JP5811041B2 - Far red light emitting phosphor and light emitting device using the same - Google Patents
Far red light emitting phosphor and light emitting device using the same Download PDFInfo
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Description
本発明は、発光ダイオード等に使用される蛍光体に関し、特に可視光の短波長側の光によって励起され、遠赤色域に発光スペクトルを有するＭｎ付活の酸化物蛍光体およびそれを用いた発光装置に関する。 The present invention relates to a phosphor used for a light-emitting diode and the like, and in particular, an Mn-activated oxide phosphor having an emission spectrum in a far red region excited by light on the short wavelength side of visible light and light emission using the same Relates to the device.
発光ダイオード（Light emitting diode：LED）は、白熱灯のような光源の代用品として使用される発光装置である。発光ダイオードはバックライト、ディスプレイ灯、警告灯、表示用灯具、照明用灯具として有用である。またレーザーダイオード（Laser diode:LD）も発光ダイオードと同様に蛍光体と組み合わせた発光装置が種々提案されている。 A light emitting diode (LED) is a light emitting device used as a substitute for a light source such as an incandescent lamp. The light-emitting diode is useful as a backlight, a display lamp, a warning lamp, a display lamp, and an illumination lamp. In addition, various laser diodes (LDs) that combine phosphors with phosphors have been proposed in the same way as light emitting diodes.
一般に、植物の栽培用光源として、赤色発光蛍光体と青色発光蛍光体とを配合してなる蛍光体層を具備した蛍光ランプが普及している。 In general, fluorescent lamps having a phosphor layer formed by blending a red light-emitting phosphor and a blue light-emitting phosphor are widely used as plant cultivation light sources.
また三波長系蛍光体に遠赤色発光蛍光体を混合した蛍光体層を具備した植物栽培用の蛍光ランプも提案されている。遠赤色光が所定の品種の植物に照射されると、植物のフィトクロム反応によって植物の成長を制御することが可能になることが知られている（例えば、特許文献１参照）。 A fluorescent lamp for plant cultivation having a phosphor layer in which a far-red phosphor is mixed with a three-wavelength phosphor has also been proposed. It is known that when a plant of a predetermined variety is irradiated with far-red light, the growth of the plant can be controlled by the phytochrome reaction of the plant (see, for example, Patent Document 1).
さらに、この遠赤色光を放射する蛍光体として、鉄付活アルミン酸リチウム（ＬｉＡｌＯ２：Ｆｅ）などが知られており、紫外線を励起源とする植物育成用ランプに使用されている（例えば、特許文献２参照）。 Further, as phosphors emitting far-red light, iron-activated lithium aluminate (LiAlO2: Fe) and the like are known, and are used in plant growth lamps using ultraviolet light as an excitation source (for example, patents). Reference 2).
しかしながら、従来においては、可視光の短波長側の光に励起されて、発光強度の高い遠赤色発光蛍光体が知られていない。特に植物育成用途に好適とされる、遠赤色発光の蛍光体およびそれを用いた発光装置の実用化が望まれているが、従来品では充分な発光特性が得られていない。 However, conventionally, far-red light emitting phosphors that are excited by light on the short wavelength side of visible light and have high emission intensity have not been known. In particular, there is a demand for practical use of a far-red light-emitting phosphor and a light-emitting device using the phosphor, which are suitable for plant growing applications, but sufficient light-emitting characteristics are not obtained with conventional products.
以上のことから、本発明は従来の問題を解決すべく、可視光の短波長側の光に励起されて、発光強度の高い遠赤色発光の蛍光体及びそれを用いた発光装置を提供することを目的とする。 In view of the above, the present invention provides a far-red phosphor that emits light with high emission intensity and is excited by light on the short wavelength side of visible light, and a light-emitting device using the same, in order to solve the conventional problems. With the goal.
上記の問題点を解決すべく、本発明者は鋭意検討を重ねた結果、本発明を完成するに到った。本明細書において、可視光の短波長側の光は、特に限定されないが４００ｎｍ〜５００ｎｍの領域をいう。 In order to solve the above-mentioned problems, the present inventor has intensively studied, and as a result, the present invention has been completed. In this specification, the light on the short wavelength side of visible light is not particularly limited, but refers to a region of 400 nm to 500 nm.
本発明は、以下の一般式で示される蛍光体に関する。 The present invention relates to a phosphor represented by the following general formula.
Ｍ１Ｍ２（Ｍ３ １−ｘ−ｙＭｎｘＭｇｙ）Ｏ４＋ｘ/２−ｙ/２
（ただし、Ｍ１はＣａ、Ｓｒ、Ｂａの第２族元素から選ばれる少なくとも１種以上であり、Ｍ２はＳｃ、Ｙ、Ｌｎ（ランタノイド）の第３族元素から選ばれる少なくとも１種以上であり、Ｍ３はＡｌ、Ｇａ、Ｉｎの第１３族元素から選ばれる少なくとも１種以上である。ｘ、ｙは、０．００１≦ｘ≦０．２、０≦ｙ≦０．２である。）これにより、可視光の短波長側の光に励起されて遠赤色域に発光する、発光強度の高い酸化物蛍光体を提供することができる。
M 1 M 2 (M 3 1-xy Mn x Mg y ) O 4 + x / 2−y / 2
(However, M 1 is at least one selected from the group 2 elements of Ca, Sr, and Ba, and M 2 is at least one selected from the group 3 elements of Sc, Y, Ln (lanthanoid)) And M 3 is at least one selected from the group 13 elements of Al, Ga and In. X and y are 0.001 ≦ x ≦ 0.2 and 0 ≦ y ≦ 0.2. Thus, it is possible to provide an oxide phosphor having high emission intensity that is excited by light on the short wavelength side of visible light and emits light in the far red region.
前記蛍光体は、４価Ｍｎで付活されており、Ｍ１はＣａ、Ｓｒの第２族元素から選ばれる少なくとも１種以上であり、Ｍ２はＹ、Ｇｄ、Ｌａの第３族元素から選ばれる少なくとも１種以上であり、Ｍ３はＡｌ、Ｇａの第１３族元素から選ばれる少なくとも１種以上であり、ｘ、ｙは、０．００５≦ｘ≦０．０１５、０≦ｙ≦０．０３であることが好ましい。これにより、発光強度の高い蛍光体を提供することができる。 The phosphor is activated by tetravalent Mn, M 1 is at least one selected from the group 2 elements of Ca and Sr, and M 2 is from the group 3 elements of Y, Gd, and La. At least one selected, M 3 is at least one selected from group elements of Al and Ga, and x and y are 0.005 ≦ x ≦ 0.015, 0 ≦ y ≦ 0. 0.03 is preferred. Thereby, a phosphor with high emission intensity can be provided.
前記蛍光体は、可視光の短波長側の光に励起されて遠赤色に発光する。 The phosphor is excited by light on the short wavelength side of visible light and emits far red light.
前記蛍光体は、７００ｎｍから７４０ｎｍの遠赤色域に発光ピークを有する。 The phosphor has an emission peak in a far red region from 700 nm to 740 nm.
本発明は、可視光の短波長側の光を発する光源と、該光源からの光を吸収して遠赤色に発光する前記蛍光体と、を有する発光装置に関する。 The present invention relates to a light emitting device having a light source that emits light on a short wavelength side of visible light and the phosphor that absorbs light from the light source and emits light in a far red color.
本発明は、以上説明したように構成されているので、可視光の短波長側の光に励起されて遠赤色域に発光する、発光強度に優れた遠赤色発光蛍光体を得ることができる。さらに、本発明の酸化物蛍光体を用いることで、従来よりも発光特性に優れた発光装置を得ることができる。 Since the present invention is configured as described above, it is possible to obtain a far red light emitting phosphor excellent in emission intensity that is excited by light on the short wavelength side of visible light and emits light in the far red region. Furthermore, by using the oxide phosphor of the present invention, a light-emitting device having better light emission characteristics than before can be obtained.
以下、本発明に係る蛍光体及びそれを用いた発光装置、並びに、それらの製造方法について、実施の形態及び実施例を用いて説明する。だたし、本発明は、この実施の形態及び実施例に限定されない。
＜蛍光体＞
実施の形態に係る酸化物の蛍光体は、４価Ｍｎで付活され、可視光の短波長側の光に励起されて遠赤色域に発光する。該蛍光体は、一般式がＭ１Ｍ２（Ｍ３ １−ｘ−ｙＭｎｘＭｇｙ）Ｏ４＋ｘ/２−ｙ/２で示され、式中のＭ１はＣａ、Ｓｒ、Ｂａの第２族元素から選ばれる少なくとも１種以上であり、Ｍ２はＳｃ、Ｙ、Ｌｎ（ランタノイド）の第３族元素から選ばれる少なくとも１種以上であり、Ｍ３はＡｌ、Ｇａ、Ｉｎの第１３族元素から選ばれる少なくとも１種以上である。ｘ、ｙは、０．００１≦ｘ≦０．２、０≦ｙ≦０．２である。ここでＬｎ（ランタノイド）とは、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕを意味する。
Hereinafter, a phosphor according to the present invention, a light emitting device using the phosphor, and a method for manufacturing the same will be described with reference to embodiments and examples. However, the present invention is not limited to this embodiment and example.
<Phosphor>
The oxide phosphor according to the embodiment is activated by tetravalent Mn, and is excited by light on the short wavelength side of visible light to emit light in a far red region. The phosphor is represented by the general formula M 1 M 2 (M 3 1-xy Mn x Mg y ) O 4 + x / 2−y / 2 , where M 1 is the number of Ca, Sr, or Ba. At least one selected from Group 2 elements, M 2 is at least one selected from Group 3 elements of Sc, Y, and Ln (lanthanoid), and M 3 is a thirteenth selected from Al, Ga, and In. At least one selected from group elements. x and y are 0.001 ≦ x ≦ 0.2 and 0 ≦ y ≦ 0.2. Here, Ln (lanthanoid) means La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
特に、Ｍ１はＣａ、Ｓｒであり、Ｍ２はＹ、Ｇｄ、Ｌａであり、Ｍ３はＡｌ、Ｇａであり、ｘ、ｙは、０．００１≦ｘ≦０．０３、０≦ｙ≦０．０３であることが好ましい。さらに、Ｍ１はＣａであり、Ｍ２はＹであり、Ｍ３はＡｌであり、ｘ、ｙは、０．００５≦ｘ≦０．０１５、０≦ｙ≦０．０３であることが好ましい。Ｍｎは付活剤として働くため、０．００１ｍｏｌ以上有していればよく、０．２ｍｏｌ以下であれば効率よく作用する。
＜発光スペクトル＞
酸化物の蛍光体は、可視光の短波長側の光を吸収して、励起光の発光ピーク波長よりも長波長側に蛍光体の発光ピーク波長を有する。可視光の短波長側の光は、主に青色光領域となる。具体的には４００ｎｍ〜５００ｎｍに発光ピーク波長を有する励起光源からの光により励起され、７００から７４０ｎｍの波長の範囲に発光ピーク波長を有する。励起光源には４２０ｎｍ〜５００ｎｍに主発光ピーク波長を有する光源を用いることが好ましく、更に４４０〜４８０ｎｍに発光ピーク波長を有する光源を用いることが好ましい。
＜製造方法＞
原料となるＣａＣＯ３、Ｙ２Ｏ３、Ａｌ２Ｏ３、ＭｎＣＯ３を所定の組成となるように秤量する。また、ＡｌＦ３のようなフラックスを用いることもできる。フラックスも含むこれらの原料混合物を坩堝に充填し、蓋をして、大気中１０００℃〜１８００℃で数時間焼成を行う。これにより、所定の酸化物蛍光体を生成することができる。
In particular, M 1 is Ca and Sr, M 2 is Y, Gd, and La, M 3 is Al and Ga, and x and y are 0.001 ≦ x ≦ 0.03 and 0 ≦ y ≦. It is preferable that it is 0.03. Further, M 1 is Ca, M 2 is Y, M 3 is Al, and x and y are preferably 0.005 ≦ x ≦ 0.015 and 0 ≦ y ≦ 0.03. . Since Mn works as an activator, it is sufficient to have 0.001 mol or more, and if it is 0.2 mol or less, it works efficiently.
<Emission spectrum>
The oxide phosphor absorbs light on the short wavelength side of visible light and has the emission peak wavelength of the phosphor on the longer wavelength side than the emission peak wavelength of excitation light. The light on the short wavelength side of visible light is mainly in the blue light region. Specifically, it is excited by light from an excitation light source having an emission peak wavelength at 400 nm to 500 nm and has an emission peak wavelength in a wavelength range of 700 to 740 nm. As the excitation light source, a light source having a main emission peak wavelength at 420 nm to 500 nm is preferably used, and a light source having an emission peak wavelength at 440 to 480 nm is further preferably used.
<Manufacturing method>
The raw materials CaCO 3 , Y 2 O 3 , Al 2 O 3 , and MnCO 3 are weighed so as to have a predetermined composition. A flux such as AlF 3 can also be used. The raw material mixture including the flux is filled in a crucible, covered, and fired at 1000 ° C. to 1800 ° C. for several hours in the atmosphere. Thereby, a predetermined oxide phosphor can be generated.
ＣａＣＯ３の全部若しくは一部をＳｒＣＯ３、ＢａＣＯ３に代えることもできる。また、Ｙ２Ｏ３の全部若しくは一部をＳｃ２Ｏ３、Ｌｎ２Ｏ３に代えることもできる。また、Ａｌ２Ｏ３の全部若しくは一部をＧａ２Ｏ３、Ｉｎ２Ｏ３に代えることもできる。さらに、ＭｎＣＯ３の全部若しくは一部をＭｎＯ２に代えることもできる。 All or part of CaCO 3 may be replaced with SrCO 3 or BaCO 3 . Further, all or part of Y 2 O 3 can be replaced with Sc 2 O 3 or Ln 2 O 3 . Further, all or part of Al 2 O 3 can be replaced with Ga 2 O 3 or In 2 O 3 . Furthermore, all or part of MnCO 3 can be replaced with MnO 2 .
以下、実施例１〜１０に係る４価Ｍｎ付活酸化物蛍光体について説明する。 Hereinafter, the tetravalent Mn activated oxide phosphor according to Examples 1 to 10 will be described.
表１は、実施例１〜１０に係る酸化物蛍光体の仕込み組成、励起ピーク波長（４Ａ２→４Ｔ２）、発光ピーク波長（２Ｅ→４Ａ２）、相対発光ピーク強度（％）を示す。図１は、実施例１に係る酸化物蛍光体の励起スペクトルを示す。図２は、実施例１に係る酸化物蛍光体の発光スペクトルを示す。図３は、実施例４に係る酸化物蛍光体の励起スペクトルを示す。図４は、実施例４に係る酸化物蛍光体の発光スペクトルを示す。
Table 1 shows preparation compositions, excitation peak wavelengths ( 4 A 2 → 4 T 2 ), emission peak wavelengths ( 2 E → 4 A 2 ), and relative emission peak intensities (%) of the oxide phosphors according to Examples 1 to 10. ). FIG. 1 shows an excitation spectrum of the oxide phosphor according to Example 1. FIG. 2 shows an emission spectrum of the oxide phosphor according to Example 1. FIG. 3 shows an excitation spectrum of the oxide phosphor according to Example 4. FIG. 4 shows an emission spectrum of the oxide phosphor according to Example 4.
実施例１に係る、一般式がＣａ１．００Ｙ１．００Ａｌ０．９９０Ｍｎ０．０１０Ｏ４．００５で表わされる４価Ｍｎ付活酸化物蛍光体は、以下の方法により作製した。 The tetravalent Mn-activated oxide phosphor represented by the general formula Ca 1.00 Y 1.00 Al 0.990 Mn 0.010 O 4.005 according to Example 1 was produced by the following method.
所定の仕込み組成比となるように、原料となるＣａＣＯ３を７．５３ｇ、Ｙ２Ｏ３を８．５０ｇ、Ａｌ２Ｏ３を３．７５ｇ、ＭｎＣＯ３を０．０９ｇ秤量し、フラックスとしてＡｌＦ３を０．１３ｇ添加して混合した原料混合物をアルミナ坩堝に充填し、蓋をして、大気中１４００℃で６時間焼成を行った。これにより４価Ｍｎ付活酸化物蛍光体を得た。この蛍光体は、４６０ｎｍ付近の青色光で励起することにより、主発光ピークが７１２ｎｍの遠赤色発光を示した。 As a predetermined charging composition ratio, AlF the CaCO 3 as a raw material 7.53 g, 8.50 g of Y 2 O 3, 3.75 g of Al 2 O 3, and MnCO 3 was 0.09g weighed, as flux The raw material mixture obtained by adding 0.13 g of 3 and mixing was filled in an alumina crucible, covered, and baked at 1400 ° C. in the atmosphere for 6 hours. As a result, a tetravalent Mn activated oxide phosphor was obtained. This phosphor exhibited far-red emission with a main emission peak of 712 nm when excited with blue light near 460 nm.
原料としてＣａＣＯ３を７．５４ｇ、Ｙ２Ｏ３を８．５１ｇ、Ａｌ２Ｏ３を３．７８ｇ、ＭｎＣＯ３を０．０５ｇ、ＡｌＦ３を０．１３ｇ使用する以外は実施例１と同様に行い、一般式がＣａ１．００Ｙ１．００Ａｌ０．９９５Ｍｎ０．００５Ｏ４．００２５で表わされる実施例２に係る酸化物蛍光体を得た。実施例２に係る蛍光体の４６０ｎｍ励起での相対発光ピーク強度は実施例１の９７％であった。 The CaCO 3 as a raw material 7.54g, Y 2 O 3 to 8.51 g, the Al 2 O 3 3.78g, the MnCO 3 0.05 g, the AlF 3 in the same manner as in Example 1 except that 0.13g use Then , an oxide phosphor according to Example 2 having a general formula represented by Ca 1.00 Y 1.00 Al 0.995 Mn 0.005 O 4.0025 was obtained. The relative emission peak intensity of the phosphor according to Example 2 at 460 nm excitation was 97% of Example 1.
原料としてＣａＣＯ３を７．５２ｇ、Ｙ２Ｏ３を８．４８ｇ、Ａｌ２Ｏ３を３．７３ｇ、ＭｎＣＯ３を０．１４ｇ、ＡｌＦ３を０．１３ｇ使用する以外は実施例１と同様に行い、一般式がＣａ１．００Ｙ１．００Ａｌ０．９８５Ｍｎ０．０１５Ｏ４．００７５で表わされる実施例３に係る酸化物蛍光体を得た。実施例３に係る蛍光体の４６０ｎｍ励起での相対発光ピーク強度は実施例１の８５％であった。 A CaCO 3 as a starting material 7.52 g, Y a 2 O 3 8.48 g, the Al 2 O 3 3.73g, the MnCO 3 0.14 g, the AlF 3 in the same manner as in Example 1 except that 0.13g use The oxide phosphor according to Example 3 having the general formula represented by Ca 1.00 Y 1.00 Al 0.985 Mn 0.015 O 4.0075 was obtained. The relative emission peak intensity of the phosphor according to Example 3 at 460 nm excitation was 85% of Example 1.
原料としてＣａＣＯ３を７．５５ｇ、Ｙ２Ｏ３を８．５１ｇ、Ａｌ２Ｏ３を３．７２ｇ、ＭｎＣＯ３を０．０９ｇ、ＭｇＯを０．０３ｇ、ＡｌＦ３を０．１３ｇ使用する以外は実施例１と同様に行い、一般式がＣａ１．００Ｙ１．００Ａｌ０．９８Ｍｇ０．０１Ｍｎ０．０１Ｏ４．０００で表わされる実施例４に係る酸化物蛍光体を得た。実施例４に係る蛍光体の４６０ｎｍ励起での相対発光ピーク強度は実施例１の１４４％であり、Ｍｇ２＋による電荷保障の効果が確認された。 The CaCO 3 as a raw material 7.55g, Y 2 O 3 and 8.51g, Al 2 O 3 and 3.72 g, 0.09 g of MnCO 3, MgO and 0.03 g, except for the AlF 3 0.13 g using The same procedure as in Example 1 was performed to obtain an oxide phosphor according to Example 4 represented by the general formula Ca 1.00 Y 1.00 Al 0.98 Mg 0.01 Mn 0.01 O 4.0000 . . The relative emission peak intensity at 460 nm excitation of the phosphor according to Example 4 was 144% of Example 1, and the effect of charge assurance by Mg 2+ was confirmed.
原料としてＣａＣＯ３を７．５６ｇ、Ｙ２Ｏ３を８．５３ｇ、Ａｌ２Ｏ３を３．６９ｇ、ＭｎＣＯ３を０．０９ｇ、ＭｇＯを０．０６ｇ、ＡｌＦ３を０．１３ｇ使用する以外は実施例１と同様に行い、一般式がＣａ１．００Ｙ１．００Ａｌ０．９７Ｍｇ０．０２Ｍｎ０．０１Ｏ３．９９５で表わされる実施例５に係る酸化物蛍光体を得た。実施例５に係る蛍光体の４６０ｎｍ励起での相対発光ピーク強度は実施例１の１３５％であった。 The CaCO 3 as a raw material 7.56g, Y 2 O 3 and 8.53g, Al 2 O 3 and 3.69 g, 0.09 g of MnCO 3, MgO and 0.06 g, except for the AlF 3 0.13 g using The oxide phosphor according to Example 5 having the general formula Ca 1.00 Y 1.00 Al 0.97 Mg 0.02 Mn 0.01 O 3.995 was obtained in the same manner as in Example 1. . The relative emission peak intensity of the phosphor according to Example 5 at 460 nm excitation was 135% of Example 1.
原料としてＣａＣＯ３を７．５７ｇ、Ｙ２Ｏ３を８．５４ｇ、Ａｌ２Ｏ３を３．６６ｇ、ＭｎＣＯ３を０．０９ｇ、ＭｇＯを０．０９ｇ、ＡｌＦ３を０．１３ｇ使用する以外は実施例１と同様に行い、一般式がＣａ１．００Ｙ１．００Ａｌ０．９６Ｍｇ０．０３Ｍｎ０．０１Ｏ３．９９０で表わされる実施例６に係る酸化物蛍光体を得た。実施例６に係る蛍光体の４６０ｎｍ励起での相対発光ピーク強度は実施例１の１２８％であった。 The CaCO 3 as a raw material 7.57g, Y 2 O 3 and 8.54g, Al 2 O 3 and 3.66 g, 0.09 g of MnCO 3, MgO and 0.09 g, except for the AlF 3 0.13 g using The oxide phosphor according to Example 6 having the general formula Ca 1.00 Y 1.00 Al 0.96 Mg 0.03 Mn 0.01 O 3.990 was obtained in the same manner as in Example 1. . The relative emission peak intensity of the phosphor according to Example 6 at 460 nm excitation was 128% of Example 1.
原料としてＣａＣＯ３を５．９９ｇ、Ｇｄ２Ｏ３を１０．８５ｇ、Ａｌ２Ｏ３を２．９６ｇ、ＭｎＣＯ３を０．０７ｇ、ＭｇＯを０．０２ｇ、ＡｌＦ３を０．１０ｇ使用する以外は実施例１と同様に行い、一般式がＣａ１．００Ｇｄ１．００Ａｌ０．９８Ｍｇ０．０１Ｍｎ０．０１Ｏ４．００で表わされる実施例７に係る酸化物蛍光体を得た。実施例７に係る蛍光体の４６０ｎｍ励起での相対発光ピーク強度は実施例１の５２％であった。 The CaCO 3 as a raw material 5.99g, Gd 2 O 3 and 10.85g, Al 2 O 3 to 2.96 g, the MnCO 3 0.07 g, MgO and 0.02 g, except that 0.10g use AlF 3 The oxide phosphor according to Example 7 having the general formula Ca 1.00 Gd 1.00 Al 0.98 Mg 0.01 Mn 0.01 O 4.00 was obtained in the same manner as in Example 1. . The relative emission peak intensity of the phosphor according to Example 7 at 460 nm excitation was 52% of Example 1.
原料としてＳｒＣＯ３を８．１７ｇ、Ｌａ２Ｏ３を８．９４ｇ、Ａｌ２Ｏ３を２．７１ｇ、ＭｎＣＯ３を０．０７ｇ、ＭｇＯを０．０２ｇ、ＡｌＦ３を０．０９ｇ使用する以外は実施例１と同様に行い、一般式がＳｒ１．００Ｌａ１．００Ａｌ０．９８Ｍｇ０．０１Ｍｎ０．０１Ｏ４．００で表わされる実施例８に係る酸化物蛍光体を得た。実施例８に係る蛍光体の４６０ｎｍ励起での相対発光ピーク強度は実施例１の４％であった。 Raw material as a SrCO 3 8.17g, La 2 O 3 and 8.94g, Al 2 O 3 to 2.71 g, the MnCO 3 0.07 g, MgO and 0.02 g, except that the AlF 3 using 0.09g The oxide phosphor according to Example 8 having the general formula Sr 1.00 La 1.00 Al 0.98 Mg 0.01 Mn 0.01 O 4.00 was obtained in the same manner as in Example 1. . The relative emission peak intensity of the phosphor according to Example 8 at 460 nm excitation was 4% of Example 1.
原料としてＳｒＣＯ３を７．７８ｇ、Ｇｄ２Ｏ３を９．４７ｇ、Ａｌ２Ｏ３を２．５８ｇ、ＭｎＣＯ３を０．０６ｇ、ＭｇＯを０．０２ｇ、ＡｌＦ３を０．０９ｇ使用する以外は実施例１と同様に行い、一般式がＳｒ１．００Ｇｄ１．００Ａｌ０．９８Ｍｇ０．０１Ｍｎ０．０１Ｏ４．００で表わされる実施例９に係る酸化物蛍光体を得た。実施例９に係る蛍光体の４６０ｎｍ励起での相対発光ピーク強度は実施例１の２７％であった。 Raw material as a SrCO 3 7.78g, Gd 2 O 3 and 9.47g, Al 2 O 3 to 2.58 g, the MnCO 3 0.06 g, MgO and 0.02 g, except that the AlF 3 using 0.09g The oxide phosphor according to Example 9 having the general formula represented by Sr 1.00 Gd 1.00 Al 0.98 Mg 0.01 Mn 0.01 O 4.00 was obtained in the same manner as in Example 1. . The relative emission peak intensity of the phosphor according to Example 9 at 460 nm excitation was 27% of Example 1.
原料としてＳｒＣＯ３を７．３５ｇ、Ｌａ２Ｏ３を８．０４ｇ、Ｇａ２Ｏ３を４．４４ｇ、ＭｎＣＯ３を０．０６ｇ、ＭｇＯを０．０２ｇ、ＡｌＦ３を０．０８ｇ使用する以外は実施例１と同様に行い、一般式がＳｒ１．００Ｌａ１．００Ｇａ０．９８Ｍｇ０．０１Ｍｎ０．０１Ｏ４．００で表わされる実施例１０に係る酸化物蛍光体を得た。実施例１０に係る蛍光体の４６０ｎｍ励起での相対発光ピーク強度は実施例１の１１％であった。 Raw material as a SrCO 3 7.35g, La 2 O 3 and 8.04g, Ga 2 O 3 to 4.44 g, the MnCO 3 0.06 g, MgO and 0.02 g, except that the AlF 3 using 0.08g The oxide phosphor according to Example 10 having the general formula Sr 1.00 La 1.00 Ga 0.98 Mg 0.01 Mn 0.01 O 4.00 was obtained in the same manner as in Example 1. . The relative emission peak intensity of the phosphor according to Example 10 at 460 nm excitation was 11% of Example 1.
本発明の４価Ｍｎ付活酸化物蛍光体及びこれらを用いた発光装置は、特に青色発光ダイオードを光源とする植物育成用照明に好適に利用できる。 The tetravalent Mn-activated oxide phosphor of the present invention and the light-emitting device using these can be suitably used particularly for plant growth illumination using a blue light-emitting diode as a light source.
Claims (5)
Ｍ１Ｍ２（Ｍ３ １−ｘ−ｙＭｎｘＭｇｙ）Ｏ４＋ｘ/２−ｙ/２
（ただし、Ｍ１はＣａ、Ｓｒ、Ｂａの第２族元素から選ばれる少なくとも１種以上であり、Ｍ２はＳｃ、Ｙ、Ｌｎ（ランタノイド）の第３族元素から選ばれる少なくとも１種以上であり、Ｍ３はＡｌ、Ｇａ、Ｉｎの第１３族元素から選ばれる少なくとも１種以上である。ｘ、ｙは、０．００１≦ｘ≦０．２、０≦ｙ≦０．２である。） A phosphor represented by the following general formula.
M 1 M 2 (M 3 1-xy Mn x Mg y ) O 4 + x / 2−y / 2
(However, M 1 is at least one selected from the group 2 elements of Ca, Sr, and Ba, and M 2 is at least one selected from the group 3 elements of Sc, Y, Ln (lanthanoid)) And M 3 is at least one selected from the group 13 elements of Al, Ga and In. X and y are 0.001 ≦ x ≦ 0.2 and 0 ≦ y ≦ 0.2. )
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