JP2015137328A - Ce3+ ACTIVATED OXIDE PHOSPHOR - Google Patents
Ce3+ ACTIVATED OXIDE PHOSPHOR Download PDFInfo
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- JP2015137328A JP2015137328A JP2014010335A JP2014010335A JP2015137328A JP 2015137328 A JP2015137328 A JP 2015137328A JP 2014010335 A JP2014010335 A JP 2014010335A JP 2014010335 A JP2014010335 A JP 2014010335A JP 2015137328 A JP2015137328 A JP 2015137328A
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Abstract
Description
本発明は、母体化合物に発光中心イオンとしてセリウム（Ｃｅ３＋）を含有してなる蛍光体に関するものである。 The present invention relates to a phosphor comprising cerium (Ce 3+ ) as a luminescent center ion in a base compound.
近年、青色発光ダイオードと蛍光体とを組み合わせて構成された白色発光の発光素子は、消費電力が小さく長寿命であるという特徴を有することから、照明用光源として注目されている。 2. Description of the Related Art In recent years, white light-emitting elements configured by combining blue light-emitting diodes and phosphors have attracted attention as illumination light sources because of their low power consumption and long lifetime.
この発光素子は、青色発光ダイオードの発する青色光と、青色光を吸収して黄色発光する蛍光体の黄色光との混色により白色の発光が得られるものであるが、光の３原色のうち緑色と赤色が欠けているため、色純度が低いという問題があった。 This light-emitting element can obtain white light emission by mixing the blue light emitted from the blue light-emitting diode and the yellow light of the phosphor that absorbs blue light and emits yellow light. In addition, there is a problem that the color purity is low due to lack of red.
なお、従来より、青色光を吸収して赤色発光する蛍光体として、窒化物蛍光体及び酸窒化物蛍光体があるが、これらの蛍光体の合成には高温（より具体的には、２０００℃近く）、高圧（より具体的には、５〜１０気圧程度）が必要であるため、これらの蛍光体の製造が必ずしも容易と言えるものではなかった。 Conventionally, as phosphors that absorb blue light and emit red light, there are nitride phosphors and oxynitride phosphors, but these phosphors are synthesized at a high temperature (more specifically, 2000 ° C. Nearly) and high pressure (more specifically, about 5 to 10 atm) are required, and thus it is not always easy to produce these phosphors.
そこで、本発明では上記問題点に鑑み、製造が容易な酸化物蛍光体を、更には、より色純度の高い発光素子を得ることができる蛍光体を提供することを目的とする。 In view of the above problems, an object of the present invention is to provide an easy-to-manufacture oxide phosphor and a phosphor capable of obtaining a light-emitting element with higher color purity.
本発明者らは、前記課題を解決すべく鋭意検討した結果、特定の化合物を母体とし、核母体内に発光中心イオンとしてＣｅ３＋を含有してなる蛍光体が、前記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a phosphor comprising a specific compound as a host substance and containing Ce 3+ as a luminescent center ion in the nucleus host body can achieve the object. The present invention has been completed.
すなわち本発明は、以下の構成・特徴を備えるものである。 That is, the present invention has the following configuration / features.
（態様１）
一般式（Ｉ）： Ｍ１ ａＭ２ ｂＭ３ ｃＯｄ（但し、前記式（Ｉ）中、Ｍ１は少なくともＳｒを含む２価の金属元素であり、Ｍ２はＳｃ、Ｙ及びＬｕからなる群から選択された少なくとも１種を含む３価の金属元素であり、Ｍ３は少なくともＡｌを含む３価の金属元素である。ａは５．４〜６．６、ｂは１．８〜２．２、ｃは３．６〜４．４、ｄは１４．０〜１６．０の範囲の数である。）で表される化合物を母体とし、該母体内に発光中心イオンとしてＣｅを含有してなることを特徴とする蛍光体。
（態様２）
Ｍ１はＳｒであり、かつ、Ｍ３はＡｌであることを特徴とする態様１に記載の蛍光体。
（態様３）
仕込み時の組成として、Ｓｒ６（Ｙ１−ｘＣｅｘ）２Ａｌ４Ｏ１５（但し、０．０５≦ｘ≦０．２５）で表され、かつ、その発光色が橙色又は赤色であることを特徴とする態様２に記載の蛍光体。
（態様４）
ｘ＝０．１０〜０．１５であることを特徴とする態様３に記載の蛍光体。
（態様５）
態様１〜４のいずれか１項に記載の蛍光体を含み、波長３８０〜５００ｎｍの紫外線又は青色光を励起源として、波長５００〜７００ｎｍの可視光を発することを特徴とする光源。
(Aspect 1)
General formula (I): M 1 a M 2 b M 3 c O d (wherein, in formula (I), M 1 is a divalent metal element containing at least Sr, and M 2 is Sc, Y and Lu A trivalent metal element including at least one selected from the group consisting of M 3 and a trivalent metal element including at least Al, a is 5.4 to 6.6, and b is 1.8. ~ 2.2, c is a number in the range of 3.6 to 4.4, d is a number in the range of 14.0 to 16.0), and Ce is used as the luminescent center ion in the matrix. A phosphor comprising:
(Aspect 2)
The phosphor according to aspect 1, wherein M 1 is Sr and M 3 is Al.
(Aspect 3)
The composition at the time of preparation is represented by Sr 6 (Y 1-x Ce x ) 2 Al 4 O 15 (where 0.05 ≦ x ≦ 0.25), and the emission color is orange or red The phosphor according to
(Aspect 4)
The phosphor according to aspect 3, wherein x = 0.10 to 0.15.
(Aspect 5)
A light source comprising the phosphor according to any one of aspects 1 to 4 and emitting visible light having a wavelength of 500 to 700 nm using ultraviolet light or blue light having a wavelength of 380 to 500 nm as an excitation source.
本発明によれば、従来の窒化物蛍光体などの製造方法と比較して、より低い焼成温度・圧力（例えば、１２００℃〜１６００℃・常圧）の下で製造できる（つまり、製造が容易である）と共に、色純度の高い発光素子を得ることができる蛍光体、及び、その蛍光体を用いた光源を提供することができる。 According to the present invention, it can be manufactured at a lower firing temperature and pressure (for example, 1200 ° C. to 1600 ° C. and normal pressure) as compared with a conventional method of manufacturing a nitride phosphor (ie, easy to manufacture). In addition, a phosphor capable of obtaining a light-emitting element with high color purity and a light source using the phosphor can be provided.
本発明の蛍光体は、前記式（Ｉ）Ｍ１ ａＭ２ ｂＭ３ ｃＯｄ：Ｃｅ３+で表される化合物を母体とするものであり、一般に、Ｍ１、Ｍ２、及びＭ３の金属元素を含む複合酸化物である。Ｍ１が少なくともＳｒ（ストロンチウム）を含む２価、Ｍ２がＳｃ（スカンジウム）、Ｙ（イットリウム）及びＬｕ（ルテチウム）からなる群から選択された少なくとも１種を含む３価、Ｍ３が少なくともＡｌ（アルミニウム）を含む３価の金属元素である化合物を蛍光体の母体とすることを特徴とする。 The phosphor of the present invention is based on a compound represented by the formula (I) M 1 a M 2 b M 3 c O d : Ce 3+ , and generally, M 1 , M 2 , and M 3 is a composite oxide containing three metal elements. M 1 is divalent including at least Sr (strontium), M 2 is trivalent including at least one selected from the group consisting of Sc (scandium), Y (yttrium) and Lu (lutetium), and M 3 is at least Al. A compound which is a trivalent metal element containing (aluminum) is used as a base material of a phosphor.
前記蛍光体は、Ｍ１はＳｒであり、かつ、Ｍ３はＡｌであることが好ましい。 In the phosphor, M 1 is preferably Sr and M 3 is preferably Al.
前記蛍光体は、仕込み時の組成として、Ｓｒ６（Ｙ１−ｘＣｅｘ）２Ａｌ４Ｏ１５（但し、０．０５≦ｘ≦０．２５）で表され、かつ、その発光色が橙色又は赤色であることが好ましい。なお、前記一般式（Ｉ）は製造した結果物の構造として表示されるが、仕込み時には化学量論比となるよう秤量されなければならない。そして、製造後には、Ｃｅ３+が製造された蛍光体の結晶構造のうち、どのサイトに結合されたかの特定は現実的には困難であるため、上記仕込み時の組成で表すことにした。 The phosphor is represented by Sr 6 (Y 1-x Ce x ) 2 Al 4 O 15 (provided that 0.05 ≦ x ≦ 0.25) as the composition at the time of preparation, and the emission color is orange. Or it is preferable that it is red. In addition, although the said general formula (I) is displayed as a structure of the manufactured result, it must be weighed so that it may become a stoichiometric ratio at the time of preparation. And after manufacture, since it was difficult to specify which site was bonded among the crystal structure of the phosphor from which Ce 3+ was manufactured, it was expressed by the composition at the time of preparation.
前記蛍光体は、ｘ＝０．１０〜０．１５であることが好ましい。 The phosphor preferably has x = 0.10 to 0.15.
本発明によれば、前記蛍光体を含み、波長３８０〜５００ｎｍの紫外線又は青色光を励起源として、波長５００〜７００ｎｍの可視光を発することを特徴とする光源も提供される。 According to the present invention, there is also provided a light source including the phosphor and emitting visible light having a wavelength of 500 to 700 nm using ultraviolet light or blue light having a wavelength of 380 to 500 nm as an excitation source.
（Ｓｒ６Ｙ２Ａｌ４Ｏ１５：Ｃｅ３+の蛍光体の製造方法）
ＳｒＣＯ３、Ｙ２Ｏ３、Ａｌ２Ｏ３、ＣｅＯ２の各原料粉末をＳｒ６（Ｙ１−ｘＣｅｘ）２Ａｌ４Ｏ１５ （ｘ＝０．１０、０．１５、又は０．２０）の化学量論比となるよう秤量し、メノウ乳鉢でアセトン湿式混合した後、還元雰囲気下（常圧）１５００℃、１２時間で焼成した。なお、前記焼成温度・焼成時間は例示に過ぎず、１２００℃〜１６００℃・６時間〜２４時間の範囲で選択可能である。
(Manufacturing method of phosphor of Sr 6 Y 2 Al 4 O 15 : Ce 3+ )
Each raw material powder of SrCO 3 , Y 2 O 3 , Al 2 O 3 , and CeO 2 is converted into Sr 6 (Y 1-x Ce x ) 2 Al 4 O 15 (x = 0.10, 0.15, or 0.20). ) And stoichiometrically mixed with acetone in an agate mortar, followed by firing in a reducing atmosphere (normal pressure) at 1500 ° C. for 12 hours. In addition, the said baking temperature and baking time are only illustrations, It can select in the range of 1200 to 1600 degreeC and 6 hours to 24 hours.
（Ｓｒ６Ｙ２Ａｌ４Ｏ１５：Ｃｅ３+の蛍光体の評価方法）
合成した蛍光体は、アルミナ乳鉢で粉砕後、粉末Ｘ線回折装置により試料の同定を行なった。さらに、蛍光分光光度計を用いて、合成した蛍光体の蛍光特性を評価した。
(Sr 6 Y 2 Al 4 O 15 : Ce 3+ phosphor evaluation method)
The synthesized phosphor was pulverized in an alumina mortar, and then the sample was identified by a powder X-ray diffractometer. Furthermore, the fluorescence characteristics of the synthesized phosphors were evaluated using a fluorescence spectrophotometer.
（実施例に係る蛍光体のＸＲＤパターン）
図１の第２〜第４段に、得られた試料（Ｓｒ６Ｙ２Ａｌ４Ｏ１５：Ｃｅ３+）の粉末Ｘ線回折（ＸＲＤ）パターンを示す。得られた粉末は、目的物であるＳｒ６Ｙ２Ａｌ４Ｏ１５相（図１の最上段を参照）と同定された。他に不純物相が観察されないことから、賦活したＣｅ３＋はＳｒ６Ｙ２Ａｌ４Ｏ１５相に取り込まれたと考えられる。
(XRD pattern of phosphor according to example)
The powder X-ray diffraction (XRD) pattern of the obtained sample (Sr 6 Y 2 Al 4 O 15 : Ce 3+ ) is shown in the second to fourth stages of FIG. The obtained powder was identified as the target Sr 6 Y 2 Al 4 O 15 phase (see the top row in FIG. 1). Since no other impurity phase is observed, it is considered that the activated Ce 3+ was incorporated into the Sr 6 Y 2 Al 4 O 15 phase.
（実施例に係る蛍光体の蛍光特性）
図２は、実施例の蛍光体の蛍光特性（励起スペクトルおよび発光スペクトル）を示した図である。図２の横軸における短波長側が各Ｃｅ３＋濃度条件における励起スペクトル（図２中の破線を参照）を示し、一方、長波長側が、前記条件における発光スペクトルを示す（図２中の実線を参照）。
(Fluorescence characteristics of phosphors according to examples)
FIG. 2 is a diagram showing the fluorescence characteristics (excitation spectrum and emission spectrum) of the phosphor of the example. The short wavelength side on the horizontal axis of FIG. 2 shows the excitation spectrum (see the broken line in FIG. 2) under each Ce 3+ concentration condition, while the long wavelength side shows the emission spectrum under the above condition (see the solid line in FIG. 2). ).
この図２に示すように、約４６０ｎｍの青色光を著しく吸収し、５００〜７００ｎｍの範囲に亘るブロードな橙色〜赤色の発光を示すことを確認した。なお、発光のピーク波長は約５９０ｎｍ付近であることが確認された。 As shown in FIG. 2, it was confirmed that blue light of about 460 nm was remarkably absorbed and broad orange to red light emission ranging from 500 to 700 nm was exhibited. In addition, it was confirmed that the peak wavelength of light emission is about 590 nm.
また、ｘ＝０．１０の条件にて最も高い発光強度を示し、ｘ＝０．１５の条件にて２番目に高い発光強度を示すことが分かり、本実施例の場合、ｘ＝０．１０〜０．１５に設定することが好ましいことが分かった。 It can also be seen that the highest light emission intensity is exhibited under the condition of x = 0.10, and the second highest light emission intensity is exhibited under the condition of x = 0.15. In the case of this example, x = 0.10. It was found that setting to ~ 0.15 is preferable.
本発明により製造された酸化物蛍光体は、製造が容易であるため、青色光を吸収して赤色発光する蛍光体として使用されている既存の窒化物蛍光体及び酸窒化物蛍光体の安価な代替材料として期待できる。また、本発明の蛍光体を使用すれば、色純度の高い発光素子を得ることもできる。従って、本発明は、産業上の利用価値及び利用可能性が非常に高い。 Since the oxide phosphor manufactured according to the present invention is easy to manufacture, existing nitride phosphors and oxynitride phosphors that are used as phosphors that absorb blue light and emit red light are inexpensive. It can be expected as an alternative material. Moreover, if the phosphor of the present invention is used, a light emitting element with high color purity can be obtained. Therefore, the present invention has very high industrial utility value and applicability.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011342A (en) * | 2022-05-09 | 2022-09-06 | 广东省科学院资源利用与稀土开发研究所 | Bi 3+ Doped cyan fluorescent powder and preparation method thereof |
| CN115093853A (en) * | 2022-06-06 | 2022-09-23 | 电子科技大学 | Fluorescent powder Ba with negative thermal quenching behavior 3 Eu 1-x RE x Al 2-y M y O 7.5 And method for preparing the same |
| CN115232618A (en) * | 2022-07-11 | 2022-10-25 | 电子科技大学 | Phase-change induced up-conversion green light near-zero thermal quenching fluorescent powder and preparation method thereof |
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2014
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011342A (en) * | 2022-05-09 | 2022-09-06 | 广东省科学院资源利用与稀土开发研究所 | Bi 3+ Doped cyan fluorescent powder and preparation method thereof |
| CN115011342B (en) * | 2022-05-09 | 2023-04-07 | 广东省科学院资源利用与稀土开发研究所 | Bi 3+ Doped cyan fluorescent powder and preparation method thereof |
| CN115093853A (en) * | 2022-06-06 | 2022-09-23 | 电子科技大学 | Fluorescent powder Ba with negative thermal quenching behavior 3 Eu 1-x RE x Al 2-y M y O 7.5 And method for preparing the same |
| CN115093853B (en) * | 2022-06-06 | 2023-04-11 | 电子科技大学 | Fluorescent powder Ba with negative thermal quenching behavior 3 Eu 1-x RE x Al 2-y M y O 7.5 And method for preparing the same |
| CN115232618A (en) * | 2022-07-11 | 2022-10-25 | 电子科技大学 | Phase-change induced up-conversion green light near-zero thermal quenching fluorescent powder and preparation method thereof |
| CN115232618B (en) * | 2022-07-11 | 2023-04-07 | 电子科技大学 | Phase-change induced upconversion green light near-zero thermal quenching fluorescent powder and preparation method thereof |
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