JP5757336B2 - Luminescent ceramics - Google Patents
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Description
本発明は、発光セラミックスに関する。 The present invention relates to luminescent ceramics.
従来、パルスレーザーの光源として、例えば、Nd:YAGなどが知られている(特許文献1を参照)。 Conventionally, as a light source of a pulse laser, for example, Nd: YAG is known (see Patent Document 1).
しかしながら、Nd:YAGでは、十分に広い発光帯域が得られないため短パルス化に限界がある。このため、発光帯域が広い発光材料が求められている。 However, Nd: YAG has a limitation in shortening the pulse because a sufficiently wide light emission band cannot be obtained. For this reason, a light emitting material having a wide light emission band is required.
本発明は、発光帯域が広い発光セラミックスを提供することを主な目的とする。 The main object of the present invention is to provide a luminescent ceramic having a wide emission band.
本発明に係る発光セラミックスは、組成式:(M11−xM2x)(M31−yM4y)Ow (1)で表されるペロブスカイト型化合物を主成分とするセラミックスである。組成式(1)において、M1は、La,Y,Gd及びLuからなる群から選ばれる少なくとも一種である。M2は、Ba,Sr及びCaからなる群から選ばれる少なくとも一種である。M3は、Al及びGaの少なくとも一方である。M4は、Ta及びNbの少なくとも一方である。xは、0.2≦x≦0.95の関係を満たす。yは、0<y<0.5の関係を満たす。xとyは、0.45≦y/x≦0.55の関係を満たす。wは、電気的中性を保つための正の数である。セラミックスは、0.1mol%〜5mol%のNdを含む。The luminescent ceramic according to the present invention is a ceramic whose main component is a perovskite type compound represented by a composition formula: (M1 1-x M2 x ) (M3 1-y M4 y ) O w (1). In the composition formula (1), M1 is at least one selected from the group consisting of La, Y, Gd, and Lu. M2 is at least one selected from the group consisting of Ba, Sr and Ca. M3 is at least one of Al and Ga. M4 is at least one of Ta and Nb. x satisfies the relationship 0.2 ≦ x ≦ 0.95. y satisfies the
本発明に係る発光セラミックスのある特定の局面では、セラミックスが、Crをさらに含む。 In a specific aspect of the luminescent ceramic according to the present invention, the ceramic further includes Cr.
本発明に係る発光セラミックスの別の特定の局面では、セラミックスにおけるCrの含有量が、0.2mol%以上である。 In another specific aspect of the luminescent ceramic according to the present invention, the content of Cr in the ceramic is 0.2 mol% or more.
本発明に係る発光セラミックスの他の特定の局面では、波長600nmの光を照射したときに得られるNd発光の半値幅が、20nm以上である。 In another specific aspect of the luminescent ceramic according to the present invention, the half width of Nd emission obtained when irradiated with light having a wavelength of 600 nm is 20 nm or more.
本発明によれば、発光帯域が広い発光セラミックスを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the luminescent ceramics with a wide light emission zone can be provided.
以下、本発明を実施した好ましい形態の一例について説明する。但し、下記の実施形態は、単なる例示である。本発明は、下記の実施形態に何ら限定されない。 Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiment is merely an example. The present invention is not limited to the following embodiments.
本実施形態に係る発光セラミックスは、下記組成式(1)で表されるペロブスカイト型化合物を主成分とするセラミックスである。 The luminescent ceramic according to the present embodiment is a ceramic whose main component is a perovskite compound represented by the following composition formula (1).
(M11−xM2x)(M31−yM4y)Ow (1)
[組成式(1)において、M1は、La,Y,Gd及びLuからなる群から選ばれる少なくとも一種であり、M2は、Ba,Sr及びCaからなる群から選ばれる少なくとも一種であり、M3は、Al及びGaの少なくとも一方であり、M4は、Ta及びNbの少なくとも一方であり、0.2≦x≦0.95、0<y<0.5、0.45≦y/x≦0.55、wは、電気的中性を保つための正の数である。](M1 1-x M2 x ) (M3 1-y M4 y ) O w (1)
[In composition formula (1), M1 is at least one selected from the group consisting of La, Y, Gd and Lu, M2 is at least one selected from the group consisting of Ba, Sr and Ca, and M3 is M4 is at least one of Ta and Nb, 0.2 ≦ x ≦ 0.95, 0 <y <0.5, 0.45 ≦ y / x ≦ 0. 55 and w are positive numbers for maintaining electrical neutrality. ]
組成式(1)において、M1は、Laを含むことが好ましい。M2は、Srを含むことが好ましい。M3は、Alを含むことが好ましい。M4は、Taを含むことが好ましい。xは0.2≦x≦0.95の範囲にあり、かつyは0<y<0.5の範囲にあり、かつy/xは0.45≦y/x≦0.55の関係を満たすことが好ましい。wとしては、例えば、3が挙げられる。 In the composition formula (1), M1 preferably contains La. M2 preferably contains Sr. M3 preferably contains Al. M4 preferably contains Ta. x is in a range of 0.2 ≦ x ≦ 0.95, y is in a range of 0 <y <0.5, and y / x has a relationship of 0.45 ≦ y / x ≦ 0.55. It is preferable to satisfy. As w, for example, 3 may be mentioned.
なお、セラミックスにおいて、ペロブスカイト型化合物は、理論上、(M11−xM2x)(M31−yM4y)Owで表されるが、(M11−xM2x)と(M31−yM4y)のモル比((M11−xM2x):(M31−yM4y))は、厳密に1:1に限定されない。本発明において、ペロブスカイト型化合物(M11−xM2x)(M31−yM4y)Owには、(M11−xM2x)と(M31−yM4y)のモル比((M11−xM2x)/(M31−yM4y))が0.95〜1.05であるものが含まれるとする。In ceramics, perovskite type compounds are theoretically represented by (M1 1-x M2 x ) (M3 1-y M4 y ) O w , but (M1 1-x M2 x ) and (M3 1- The molar ratio of y M4 y ) ((M1 1-x M2 x ) :( M3 1-y M4 y )) is not strictly limited to 1: 1. In the present invention, the perovskite compound (M1 1-x M2 x ) (M3 1-y M4 y ) O w has a molar ratio of (M1 1-x M2 x ) to (M3 1-y M4 y ) (( M1 1-x M2 x ) / (M3 1-y M4 y )) is assumed to be 0.95 to 1.05.
セラミックスは、0.1mol%〜5mol%程度のNdを含む。セラミックスは、0.5mol%〜3mol%程度のNdを含むことがより好ましい。これは、セラミックスが励起光を吸収してNdの発光を得る過程において、添加量が少なすぎると励起光を吸収しにくく、強い発光が得られ難いためであり、逆に大きすぎると濃度消光により発光しにくくなるためである。なお、セラミックスにおいて、Ndは、ABOwで表されるペロブスカイト型化合物のAサイトやBサイトにサイト置換していてもよいし、していなくてもよい。The ceramic contains about 0.1 mol% to 5 mol% of Nd. More preferably, the ceramic contains about 0.5 mol% to 3 mol% of Nd. This is because, in the process where ceramics absorbs excitation light and obtains Nd emission, if the addition amount is too small, it is difficult to absorb excitation light and it is difficult to obtain strong light emission. This is because it becomes difficult to emit light. In ceramics, Nd may or may not be site-substituted at the A site or B site of the perovskite type compound represented by ABO w .
本実施形態に係る発光セラミックスは、組成式:(M11−xM2x)(M31−yM4y)Ow (1)で表されるペロブスカイト型化合物を主成分とするセラミックスであって、0.1mol%〜5mol%のNdとを含む。本実施形態に係る発光セラミックスは、従来のNd:YAGと比べて、発光帯域が広い。例えば、発光セラミックスは、波長600nmの励起光を照射したときの900nm近傍でのNd発光の半値幅を20nm以上、さらには30nm以上とすることができる。The luminescent ceramic according to the present embodiment is a ceramic whose main component is a perovskite type compound represented by a composition formula: (M1 1-x M2 x ) (M3 1-y M4 y ) O w (1) 0.1 mol% to 5 mol% of Nd. The luminescent ceramic according to the present embodiment has a wider emission band than conventional Nd: YAG. For example, in the case of luminescent ceramics, the half-value width of Nd emission near 900 nm when irradiated with excitation light having a wavelength of 600 nm can be set to 20 nm or more, and further to 30 nm or more.
セラミックスは、Crをさらに含むことが好ましい。これは、セラミックスが励起光を吸収してNdの発光を得る過程において、Crをさらに含むことで励起光の吸収強度や吸収可能な波長の範囲が増加するためである。これにより、セラミックスは、太陽光のような広帯域な光を用いて励起するような場合、より強く発光することができる。セラミックスは、0.2mol%〜5mol%程度のCrをさらに含むことが好ましく、0.5mol%〜3mol%程度のCrをさらに含むことがより好ましい。これは、セラミックスが広帯域の励起光を吸収してNdの発光を得る過程において、添加量が少なすぎるとセラミックスが励起光を十分吸収できず、強い発光が得られ難いためであり、逆に大きすぎると濃度消光により発光しにくくなるためである。なお、セラミックスにおいて、Crは、ABOwで表されるペロブスカイト型化合物のAサイトやBサイトにサイト置換していてもよいし、していなくてもよい。The ceramic preferably further contains Cr. This is because the absorption intensity of the excitation light and the range of wavelengths that can be absorbed are increased by further including Cr in the process in which the ceramics absorbs the excitation light to obtain Nd emission. Thereby, ceramics can emit light more strongly when excited using broadband light such as sunlight. The ceramic preferably further contains about 0.2 mol% to 5 mol% of Cr, and more preferably about 0.5 mol% to 3 mol% of Cr. This is because when ceramics absorbs broadband excitation light and obtains Nd emission, if the addition amount is too small, ceramics cannot sufficiently absorb excitation light and it is difficult to obtain strong light emission. This is because it is difficult to emit light due to concentration quenching. In ceramics, Cr may or may not be site-substituted at the A site or B site of the perovskite type compound represented by ABO w .
なお、本発明における半値幅とは発光強度が最大発光強度の半分以上となる波長の幅を示したものである。最大発光強度とは、セラミックスより得られる発光スペクトルにおける、880nmでの発光ピークの最大値を示したものである。 In addition, the half value width in this invention shows the width | variety of the wavelength from which light emission intensity becomes more than half of maximum light emission intensity. The maximum emission intensity indicates the maximum value of the emission peak at 880 nm in the emission spectrum obtained from ceramics.
また、本発明において、波長365nm〜850nmの光の吸収量は、以下の式により算出したものであり、広帯域の波長を有する光の、吸収の程度を示す指標として用いている。 In the present invention, the amount of absorption of light having a wavelength of 365 nm to 850 nm is calculated by the following formula, and is used as an index indicating the degree of absorption of light having a broad wavelength.
I:波長λにおける基板の直線透過率
I0:波長700nmにおける基板の直線透過率
t:基板の肉厚(cm)I: Linear transmittance of substrate at wavelength λ I 0 : Linear transmittance of substrate at
セラミックスは、(M11−xM2x)(M31−yM4y)Owで表される成分を構成するM1、M2、M3、M4や、Nd、Cr以外に、不可避的に混入する不純物(以下、「不可避的不純物」とする。)を含んでいてもよい。不可避的不純物の具体例としては、Si、B、Zr、Alなどが挙げられる。Ceramics are impurities inevitably mixed in addition to M1, M2, M3, M4 and Nd, Cr constituting the component represented by (M1 1-x M2 x ) (M3 1-y M4 y ) O w (Hereinafter referred to as “inevitable impurities”). Specific examples of inevitable impurities include Si, B, Zr, Al, and the like.
以下、本発明について、具体的な実施例に基づいて、さらに詳細に説明する。但し、本発明は、以下の実施例に何ら限定されるものではなく、その要旨を変更しない範囲において適宜変更して実施することが可能である。 Hereinafter, the present invention will be described in more detail based on specific examples. However, the present invention is not limited to the following examples, and can be appropriately modified and implemented without departing from the scope of the invention.
(実験例)
まず、原料として、高純度のLa(OH)3、Lu2O3、Gd2O3、SrCO3、BaCO3、Al2O3、Ga2O3、Ta2O5、Nb2O5を準備した。これらの原料を下記の表1の組成になるように秤量し、ボールミルで20時間湿式混合した。得られた混合物を乾燥させた後、1400℃で3時間仮焼し、仮焼物を得た。この仮焼物を、水および有機分散剤とともにボールミルに入れ、12時間湿式粉砕した。この粉砕物を、湿式成形にて直径15mm、厚さ5mmの円板状に成形した。(Experimental example)
First, high-purity La (OH) 3 , Lu 2 O 3 , Gd 2 O 3 , SrCO 3 , BaCO 3 , Al 2 O 3 , Ga 2 O 3 , Ta 2 O 5 , and Nb 2 O 5 are used as raw materials. Got ready. These raw materials were weighed so as to have the composition shown in Table 1 below, and wet mixed in a ball mill for 20 hours. The obtained mixture was dried and calcined at 1400 ° C. for 3 hours to obtain a calcined product. This calcined product was placed in a ball mill together with water and an organic dispersant, and wet pulverized for 12 hours. This pulverized product was formed into a disk shape having a diameter of 15 mm and a thickness of 5 mm by wet molding.
次に、上記成形物を同組成からなる粉体に埋め、酸素雰囲気下(約98%酸素濃度)で、1700℃で20時間焼成し、焼結体を得た。得られた焼成体は、X線回折(XRD)法により、単純立方晶のペロブスカイト型化合物を主成分としていることが分かった。 Next, the molded product was embedded in a powder having the same composition and fired at 1700 ° C. for 20 hours in an oxygen atmosphere (about 98% oxygen concentration) to obtain a sintered body. The obtained fired product was found by X-ray diffraction (XRD) method to contain a simple cubic perovskite compound as a main component.
次に、焼結体の両面を、厚みが2.0mmの基板となるように鏡面研磨した。その後、H2/H2O還元雰囲気(酸素分圧:1×10−15MPa)中において熱処理を行い、サンプルを作製した。熱処理の最高温度は、1000℃とし、1000℃における保持時間は、3時間とした。Next, both surfaces of the sintered body were mirror-polished so as to form a substrate having a thickness of 2.0 mm. Thereafter, heat treatment was performed in a H 2 / H 2 O reducing atmosphere (oxygen partial pressure: 1 × 10 −15 MPa) to prepare a sample. The maximum temperature of the heat treatment was 1000 ° C., and the holding time at 1000 ° C. was 3 hours.
次に、サンプル1,2について、島津製作所製の紫外可視分光光度計UV−2500PCを用いて光透過率の測定を行った。結果を図1に示す。図1には、Ndを含むサンプル1(一点破線)と、NdとCrとを含むサンプル2(実線)の結果を示した。 Next, for samples 1 and 2, light transmittance was measured using an ultraviolet-visible spectrophotometer UV-2500PC manufactured by Shimadzu Corporation. The results are shown in FIG. In FIG. 1, the result of the sample 1 (one-dot broken line) containing Nd and the sample 2 (solid line) containing Nd and Cr was shown.
各サンプルの波長365nm〜850nmにおける光の吸収量(nm・cm−1)を表1に示す。ここで吸収量は、以下の式により算出した。Table 1 shows the amount of light absorption (nm · cm −1 ) of each sample at wavelengths of 365 nm to 850 nm. Here, the amount of absorption was calculated by the following equation.
I:波長λにおける基板の直線透過率
I0:波長700nmにおける基板の直線透過率
t:基板の肉厚(cm)I: Linear transmittance of substrate at wavelength λ I 0 : Linear transmittance of substrate at
次に、サンプル1,2について、株式会社浜松ホトニクス製マルチチャンネル分光器PMA−12を用い、Nd3+イオンの4I9/2→4G5/2+2G7/2遷移に相当する波長600nm、及びCr3+の3d−3d遷移に相当する波長450nmの光で励起したときの発光スペクトル測定を行った。発光スペクトルの例として、サンプル1及びサンプル2の測定結果を図2(波長600nm)及び図3(波長450nm)に示す。図2及び図3において、サンプル1は、一点破線で示し、サンプル2は、実線で示す。波長600nmの光で励起したときのNd3+イオンの4F3/2→4I9/2遷移に相当する、波長880nmの発光ピークについて、その最大発光強度と半値幅を表1に示した。ここで、最大発光強度は、発光ピークの最大値を示したものであり、サンプル1の最大発光強度を1とした場合における、相対値で示した。また、半値幅は発光強度が最大発光強度の半分以上となる波長の幅とした。参考サンプルとして、1原子%のNdを添加したNd:YAG単結晶(オキサイド社製、直径φ10mm、厚み2mm)においても同様の測定を行い、測定結果を表1に示した。なお、本実験例では、レーザー発振に用いられる4F3/2→4I11/2遷移(波長1060nm付近の発光)によって評価されるNdの発光特性を、波長900nm付近のNd発光(4F3/2→4I9/2)で代用して測定した。Next, for samples 1 and 2, using a multi-channel spectrometer PMA-12 manufactured by Hamamatsu Photonics Co., Ltd., a wavelength corresponding to the 4 I 9/2 → 4 G 5/2 + 2 G 7/2 transition of Nd 3+ ions An emission spectrum was measured when excited with light having a wavelength of 450 nm corresponding to 600 nm and Cr 3+ 3d-3d transition. As an example of the emission spectrum, the measurement results of Sample 1 and Sample 2 are shown in FIG. 2 (
図1に示されるように、Ndを含むサンプル1において、可視光域にNd3+イオンの4f−4f電子遷移に伴う吸収が見られた。NdとCrとを含むサンプル2においては、Cr3+イオンの3d−3d電子遷移による広い吸収(波長600nm付近と波長450nm付近)が見られた。As shown in FIG. 1, in Sample 1 containing Nd, absorption due to 4f-4f electron transition of Nd 3+ ions was observed in the visible light region. In Sample 2 containing Nd and Cr, wide absorption (around
サンプル1,6においては、図2及び図4に示されるように、Nd3+イオンの4I9/2→4G5/2+2G7/2遷移に相当する波長600nmの光を照射した場合、波長900nm付近にNd3+イオンの4F3/2→4I9/2遷移に相当する発光が見られた。サンプル1,6における波長880nmの発光における半値幅は、表1に示されるように、参考サンプルとしたNd:YAG(細線)と比較すると約20倍大きい。サンプル1,6の発光帯域は、広いことが分かる。Samples 1 and 6 were irradiated with light having a wavelength of 600 nm corresponding to the 4 I 9/2 → 4 G 5/2 + 2 G 7/2 transition of Nd 3+ ions, as shown in FIGS. In this case, light emission corresponding to the 4 F 3/2 → 4 I 9/2 transition of Nd 3+ ions was observed near the wavelength of 900 nm. As shown in Table 1, the full width at half maximum of light emission at a wavelength of 880 nm in samples 1 and 6 is about 20 times larger than Nd: YAG (thin line) as a reference sample. It can be seen that the emission bands of samples 1 and 6 are wide.
サンプル2,13においても、図2、図4及び表1に示されるように、波長880nmの発光における半値幅は大きく、サンプル2,13の発光帯域も、サンプル1,6と同様に、広いことが分かる。なお、図2において、サンプル2における波長700〜800nmの発光はCr3+の2E→4A2遷移発光によるものである。Also in samples 2 and 13, as shown in FIGS. 2, 4 and Table 1, the full width at half maximum for light emission at a wavelength of 880 nm is large, and the light emission band of samples 2 and 13 is wide as in samples 1 and 6. I understand. In FIG. 2, light emission with a wavelength of 700 to 800 nm in Sample 2 is due to Cr 3+ 2 E → 4 A 2 transition light emission.
サンプル2においては、図3に示されるように、Cr3+の吸収波長に相当する波長450nmの光を照射した場合、本来であればNd原子が励起されない波長であるにもかかわらず、図2と同様のNd3+イオンの発光が見られた。このことから、サンプル2では、Cr3+からNd3+へエネルギー移動が生じているものと考えられる。In sample 2, as shown in FIG. 3, when light having a wavelength of 450 nm corresponding to the absorption wavelength of Cr 3+ is irradiated, although Nd atoms are originally not excited, the sample 2 and FIG. Similar Nd 3+ ion emission was observed. From this, it is considered that in Sample 2, energy transfer occurs from Cr 3+ to Nd 3+ .
表1に示されるように、Crを含むサンプル2では、Crを含まないサンプル1よりも波長365nm〜850nmの光の吸収量が大きかった。Crを含むサンプル9〜11の吸収量と、Crを含まないサンプル5〜7の吸収量との比較から、Crは、セラミックスにおける波長365nm〜850nmの光の吸収量をより大きくすることができることが分かる。 As shown in Table 1, the absorption amount of light having a wavelength of 365 nm to 850 nm was larger in the sample 2 containing Cr than in the sample 1 not containing Cr. From the comparison of the absorption amount of Samples 9 to 11 containing Cr and the absorption amount of Samples 5 to 7 not containing Cr, Cr can increase the absorption amount of light with a wavelength of 365 nm to 850 nm in ceramics. I understand.
なお、表1の最大発光強度より、Ndの添加量は0.5mol%〜5mol%、Crの添加量は0.2mol%〜5mol%の範囲にあることが好ましいことが分かる。 In addition, it turns out that it is preferable that the addition amount of Nd exists in the range of 0.5 mol%-5 mol% and the addition amount of Cr exists in the range of 0.2 mol%-5 mol% from the maximum light emission intensity of Table 1.
Claims (3)
[組成式(1)において、M1は、La,Y,Gd及びLuからなる群から選ばれる少なくとも一種であり、M2は、Ba,Sr及びCaからなる群から選ばれる少なくとも一種であり、M3は、Al及びGaの少なくとも一方であり、M4は、Ta及びNbの少なくとも一方であり、0.2≦x≦0.95、0<y<0.5、0.45≦y/x≦0.55、wは、電気的中性を保つための正の数である。]で表されるペロブスカイト型化合物を主成分とするセラミックスであって、0.1mol%〜5mol%のNdを含み、さらにCrを含む、発光セラミックス。 Composition formula: (M1 1-x M2 x ) (M3 1-y M4 y ) O w (1)
[In composition formula (1), M1 is at least one selected from the group consisting of La, Y, Gd and Lu, M2 is at least one selected from the group consisting of Ba, Sr and Ca, and M3 is M4 is at least one of Ta and Nb, 0.2 ≦ x ≦ 0.95, 0 <y <0.5, 0.45 ≦ y / x ≦ 0. 55 and w are positive numbers for maintaining electrical neutrality. A ceramic consisting mainly of perovskite-type compound represented by, viewed contains a 0.1 mol% 5 mol% of Nd, further including Cr, luminescent ceramics.
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