CN101831294A - 蓝色发光荧光体 - Google Patents
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Abstract
本发明提供一种发光强度高且对热的稳定性高的蓝色发光荧光体。一种蓝色发光荧光体，其基本组成式由Sr3-xMgSi2O8:Eux(其中，x为0.008～0.110范围的数值)表示，具有与镁硅钙石相同的晶体结构，由使用入射角为θ的CuKα射线测得的衍射角2θ在20～130度范围的X射线衍射图案，通过Le Bail法求得的晶格应变为0.055％以下。
Description
技术领域
本发明涉及基本组成式由Sr3-xMgSi2O8:Eux表示的蓝色发光荧光体。
背景技术
已知以具有镁硅钙石(Ca3MgSi2O8)的晶体结构的Sr3MgSi2O8为母体，并激活Eu2+而得到的组成式由Sr3-xMgSi2O8:Eux表示的蓝色发光荧光体(以下也称作SMS蓝色发光荧光体)。该SMS蓝色发光荧光体通过紫外线、真空紫外线激发而显示蓝色发光，因此，探讨将其用作水银放电灯、等离子显示面板等各种荧光发光装置的蓝色发光源。
专利文献1中记载了组成式由3(Sr1-p·Eup)O·1MgO·2SiO2(0.003≤p≤0.05)表示的SMS蓝色发光荧光体。该专利文献1中，作为SMS蓝色发光荧光体的制造方法，记载了在氮和氢的混合气体气氛中将含有SrCO3、SrF2、Eu2O3、MgCO3和SiO2的原料粉末混合物烧成(焼成)的方法。
专利文献2中记载了组成式由xSrO·yEuO·MgO·zSiO2(2.970≤x≤3.500、0.006≤y≤0.030、1.900≤z≤2.100)表示的SMS蓝色发光荧光体。该专利文献2中还记载了，当SMS蓝色发光荧光体的由波长0.773
的X射线测定的X射线衍射图案的2θ为22.86度附近的衍射峰的1/5值宽度(1/5価幅)为0.17度以下时，Sr原子从正常位置的错位(ずれ)小，作为发光装置的蓝色发光源使用时的经时耐劣化性提高。另外，该专利文献2中，作为SMS蓝色发光荧光体的制造方法，记载了在将氧分压调节在特定范围的弱还原性气体气氛中将原料粉末混合物烧成的方法。
专利文献1：日本特公昭48-37715号公报
专利文献2：国际公开07/091603号小册子
发明内容
在水银放电灯、等离子显示面板等荧光发光装置中，荧光体作为荧光体层形成于基体上。基体上的荧光体层通常通过将荧光体的分散液涂布于基体上，接着将该涂布膜干燥、烧成而形成。因此，要求荧光体对热的稳定性高，以使发光强度不因涂布膜的干燥、烧成而降低。但是，至今对SMS蓝色发光荧光体的热稳定性没有进行探讨。
因此，本发明的目的在于，提供一种发光强度高、且对热的稳定性高的SMS蓝色发光荧光体。
本发明人发现由Sr3-xMgSi2O8:Eux表示的基本组成式中的x在0.008～0.110的范围、且由使用入射角为θ的CuKα射线测定的衍射角2θ在20～130度范围的X射线衍射图案通过Le Bail法求得的晶格应变为0.055％以下的SMS蓝色发光荧光体显示高的发光强度且对热的稳定性高，从而完成了本发明。
因此，本发明提供一种蓝色发光荧光体，其基本组成式由Sr3-xMgSi2O8:Eux(其中，x为0.008～0.110范围的数值)表示，具有与镁硅钙石相同的晶体结构，由使用入射角为θ的CuKα射线测定的衍射角2θ在20～130度范围的X射线衍射图案通过Le Bail法求得的晶格应变为0.055％以下。
本发明的优选方式如下：
(1)晶格应变为0.045％以下。
(2)基本组成式中的x为0.033～0.095范围的数值。
本发明的SMS蓝色发光荧光体显示高的发光强度且对热的稳定性高，因此，可以作为水银放电灯、等离子显示面板等各种荧光发光装置的蓝色发光源有效利用。
具体实施方式
本发明的SMS蓝色发光荧光体，其基本组成式由Sr3-xMgSi2O8:Eux(其中，x为0.008～0.110范围的数值)表示。x优选为0.033～0.095范围的数值，特别优选0.043～0.070范围的数值。
本发明的SMS蓝色发光荧光体，由使用CuKα射线测定的2θ在20～130度范围的X射线衍射图案通过Le Bail法求得的晶格应变为0.055％以下。晶格应变优选为0.045％以下，特别优选为0.040％以下。晶格应变的下限通常为0.025％。
本发明中，晶格应变是由使用CuKα射线测定的2θ在20～130度范围的X射线衍射图案中的起因于具有镁硅钙石晶体结构的SMS蓝色发光荧光体的衍射峰求出的值。即，本发明中规定的晶格应变是指从理想的SMS蓝色发光荧光体结晶的网面间距偏离(ずれ)的大小。
本发明中，通过LeBail法求得晶格应变。本发明中，LeBail法是指，由X射线衍射图案中衍射峰的θ、强度和半宽度(FWHM)通过Le Bail拟合法(Le Bailフイツテイング法)得到Cagliotti式的参数U、V、W，并由所得到的参数U和W通过Pseudo-Voigt函数计算晶格应变(％)的方法。Le Bail拟合法作为不使用构造模型而可得到参数U、V、W的线形拟合法(プロフアイルフイツテイング法)已知。通过Le Bail拟合法得到参数U、V、W的方法被记载于A.Le Bail等的研究报告Mat.Res.Bull.，vol.23，pp.447-452，1988中(其中，该研究报告中，将Le Bail拟合法称作修正里德伯尔德法(modifiedRietveld method))。
在求SMS蓝色发光荧光体的晶格应变时，使用不具有晶格应变的X射线衍射用标准试样校正由X射线衍射装置引起的半宽度的扩展(拡がり)。SMS蓝色发光荧光体的晶格应变例如可如下求得。
首先，使用CuKα射线对SMS蓝色发光荧光体和X射线衍射用标准试样测定2θ在20～130度范围的X射线衍射图案。X射线衍射图案使用粉末X射线衍射法测定。
接着，由SMS蓝色发光荧光体和X射线衍射用标准试样的X射线衍射图案中的衍射峰的θ、强度和半宽度(FWHM)，通过Le Bail拟合法得到下式(1)定义的Cagliotti式的参数U、V、W。
FWHM＝(Utan2θ+Vtanθ+W)1/2 (I)
其中，FWHM是衍射峰的半宽度，θ是衍射峰的布拉格角，U是与晶格应变有关的参数，V和W是与微晶有关的参数。
而且，根据所得到的SMS蓝色发光荧光体和X射线衍射用标准试样的参数的U和W，通过下式(II)定义的Pseudo-Voigt函数计算晶格应变(％)。
其中，Ui和Wi是SMS蓝色发光荧光体的参数U和W，Ustd和Wstd是X射线衍射用标准试样的参数U和W。
本发明的SMS蓝色发光荧光体例如可通过在氯化合物的存在下将下述粉末混合物烧成而制造，所述粉末混合物是将锶源粉末、镁源粉末、硅源粉末和铕源粉末各原料粉末以生成SMS蓝色发光荧光体的比例混合而得到的。
锶源粉末、镁源粉末、硅源粉末和铕源粉末各原料粉末分别可以是氧化物粉末，也可以是氢氧化物、卤化物、碳酸盐(含碱式碳酸盐)、硝酸盐、草酸盐等通过加热生成氧化物的化合物的粉末。原料粉末分别可以单独使用一种，也可以并用两种以上。
原料粉末优选纯度为99质量％以上。特别是镁源粉末优选纯度为99.95质量％以上。
锶源粉末、镁源粉末、硅源粉末和铕源粉末的配合比率为下述比例，即，以粉末混合物中的锶和铕的合计量为3摩尔，通常镁在0.9～1.1摩尔的范围，硅在1.9～2.1摩尔的范围。
氯化合物优选以粉末的状态添加到粉末混合物中。氯化合物粉末优选为锶、镁、硅和/或铕的氯化物的粉末，特别优选为氯化锶粉末。氯化合物粉末的添加量优选为下述量，即，以粉末混合物中的锶和铕的合计量为3摩尔，使氯量在0.02～0.5摩尔的范围的量。
原料粉末的混合方法可采用干式混合法和湿式混合法中的任一种方法。在以湿式混合法混合原料粉末时，可使用旋转球磨机(回転ボ一ルミル)、振动球磨机(振動ボ一ルミル)、行星磨机(遊星ミル)、涂料混合器(ペイントシエ一カ一)、摇摆磨机(ロツキングミル.)、摇摆式混合机(ロツキングミキサ一)、珠磨机(ビ一ズミル)、搅拌机(撹拌機)等。溶剂可使用水、乙醇、异丙醇等低级醇。
粉末混合物的烧成在由0.5～5.0体积％的氢和99.5～95.0体积％的惰性气体构成的还原性气体的气氛中进行。作为惰性气体的例子，可列举氩和氮。烧成温度通常在900～1300℃的范围。烧成时间通常在0.5～100小时的范围。
在原料粉末使用通过加热而生成氧化物的化合物的粉末的情况下，优选在还原性气体气氛中烧成之前，将粉末混合物在大气气氛中以600～850℃的温度煅烧(仮焼)0.5～100小时。
通过烧成得到的SMS蓝色发光荧光体根据需要也可以进行分级处理、通过盐酸、硝酸等无机酸进行的酸洗涤处理、烘焙处理。
(实施例)
[实施例1～16、比较例1～3]
按下表1所记载的摩尔量分别称量SrCO3粉末(纯度99.99质量％、平均粒径2.73μm)、SrCl2粉末(纯度99.99质量％)、SrF2粉末(纯度99.5质量％)、碱式MgCO3粉末(4MgCO3·Mg(OH)2·4H2O粉末、纯度99.99质量％、平均粒径11.08μm)、SiO2粉末(纯度99.9质量％、平均粒径3.87μm)、Eu2O3粉末(纯度99.9质量％、平均粒径2.71μm)。另外，各原料粉末的平均粒径都是通过激光衍射散射法测得的值。
将称量好的各原料粉末与纯水750mL一同投入球磨机中，湿式混合24小时后，通过加热除去水分，得到粉末混合物。将得到的粉末混合物投入氧化铝坩锅内，在大气气氛中以800℃的温度烧成3小时，接着放冷至室温后，在2体积％氢-98体积％氩的混合气体气氛中以1200℃的温度烧成3小时，得到粉末烧成物。将得到的粉末烧成物用网眼20μm的聚酰胺制筛进行湿式筛分，除去粗大粒子后干燥。
表1
对实施例1～16和比较例1～3中得到的粉末烧成物测定X射线衍射图案和利用波长254nm的紫外线激发得到的发光光谱。其结果确认，实施例1～16和比较例1～3中得到的粉末烧成物都具有镁硅钙石晶体结构，是通过紫外线激发而显示蓝色发光的SMS蓝色发光荧光体。
通过下述方法对实施例1～16和比较例1～3中得到的SMS蓝色发光荧光体测定晶格应变、初始发光强度(初期発光強度)、加热处理后的发光强度维持率。将这些结果与SMS蓝色发光荧光体的组成一同示于下表2。
[晶格应变的测定]
测定SMS蓝色发光荧光体和X射线衍射用标准试样[NIST(NationalInstitute of Standards and Technology)的LaB6粉末]的X射线衍射图案。测定条件为，X射线衍射装置：X’PertProMPD、スペクトリス(株)制、X射线：CuKα、检测器：X’Clelerator(带单色仪)、管电压：45kV、管电流：40mA、测定范围：2θ＝20～130度、步长(ステツプサイズ)：0.0167度、发散狭缝：1/2度固定狭缝、扫描速度：25.06度/分钟。
由SMS蓝色发光荧光体和标准试样的X射线衍射图案，使用X射线衍射装置所带的软件[X’Pert Highscore Plus(Ver2.2)]，通过Le Bail法计算晶格应变。
[初始发光强度的测定]
向SMS蓝色发光荧光体照射波长254nm的紫外线，测定发光光谱。求出得到的发光光谱的最大峰值，以此为初始发光强度。另外，表2中的值是以比较例3中得到的SMS蓝色发光荧光体的初始发光强度为100时的相对值。
[加热处理后的发光强度维持率的测定]
在500℃的温度下将SMS蓝色发光荧光体加热1小时后，放冷至室温。对放冷后的SMS蓝色发光荧光体照射波长254nm的紫外线，测定发光光谱。求得到的发光光谱的最大峰值，计算相对于上述初始发光强度的百分率，以此为发光强度维持率。
表2
注)组成是通过原料粉末的配合量算出的值。
由表2的结果表明，由Sr3-xMgSi2O8:Eux表示的基本组成式中的x在0.008～0.110的范围，且晶格应变为0.055％以下的本发明的SMS蓝色发光荧光体与晶格应变大于0.055％的SMS蓝色发光荧光体相比，初始发光强度都高，且加热处理后的发光强度维持率都高。
Claims (3)
1.蓝色发光荧光体，其基本组成式由Sr3-xMgSi2O8:Eux(其中，x为0.008～0.110范围的数值)表示，具有与镁硅钙石相同的晶体结构，由使用入射角为θ的CuKα射线测得的衍射角2θ在20～130度范围的X射线衍射图案，通过Le Bail法求得的晶格应变为0.055％以下。
2.如权利要求1所述的蓝色发光荧光体，其中，晶格应变为0.045％以下。
3.如权利要求1或2所述的蓝色发光荧光体，其中，基本组成式中的x为0.033～0.095范围的数值。
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| TWI595076B (zh) * | 2011-02-28 | 2017-08-11 | Ube Industries | A blue light-emitting phosphor, and a light-emitting device using the blue light-emitting phosphor |
| CN115151845A (zh) * | 2020-03-18 | 2022-10-04 | 电化株式会社 | 荧光体板和发光装置 |
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| US10538702B2 (en) | 2015-01-07 | 2020-01-21 | Ube Industries, Ltd. | Fluorescent material, light-emitting device, and method for producing fluorescent material |
| JP6776556B2 (ja) * | 2016-03-02 | 2020-10-28 | 三菱ケミカル株式会社 | 蛍光体、発光装置、画像表示装置及び照明装置 |
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| WO2007091603A1 (ja) * | 2006-02-07 | 2007-08-16 | Matsushita Electric Industrial Co., Ltd. | 蛍光体、発光装置およびプラズマディスプレイパネル |
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| TW200528537A (en) * | 2004-02-27 | 2005-09-01 | Sumitomo Chemical Co | Method for producing silicate phosphor and vacuum ultraviolet excited light-emitting devicemethod for producing silicate phosphor and vacuum ultraviolet excited light-emitting device |
| JP2006012770A (ja) * | 2004-05-27 | 2006-01-12 | Hitachi Ltd | 発光装置及び該発光装置を用いた画像表示装置 |
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| WO2007091603A1 (ja) * | 2006-02-07 | 2007-08-16 | Matsushita Electric Industrial Co., Ltd. | 蛍光体、発光装置およびプラズマディスプレイパネル |
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| CN102344809A (zh) * | 2011-07-20 | 2012-02-08 | 彩虹集团公司 | 一种白光led荧光粉及其制备方法 |
| CN115151845A (zh) * | 2020-03-18 | 2022-10-04 | 电化株式会社 | 荧光体板和发光装置 |
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