製造方法である。
Ｍ１は、発光中心元素であり、Ｅｕ又はＣｅのいずれか一方又は双方であり、求められる発光波長によって選択される。
Ｍ１は、あまりに少ないと十分な発光ピーク強度が得られない傾向にあり、あまりに多いと濃度消光が生じるため発光ピーク強度が低くなる傾向にあるため、一般式中のａは０．００００１以上０．１５以下である。
Embodiments of the present invention will be described.
The present invention has the general formula: M1 is represented by a M2 b M3 c M4 d N e O f, either or both of Eu or Ce M1, M2 is Mg, Ca, Sr, 1 kind of Ba and Zn M3 is one or more elements of Al, Ga, In, and Sc, M4 is one or more elements of Si, Ge, Sn, Ti, Zr, and Hf, and Si is essential, N Is nitrogen, O is oxygen, a to f are 0.00001 ≦ a ≦ 0.15, a + b = 1, 0.5 ≦ c ≦ 1.5, 0.5 ≦ d ≦ 1.5, c + d = 2, 2.5 ≦ e ≦ 3.0,0 ≦ f ≦ 0.5, a e + f = 3, the specific surface area is 6.0~10.0m 2 / g, is of the phosphor process of acid treatment step It is a manufacturing method .
M1 is an emission center element, and is either one or both of Eu and Ce, and is selected according to a required emission wavelength.
If M1 is too small, sufficient emission peak intensity tends not to be obtained. If M1 is too large, concentration quenching occurs and emission peak intensity tends to be low. Therefore, a in the general formula is 0.00001 or more and 0.00. 15 or less.
Ｍ２は、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ及びＺｎのうち１種以上の元素であり、Ｃａ、Ｓｒの一方又は双方が好ましい。一般式中のｂは、Ｍ１との関係上、ａ＋ｂ＝１である。 M2 is one or more elements of Mg, Ca, Sr, Ba and Zn, and one or both of Ca and Sr are preferable. In the general formula, b is a + b = 1 in relation to M1.
Ｍ３は、Ａｌ、Ｇａ、Ｉｎ及びＳｃのうち１種以上の元素であり、Ａｌが好ましい。Ｍ３は、あまりに少なくてもあまりに多くても、蛍光体製造時に異相が生じ目的の蛍光体を得る収率が低下してしまう傾向にあるため、一般式でのｃは０．５以上１．５以下である。
Ｍ４は、Ｓｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｚｒ及びＨｆのうち１種以上の元素であると共にＳｉを必須としたものであり、Ｓｉ単体が好ましい。Ｍ４は、あまりに少なくてもあまりに多くても、蛍光体製造時に異相が生じ目的の蛍光体を得る収率が低下してしまう傾向にあるため、一般式でのｄは０．５以上１．５以下である。ｃとｄの合計は、蛍光体の組成の設計上、２である。
M3 is one or more elements of Al, Ga, In, and Sc, and Al is preferable. If M3 is too small or too large, a heterogeneous phase is produced during the production of the phosphor, and the yield of obtaining the target phosphor tends to decrease. Therefore, c in the general formula is 0.5 or more and 1.5. It is as follows.
M4 is one or more elements of Si, Ge, Sn, Ti, Zr, and Hf and essentially requires Si, and Si alone is preferable. If M4 is too small or too large, a heterogeneous phase is produced during the production of the phosphor, and the yield of obtaining the target phosphor tends to decrease. Therefore, d in the general formula is 0.5 or more and 1.5. It is as follows. The sum of c and d is 2 in designing the phosphor composition.
一般式におけるＮは窒素であり、一般式のｅは２．５以上３．０以下であり２．７以上３．０以下が好ましい。一般式におけるＯは酸素であり、一般式のｆは０以上０．５以下であり０．３以下が好ましい。ｅとｆの合計は、蛍光体の組成の設計上、３である。 N in the general formula is nitrogen, and e in the general formula is 2.5 or more and 3.0 or less, and preferably 2.7 or more and 3.0 or less. O in the general formula is oxygen, and f in the general formula is 0 or more and 0.5 or less, and preferably 0.3 or less. The sum of e and f is 3 in designing the phosphor composition.
蛍光体の比表面積が６．０ｍ２／ｇ以上１０．０ｍ２／ｇ以下であるのは、比表面積が６．０ｇ／ｍ２より小さい場合、長時間の使用により封止樹脂中の水分による加水分解や酸化による劣化により発光不良が生じ、比表面積が１０．０ｍ２／ｇより大きい場合、過度な表面凹凸・欠陥による影響で光の吸収率が低下して蛍光体の発光効率低下が生じるためである。比表面積の制御は、蛍光体の製造方法における酸処理工程での塩酸溶液の温度と濃度を変更することによって対応できる。酸処理工程時の塩酸溶液の設定温度を上げると比表面積の値が高くなる傾向にあり、酸処理工程時の塩酸溶液の酸濃度を上げると比表面積の値が高くなる傾向にある。 The specific surface area of the phosphor is 6.0 m 2 / g or more and 10.0 m 2 / g or less because, when the specific surface area is less than 6.0 g / m 2, it depends on the moisture in the sealing resin when used for a long time. If the specific surface area is greater than 10.0 m 2 / g due to degradation due to hydrolysis or oxidation, the light absorption rate is reduced due to excessive surface irregularities and defects, resulting in a decrease in the luminous efficiency of the phosphor. Because. Control of the specific surface area can correspond by changing the temperature and concentration of the hydrochloric acid solution with an acid treatment step in the production method of the phosphor. Tend to the value of increasing the specific surface area of the set temperature of the hydrochloric acid solution during the acid treatment step is high, there is a tendency that the value of the specific surface area increasing the acid concentration of the hydrochloric acid solution during the acid treatment step is high.
本発明に係る蛍光体に設けた表面層は、蛍光体の発光効率の低下を抑え、長時間の使用があっても蛍光体自体の劣化、すなわち発光効率の低下を抑えることができる。表面層は、蛍光体の母体結晶とは異なる酸素成分を主成分とした化学組成を含んだものが好ましい。 The surface layer provided in the phosphor according to the present invention can suppress a decrease in luminous efficiency of the phosphor, and can suppress deterioration of the phosphor itself, that is, a decrease in luminous efficiency even when used for a long time. The surface layer preferably contains a chemical composition mainly composed of an oxygen component different from the host crystal of the phosphor.
＜比表面積の測定方法＞
比表面積は、比表面積測定装置（マウンテック社製Ｍａｃｓｏｒｂ ＨＭ−１２０１型）を用いて、ＪＩＳ Ｚ ８８３０：２０１３ ガス吸着による粉体（固体）の比表面積測定に準拠して行った。吸着ガス量の測定方法は、同ＪＩＳ Ｚ ８８３０ ６．３．４ キャリアガス法を採用した。吸着データの解析は、同ＪＩＳ Ｚ ８８３０ ７．３ 一点法を採用した。測定試料は、あらかじめ０．３０ＭＰａでの窒素ガスフロー中、３００℃、３０分の脱気処理後、４．０gサンプリングしたものである。
<Method for measuring specific surface area>
The specific surface area was measured in accordance with JIS Z 8830: 2013 gas specific surface area measurement by gas adsorption using a specific surface area measuring device (Macsorb HM-1201 type, manufactured by Mountec Co., Ltd.). The JIS Z 8830 6.3.4 carrier gas method was adopted as a method for measuring the amount of adsorbed gas. For the analysis of the adsorption data, the same JIS Z 8830 7.3 single point method was adopted. The measurement sample was obtained by sampling 4.0 g after deaeration treatment at 300 ° C. for 30 minutes in a nitrogen gas flow at 0.30 MPa in advance.
本発明に係る蛍光体を用いた装置としては、発光素子を有する発光装置があり、この発光装置としては、照明装置、液晶モニタの背面で発光するバックライト装置、この発光装置と画像表示モニタを有する画像表示装置、及び、交通標識としての信号機がある。 As a device using the phosphor according to the present invention , there is a light-emitting device having a light-emitting element. As the light-emitting device, an illumination device, a backlight device that emits light on the back of a liquid crystal monitor, and the light-emitting device and an image display monitor are provided. There are image display devices and traffic lights as traffic signs.
本発明に係る発光装置は、上述の蛍光体の他、他の発光色の蛍光体と発光光源とを備える装置である。発光光源としては、紫外ＬＥＤ、青色ＬＥＤ、蛍光体ランプの単体又はこれらの組み合わせがある。使用する蛍光体の組み合わせにより発光装置からの発光色を白色や他の波長の色とすることができる。 The light-emitting device according to the present invention is a device that includes a phosphor of another emission color and a light-emitting light source in addition to the phosphor described above. As the light emission source, there are a single unit of ultraviolet LED, blue LED, and phosphor lamp, or a combination thereof. Depending on the combination of phosphors to be used, the color emitted from the light emitting device can be white or other wavelength.
本発明に係る蛍光体及び発光装置は、長期信頼性に優れるものであり、具体的には、発光効率の低下が少なく、長時間の使用があっても発光不良が少ないものである。 The phosphor and the light emitting device according to the present invention are excellent in long-term reliability. Specifically, the phosphor and the light emitting device are less likely to emit light even when used for a long time with little decrease in light emission efficiency.
以下、本発明に係る蛍光体を比較例と対比し、表１を参照しつつ説明する。
Hereinafter, the phosphor according to the present invention will be described with reference to Table 1 in comparison with the comparative example.
実施例１の蛍光体は、一般式：Ｍ１ａＭ２ｂＭ３ｃＭ４ｄＮｅＯｆで表される蛍光体であり、その組成は、表１に示すように、Ｅｕ０．００８Ｃａ０．１００Ｓｒ０．８９２Ａｌ１．０００Ｓｉ１．０００Ｎ２．９００Ｏ０．１００である。
実施例１の蛍光体は、Ｍ１をＥｕ、Ｍ２をＣａとＳｒ、Ｍ３をＡｌ、及びＭ４をＳiとしたものである。
Phosphor of Example 1 has the general formula: M1 a M2 b M3 c M4 d N e O a phosphor represented by f, the composition, as shown in Table 1, Eu 0.008 Ca 0. a 100 Sr 0.892 Al 1.000 Si 1.000 N 2.900 O 0.100.
The phosphor of Example 1 has M1 as Eu, M2 as Ca and Sr, M3 as Al, and M4 as Si.
実施例１の蛍光体の製造方法は、表１の組成になるように原料を混合する混合工程、混合工程後の混合物を焼成する焼成工程、焼成工程後の焼成物を粉砕し分級した後に酸溶液に浸して不純物を溶解する酸処理工程を有するものである。表１には、製造方法のうち、酸処理工程での酸処理条件のみ記載した。
実施例１の酸処理条件は、酸溶液として塩酸溶液を用い、その塩酸濃度５．０％、温度７０．０℃とした。
The manufacturing method of the phosphor of Example 1 includes a mixing step of mixing raw materials so as to have the composition shown in Table 1, a baking step of baking the mixture after the mixing step, and pulverizing and classifying the baking product after the baking step. It has an acid treatment step of dissolving impurities by dipping in a solution. Table 1 shows only the acid treatment conditions in the acid treatment step of the production method.
The acid treatment conditions of Example 1 were such that a hydrochloric acid solution was used as the acid solution, the hydrochloric acid concentration was 5.0%, and the temperature was 70.0 ° C.
表１の各項目について説明する。
＜ＣＩＥ色度座標ｘ値、ｙ値＞
ＣＩＥ色度座標ｘ値、ｙ値は、実施例、比較例の蛍光体の発光色の確認のための値である。
この測定方法は、次の通りである。
実施例１の蛍光体を試料として凹型のセルに充填し、表面を平滑にして、積分球を取り付けた。この積分球に、発光光源としてのＸｅランプから４５５ｎｍの波長に分光した単色光を、光ファイバーを用いて導入した。この単色光を励起源として試料に照射し、分光光度計（大塚電子株式会社製ＭＣＰＤ−７０００）を用いて、蛍光体の発光スペクトル測定を行った。得られた発光スペクトルにおいて、励起波長が４５５ｎｍのときの、４６５ｎｍから７８０ｎｍの範囲の波長域データからＪＩＳ Ｚ ８７２４に準じ、ＪＩＳ Ｚ ８７０１で規定されるＸＹＺ表色系におけるＣＩＥ色度座標ｘ値、ｙ値を算出した。
ＣＩＥ色度座標ｘ値、ｙ値は、赤色発光のため、０．６２０〜０．６６０、０．３３０〜０．３８０が好ましい。
Each item in Table 1 will be described.
<CIE chromaticity coordinate x value, y value>
The CIE chromaticity coordinate x value and y value are values for confirming the emission color of the phosphors of the examples and comparative examples.
This measuring method is as follows.
The phosphor of Example 1 was filled in a concave cell as a sample, the surface was smoothed, and an integrating sphere was attached. Into this integrating sphere, monochromatic light dispersed at a wavelength of 455 nm from an Xe lamp as a light source was introduced using an optical fiber. The sample was irradiated with this monochromatic light as an excitation source, and the emission spectrum of the phosphor was measured using a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). In the obtained emission spectrum, the CIE chromaticity coordinate x value in the XYZ color system defined by JIS Z 8701 according to JIS Z 8724 from the wavelength range data in the range of 465 nm to 780 nm when the excitation wavelength is 455 nm, The y value was calculated.
The CIE chromaticity coordinate x value and y value are preferably 0.620 to 0.660 and 0.330 to 0.380 for red light emission.
＜吸収率＞
吸収率は、蛍光体の表面凹凸・欠陥を確認する指標である。吸収率が低いと蛍光体の発光効率低下が生じるため好ましくない。吸収率の合格値は８０％以上である。
蛍光体の吸収率は、次式で求めた。
吸収率＝（励起光フォトン数（Ｑｅｘ）−励起反射光フォトン数（Ｑｒｅｆ）／励起光フォトン数（Ｑｅｘ））×１００）
吸収率は次のように測定し、算出した。
分光光度計（大塚電子株式会社製ＭＣＰＤ−７０００）を用いて、試料部に蛍光体を反射率が９９％の標準反射板（Ｌａｂｓｐｈｅｒｅ社スペクトラロン）をセットし、励起光のスペクトルを測定し、励起波長４５５ｎｍとして４５０ｎｍから４６５ｎｍの波長範囲のスペクトルから励起光フォトン数（Ｑｅｘ）を算出した。
試料部に蛍光体をセットし、得られたスペクトルデータから励起反射光フォトン数（Ｑｒｅｆ）を算出した。
励起反射光フォトン数（Ｑｒｅｆ）は、励起光フォトン数（Ｑｅｘ）と同じ波長範囲で算出した。
<Absorption rate>
The absorptance is an index for confirming surface irregularities and defects of the phosphor. A low absorptance is not preferable because the luminous efficiency of the phosphor is reduced. The acceptance value of the absorption rate is 80% or more.
The absorption rate of the phosphor was determined by the following equation.
Absorption rate = (excitation light photon number (Qex) −excitation reflected light photon number (Qref) / excitation light photon number (Qex)) × 100)
The absorptance was measured and calculated as follows.
Using a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.), set a standard reflector (Spectralon manufactured by Labsphere) with a reflectance of 99% on the sample part, and measure the spectrum of the excitation light. The excitation light photon number (Qex) was calculated from the spectrum in the wavelength range from 450 nm to 465 nm with an excitation wavelength of 455 nm.
A phosphor was set in the sample portion, and the number of excited reflected light photons (Qref) was calculated from the obtained spectrum data.
The excitation reflected light photon number (Qref) was calculated in the same wavelength range as the excitation light photon number (Qex).
＜相対発光ピーク強度＞
相対発光ピーク強度は、蛍光体の表面凹凸、欠陥を確認する指標である。
蛍光分光高度計（株式会社日立ハイテクノロジーズ製Ｆ−７０００）を使用し、発光光源としてのＸｅランプから所定の波長に分光した４５５ｎｍの単色光をＹＡＧ：Ｃｅ（化成オプトニクス株式会社製Ｐ４６Ｙ３）に照射して得られる発光スペクトルのピーク高さを１００％とし、被測定物としての蛍光体より得られたピーク高さを相対ピーク強度（％）で表したものである。
相対発光ピーク強度の合格値は１７０％以上である。
<Relative emission peak intensity>
The relative emission peak intensity is an index for confirming surface irregularities and defects of the phosphor.
Using a fluorescence spectrophotometer (F-7000, manufactured by Hitachi High-Technologies Corporation), YAG: Ce (P46Y3, manufactured by Kasei Optonics Co., Ltd.) is irradiated with 455 nm monochromatic light that is split into a predetermined wavelength from an Xe lamp as a light source. The peak height of the emission spectrum obtained in this way is taken as 100%, and the peak height obtained from the phosphor as the object to be measured is expressed in relative peak intensity (%).
The acceptable value of the relative light emission peak intensity is 170% or more.
＜比表面積の測定方法＞
比表面積は、比表面積測定装置（マウンテック社製Ｍａｃｓｏｒｂ ＨＭ−１２０１型）を用いて、ＪＩＳ Ｚ ８８３０：２０１３ ガス吸着による粉体（固体）の比表面積測定に準拠して行った。吸着ガス量の測定方法は、同ＪＩＳ Ｚ ８８３０ ６．３．４ キャリアガス法を採用した。吸着データの解析は、同ＪＩＳ Ｚ ８８３０ ７．３ 一点法を採用した。測定試料は、あらかじめ０．３０ＭＰａでの窒素ガスフロー中、３００℃、３０分の脱気処理後、４．０gサンプリングしたものである。
<Method for measuring specific surface area>
The specific surface area was measured in accordance with JIS Z 8830: 2013 gas specific surface area measurement by gas adsorption using a specific surface area measuring device (Macsorb HM-1201 type, manufactured by Mountec Co., Ltd.). The JIS Z 8830 6.3.4 carrier gas method was adopted as a method for measuring the amount of adsorbed gas. For the analysis of the adsorption data, the same JIS Z 8830 7.3 single point method was adopted. The measurement sample was obtained by sampling 4.0 g after deaeration treatment at 300 ° C. for 30 minutes in a nitrogen gas flow at 0.30 MPa in advance.
＜相対発光ピーク強度維持率＞
相対発光ピーク強度維持率は、高度加速寿命試験装置（エスペック株式会社ＥＨＳ−２２１Ｍ）を用いて、温度１３０℃、湿度９８％の条件で１００時間静置した前後における相対発光ピーク強度の比率を算出したものである。合格値は９７％以上である。
実施例１の蛍光体は全ての評価結果において合格値であった。結果を表１に示す。
<Relative emission peak intensity maintenance ratio>
The relative emission peak intensity maintenance ratio is calculated by calculating the ratio of the relative emission peak intensity before and after standing for 100 hours at a temperature of 130 ° C. and a humidity of 98% using an advanced accelerated life test apparatus (Espec Corporation EHS-221M). It is a thing. The passing value is 97% or more.
The phosphor of Example 1 was a pass value in all evaluation results. The results are shown in Table 1.
［実施例２〜７、比較例１及び２］
実施例２〜７、比較例１及び２の蛍光体は、実施例１の蛍光体に比べ、表１に示すように、比表面積、組成を変更させたものである。比表面積を変更するには、酸処理工程で用いた塩酸の濃度を変更した。組成の変更は、原料の組成比の変更によって行った。実施例２乃至７の蛍光体の吸収率、相対発光ピーク強度、及び、相対発光ピーク強度維持率は、いずれにおいても合格値であった。
[Examples 2 to 7, Comparative Examples 1 and 2]
As shown in Table 1, the phosphors of Examples 2 to 7 and Comparative Examples 1 and 2 have different specific surface areas and compositions as compared to the phosphor of Example 1. In order to change the specific surface area, the concentration of hydrochloric acid used in the acid treatment step was changed. The composition was changed by changing the composition ratio of the raw materials. The absorption rate, relative emission peak intensity, and relative emission peak intensity maintenance rate of the phosphors of Examples 2 to 7 were acceptable values.
表１には記載しなかったが、実施例１の一般式でのＭ１としてのＥｕを、Ｅｕ及びＣｅにした実施例、Ｃｅにした実施例を作成した。いずれの実施例も発光波長の変化があったが、相対発光ピーク強度、相対発光ピーク強度維持率において、実施例１と同様な効果を得た。 Although not described in Table 1, Examples in which Eu as M1 in the general formula of Example 1 was Eu and Ce, and Examples in which Ce was used were prepared. In all Examples, the emission wavelength changed, but the same effect as Example 1 was obtained in the relative emission peak intensity and the relative emission peak intensity maintenance rate.
表１には記載しなかったが、実施例１の一般式でのＭ２としてのＣａ及びＳｒを、Ｃａにした実施例、Ｓｒにした実施例、及び、Ｍｇ及びＳｒにした実施例を作成した。いずれの実施例も実施例１と同様な効果を得た。 Although not described in Table 1, Examples in which Ca and Sr as M2 in the general formula of Example 1 were changed to Ca, examples in which Sr was changed, and examples in which Mg and Sr were changed to were prepared. . In all examples, the same effect as in Example 1 was obtained.
表１には記載しなかったが、実施例１の一般式でのＭ３としてのＡｌを、Ｇａにした実施例、Ａｌ及びＧａにした実施例、及び、Ｉｎにした実施例を作成した。いずれの実施例も実施例１と同様な効果を得た。 Although not described in Table 1, an example in which Al as M3 in the general formula of Example 1 was changed to Ga, an example in which Al and Ga were changed, and an example in which In was made were prepared. In all examples, the same effect as in Example 1 was obtained.
表１には記載しなかったが、実施例１の一般式でのＭ４としてのＳｉを、Ｓｉ及びＧｅにした実施例、Ｓｉ及びＺｒにした実施例、及び、Ｓｉ及びＴｉにした実施例を作成した。いずれの実施例も実施例１と同様な効果を得た。 Although not described in Table 1, Examples in which Si as M4 in the general formula of Example 1 was changed to Si and Ge, examples in which Si and Zr were changed, and examples in which Si and Ti were changed to Si and Ti were used. Created. In all examples, the same effect as in Example 1 was obtained.
［比較例１］
比較例１の蛍光体は、表１に示すように酸処理工程での塩酸濃度を変化させた以外、実施例１と同じ製造方法によって製造したものであり、比表面積が４．７ｍ２／ｇと小さく、相対発光ピーク強度維持率が９７％未満であった。
[Comparative Example 1]
The phosphor of Comparative Example 1 was produced by the same production method as Example 1 except that the hydrochloric acid concentration in the acid treatment step was changed as shown in Table 1, and the specific surface area was 4.7 m 2 / g. The relative emission peak intensity maintenance rate was less than 97%.
［比較例２］
比較例２の蛍光体は、表１に示すように酸処理工程での塩酸濃度を変化させた以外、実施例１と同じ製造方法によって製造したものであり、比表面積が１１．８ｍ２／ｇと大きく、吸収率が８０％未満であり、相対発光ピーク強度維持率が９７％未満であった。
[Comparative Example 2]
The phosphor of Comparative Example 2 was produced by the same production method as Example 1 except that the hydrochloric acid concentration in the acid treatment step was changed as shown in Table 1, and the specific surface area was 11.8 m 2 / g. The absorption rate was less than 80%, and the relative emission peak intensity maintenance rate was less than 97%.
蛍光体の相対発光ピーク強度維持率をみると、比表面積が６〜１０ｍ２／ｇの範囲内であれば劣化が小さく、長期信頼性に優れていた。 Looking at the relative emission peak intensity maintenance rate of the phosphor, the deterioration was small and the long-term reliability was excellent if the specific surface area was in the range of 6 to 10 m 2 / g.
［他の比較例］
表１には示さないが、実施例１のＥｕ０．００８Ｃａ０．１００Ｓｒ０．８９２Ａｌ１．０００Ｓｉ１．０００Ｎ２．９００Ｏ０．１００での組成比を変更した比較例について説明する。
一般式でのＭ１としてのＥｕの０．００８を０．００００１未満にし、ａ＋ｂ＝１を維持しつつＣａとＳｒの合計の比率を高めた比較例にあっては、相対発光ピーク強度が１７０％を超えなかった。
一般式でのＭ１としてのＥｕの０．００８を０．１５より大きい値にして、ａ＋ｂ＝１を維持しつつＣａとＳｒの合計の比率を下げた比較例にあっては、相対発光ピーク強度が１７０％を超えなかった。
一般式でのＭ３としてのＡｌの１．０００を０．５未満にし、ｃ＋ｄ＝２を維持しつつＳｉを１．５より大きい値にした比較例にあっては、製造後の蛍光体を評価すると、異相のものが多く、収率が悪かった。
一般式でのＭ３としてのＡｌの１．０００を０．５より大きい値にし、ｃ＋ｄ＝２を維持しつつＳｉを１．５未満の値にした比較例にあっては、製造後の蛍光体を評価すると、異相のものが多く、収率が悪かった。
[Other comparative examples]
Although not shown in Table 1, the comparative example of changing the composition ratio of In Eu 0.008 Ca 0.100 Sr 0.892 Al 1.000 Si 1.000 N 2.900 O 0.100 Example 1 explain.
In the comparative example in which 0.008 of Eu as M1 in the general formula is less than 0.00001 and the total ratio of Ca and Sr is increased while maintaining a + b = 1, the relative emission peak intensity is 170%. Did not exceed.
In the comparative example in which 0.008 of Eu as M1 in the general formula is set to a value larger than 0.15 and the total ratio of Ca and Sr is reduced while maintaining a + b = 1, the relative emission peak intensity Did not exceed 170%.
In the comparative example in which 1.000 of Al as M3 in the general formula is less than 0.5, and Si is set to a value larger than 1.5 while maintaining c + d = 2, the phosphor after manufacture is evaluated. Then, there were many things of a different phase and the yield was bad.
In the comparative example in which 1.000 of Al as M3 in the general formula is set to a value greater than 0.5 and Si is set to a value less than 1.5 while maintaining c + d = 2, the phosphor after manufacture As a result, the yield was poor due to the large number of different phases.
［実施例８、９及び１０］
実施例８、９及び１０は、表１には記載しなかったが、実施例１、２及び３の蛍光体をＬＥＤの発光面に搭載した発光装置である。発光装置として照明装置を採用した。これら実施例は、相対発光ピーク強度維持率の高い蛍光体を用いたので、より時間が経過しても劣化の少ない発光装置であった。
[Examples 8, 9 and 10]
Examples 8, 9, and 10 are light emitting devices that are not described in Table 1, but in which the phosphors of Examples 1, 2, and 3 are mounted on the light emitting surface of the LED. A lighting device was adopted as the light emitting device. In these examples, since a phosphor having a high relative emission peak intensity maintenance rate was used, it was a light emitting device with little deterioration over time.
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