CN111410531B - 基于光致变色效应的上转换发光可逆调控材料及制备方法 - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 40
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- 230000002441 reversible effect Effects 0.000 title claims abstract description 25
- 230000000694 effects Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 52
- 238000000227 grinding Methods 0.000 claims abstract description 21
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 14
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims abstract description 7
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
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- 229910052593 corundum Inorganic materials 0.000 description 8
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- 229910000416 bismuth oxide Inorganic materials 0.000 description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 4
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- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 description 4
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Abstract
一种基于光致变色效应的上转换发光可逆调控材料及制备方法。材料的化学式为SrBi3.9‑ xHoxYb0.1Ti4O15，其中，x＝0.005、0.02、0.05或0.1。制备方法是以SrCO3、Bi2O3、Yb2O3、Ho2O3和TiO2作为原料，按比例进行混合研磨，进而利用简单高温固相反应法而制备出SrBi3.9‑ xHoxYb0.1Ti4O15陶瓷材料。本发明优点：在近紫外光辐照下，材料展现明显的变色，与此同时材料的上转换发光强度也随之发生改变。同时，在热刺激下，变色可以被复原到辐照前的状态，材料上转换发光也回到初态。在近紫外辐照和热刺激的交替作用下，材料上转换发光表现出优异的可逆调控性能，而且响应迅速，这表明该材料未来可用于光开关、光学存储、安全防伪等领域。
Description
技术领域
本发明属于稀土基上转换发光材料技术领域，具体涉及一种基于光致变色效应的上转换发光可逆调控材料及制备方法。
背景技术
目前，具有可逆发光调控能力的上转换发光材料因其在数据存储、光学开关、可擦写纸和多色显示器等方面具有广泛的应用前景而备受人们关注。光致变色通常是一种可逆过程，因而可以尝试利用该过程来调控某些材料的发光性能。迄今为止，科研人员对光致变色材料的研究大多集中于有机物，比如亚砜、二苯乙烯衍生物、腙类化合物、斯坦豪斯化合物、邻硝基苄基衍生物等。然而，大多数有机物材料热稳定性能差，且对环境有毒，因此限制了它们的应用。与有机光致变色材料相比，无机光致变色材料具有许多优势，比如化学稳定性好、机械强度高、抗氧化能力强等。然而，现存在的无机光致变色材料相对较少，性能也不是太理想，尤其是能基于光致变色效应实现上转换发光可逆调控的材料更少。为满足未来高性能动态调控光电器件的需求，这就需要科研工作者发明能实现上转换发光有效调控的新材料或新途径。
发明内容
为了解决上述问题，本发明的目的在于提供一种基于光致变色效应的上转换发光可逆调控材料及制备方法。
为了达到上述目的，本发明提供的基于光致变色效应的上转换发光可逆调控材料是化学式为SrBi3.9-xHoxYb0.1Ti4O15的陶瓷材料，其中，x＝0.005、0.02、0.05或0.1。
本发明提供的基于光致变色效应的上转换发光可逆调控材料的制备方法是以SrCO3、Bi2O3、Yb2O3、Ho2O3和TiO2作为原料，将上述原料按比例进行混合，以无水乙醇作为溶剂，在球磨机中研磨成混合均匀的粉末，之后将粉末进行干燥，并于1050℃下进行预烧；然后将预烧后的粉末再次进行研磨，加入粘合剂并造粒，压片后在1100℃下进行烧结，冷却到室温，经碳化硅表面抛光减薄后，获得属于上转换发光可逆调控材料的SrBi3.9- xHoxYb0.1Ti4O15陶瓷材料，其中，x＝0.005、0.02、0.05或0.1。
所述的SrCO3、Bi2O3、Yb2O3、Ho2O3和TiO2的质量比如下：
当x＝0.005时，质量比为1/6.1470/0.0064/0.1322/2.1641；
当x＝0.02时，质量比为1/6.1234/0.0254/0.1322/2.1641；
当x＝0.05时，质量比为1/6.0760/0.0634/0.1322/2.1641；
当x＝0.1时，质量比为1/5.9971/0.1269/0.1322/2.1641。
所述的球磨机采用行星式球磨机。
所述的球磨机中的研磨时间为24h。
所述的预烧时间为5小时。
所述的烧结时间为3小时。
所述的粘合剂采用聚乙烯醇缩丁醛酯。
本发明提供的基于光致变色效应的上转换发光可逆调控材料及制备方法具有如下优点和特点：
1、以SrCO3、Bi2O3、Yb2O3、Ho2O3和TiO2作为原料，并利用简单高温固相反应法而制备出SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料。
2、在980纳米近红外光激发下，SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料展现出明亮的绿光发射与相对较弱的红光发射，均属于两光子上转换过程。
3、研究表明SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料被近紫外光辐照一定时间后，材料漫反射谱强度明显降低，样品颜色发生变化，与之对应材料上转换发光强度相比于辐照前显著降低。
4、在980纳米近红外光激发下，SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料辐照前后上转换绿光峰强度调控率最高约为74％。
5、辐照后的SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料在200℃下加热1分钟后，材料颜色恢复到辐照前的初态，上转换发光也恢复到辐照前的状态。
6、研究表明，连续交替辐照与加热能实现对SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料上转换发光的可逆有效调控。
附图说明
图1是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料的X射线衍射图谱。
图2是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料在980纳米近红外光激发下的室温上转换发射谱。
图3是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.02)陶瓷材料在不同980纳米激发光功率下上转换发射光谱。
图4是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.02)陶瓷材料上转换绿光发射与红光发射强度的对数随激发功率的对数变化关系。
图5是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料在405纳米近紫外光辐照前后的上转换发射光谱。
图6是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005)陶瓷材料在近紫外光辐照前后的漫反射光谱。
图7是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.02)陶瓷材料在近紫外光辐照前后的漫反射光谱。
图8是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.05)陶瓷材料在近紫外光辐照前后的漫反射光谱。
图9是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x 0.1)陶瓷材料在近紫外光辐照前后的漫反射光谱。
图10是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.02)陶瓷材料表面照片。
图11是405纳米近紫外光照射时间对本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料上转换发光调控率R的影响
图12是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005)陶瓷材料在405纳米辐照与200℃热处理交替作用下调控率R随测试循环次数N的变化关系。
图13是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.02)陶瓷材料在405纳米辐照与200℃热处理交替作用下调控率R随测试循环次数N的变化关系。
图14是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.05)陶瓷材料在405纳米辐照与200℃热处理交替作用下调控率R随测试循环次数N的变化关系。
图15是本发明实施例提供的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.1)陶瓷材料在405纳米辐照与200℃热处理交替作用下调控率R随测试循环次数N的变化关系。
具体实施方式
现结合具体实施例对本发明做进一步地描述：
实施例1:
本实施例提供的上转换发光可逆调控材料为SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料，其中x＝0.005，其制备方法如下：
使用精度为0.0001克的电子天平称取0.8947克碳酸锶(99％)，5.4997克氧化铋(99％)，0.1183克氧化镱(99.9％)，1.9362克氧化钛(99％)，0.0057克氧化钬(99.9％)，放入干净的玛瑙罐中，加入约为罐体体积2/3的无水乙醇(99.7％)，然后置于行星式球磨机中进行研磨，时间为24小时。将产物从玛瑙罐中取出，置入玻璃烧杯中，用烘箱进行干燥，之后用研钵研磨，将产物置入刚玉坩埚，放入箱式炉，连续升温至1050℃预烧5小时，降温至550℃。之后将随炉冷却后所得产物用玛瑙研钵磨细，加入粘合剂聚乙烯醇缩丁醛酯(PVB，与产物重量比为0.5％)，充分研磨，混合均匀，进行造粒。在10MPa压力下制备成直径13mm的陶瓷生坯片。将陶瓷生坯片置于高温炉中，连续升温，在700℃下保温120分钟排塑，然后连续升温，在1100℃下烧结3小时，降温至550℃，自然冷却后获得x＝0.005的SrBi3.9- xHoxYb0.1Ti4O15陶瓷材料。
实施例2:
本实施例提供的上转换发光可逆调控材料为SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料，其中x＝0.02，其制备方法如下：
使用精度为0.0001克的电子天平称取0.8947克碳酸锶(99％)，5.4786克氧化铋(99％)，0.1183克氧化镱(99.9％)，1.9362克氧化钛(99％)，0.0227克氧化钬(99.9％)，放入干净的玛瑙罐中，加入约为罐体体积2/3的无水乙醇(99.7％)，然后置于行星式球磨机中进行研磨，时间为24小时。将产物从玛瑙罐中取出，置入玻璃烧杯中，用烘箱进行干燥，之后用研钵研磨，将产物置入刚玉坩埚，放入箱式炉，连续升温至1050℃预烧5小时，降温至550℃。之后将随炉冷却后所得产物用玛瑙研钵磨细，加入粘合剂PVB(与产物重量比为0.5％)，充分研磨，混合均匀，进行造粒。在10MPa压力下制备成直径13mm的陶瓷生坯片。将陶瓷生坯片置于高温炉中，连续升温，在700℃下保温120分钟排塑，然后连续升温，在1100℃下烧结3小时，降温至550℃，自然冷却后获得x＝0.02的SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料。
实施例3:
本实施例提供的上转换发光可逆调控材料为SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料，其中x＝0.05，其制备方法如下：
使用精度为0.0001克的电子天平称取0.8947克碳酸锶(99％)，5.4362克氧化铋(99％)，0.1183克氧化镱(99.9％)，1.9362克氧化钛(99％)，0.0567克氧化钬(99.9％)，放入干净的玛瑙罐中，加入约为罐体体积2/3的无水乙醇(99.7％)，然后置于行星式球磨机中进行研磨，时间为24小时。将产物从玛瑙罐中取出，置入玻璃烧杯中，用烘箱进行干燥，之后用研钵研磨，将产物置入刚玉坩埚，放入箱式炉，连续升温至1050℃预烧5小时，降温至550℃。之后将随炉冷却后所得产物用玛瑙研钵磨细，加入粘合剂PVB(与产物重量比为0.5％)，充分研磨，混合均匀，进行造粒。在10MPa压力下制备成直径13mm的陶瓷生坯片。将陶瓷生坯片置于高温炉中，连续升温，在700℃下保温120分钟排塑，然后连续升温，在1100℃下烧结3小时，降温至550℃，自然冷却后获得x＝0.05的SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料。
实施例4:
本实施例提供的上转换发光可逆调控材料为SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料，其中x＝0.1，其制备方法如下：
使用精度为0.0001克的电子天平称取0.8947克碳酸锶(99％)，5.3656克氧化铋(99％)，0.1183克氧化镱(99.9％)，1.9362克氧化钛(99％)，0.1135克氧化钬(99.9％)，放入干净的玛瑙罐中，加入约为罐体体积2/3的无水乙醇(99.7％)，然后置于行星式球磨机中进行研磨，时间为24小时。将产物从玛瑙罐中取出，置入玻璃烧杯中，用烘箱进行干燥，之后用研钵研磨，将产物置入刚玉坩埚，放入箱式炉，连续升温至1050℃预烧5小时，降温至550℃。之后将随炉冷却后所得产物用玛瑙研钵磨细，加入粘合剂PVB(与产物重量比为0.5％)，充分研磨，混合均匀，进行造粒。在10MPa压力下制备成直径13mm的陶瓷生坯片。将陶瓷生坯片置于高温炉中，连续升温，在700℃下保温120分钟排塑，然后连续升温，在1100℃下烧结3小时，降温至550℃，自然冷却后获得x＝0.1的SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料。
为了验证本发明的效果，本发明人进行了如下实验：
1、将上述实施例制备的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料利用碳化硅研磨粉减薄至0.5毫米厚度。
2、以980纳米近红外光为激发波长，利用光谱仪测试上述SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料的室温上转换发射光谱。
3、利用405纳米近紫外光(设定功率为80毫瓦)，辐照SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料1分钟。
4、将步骤3中辐照后的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料按照步骤2中的测试条件，测试上转换发射光谱。
5、将步骤4测试完成后的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料在200℃下保温1分钟，取出冷却到室温，然后按照步骤2中的测试条件测试上转换发射光谱。
6、用带有图案的掩膜版覆盖SrBi3.9-xHoxYb0.1Ti4O15(x＝0.02)陶瓷材料的表面，然后用405纳米近紫外光辐照1分钟，去除掩膜板，用普通相机对陶瓷表面进行拍照。
7、近紫外光辐照前后，利用反射谱测试仪表征SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料的漫反射谱光谱。
本发明实施例制备的SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料的晶体结构表征如图1所示，可见所有衍射峰都与标准数据很好地吻合，形成了单一的正交相。在980nm近红外光激发下，SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料展现出明亮的上转换绿光发射与相对较弱的红光发射，分别对应5F4/5S2→5I8、5F5→5I8和5S2→5I7电子跃迁，如图2所示。图3给出了SrBi3.9-xHoxYb0.1Ti4O15(x＝0.02)陶瓷材料在不同功率下的上转换发射光谱。图4表明SrBi3.9-xHoxYb0.1Ti4O15(x＝0.02)陶瓷材料上转换绿光(5F4/5S2→5I8)与红光(5F5→5I8和5S2→5I7)发射均属于两光子上转换过程。图5给出了SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料在405纳米近紫外光辐照前与辐照1分钟后的室温上转换发射光谱，辐照后SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料的上转换发光强度显著降低。标记辐照前后绿光发射峰积分强度分别为I1与I2，定义上转换调控率为R＝(I1-I2)/I1，从图5计算得到的调控率R分别是67.3％(x＝0.005)、74％(x＝0.02)、66.4％(x＝0.05)、62.6％(x＝0.1)。图6到图9给出了SrBi3.9-xHoxYb0.1Ti4O15(x＝0.0、0.005、0.02、0.05或0.1)陶瓷材料在近紫外光辐照前后的漫反射光谱。图10是SrBi3.9-xHoxYb0.1Ti4O15(x＝0.02)陶瓷材料表面照片，可见中心被近紫外光照射的部分颜色由黄褐色变为了灰黑色。图11是405纳米近紫外光照射时间对SrBi3.9-xHoxYb0.1 Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料上转换发光调控率R的影响，可以看出在材料被近紫外光辐照的最初10s内，其调控率R迅速上升，说明本发明提供的陶瓷材料发光调控具有快速响应的特征。图12到图15是SrBi3.9-xHoxYb0.1Ti4O15(x＝0.005、0.02、0.05或0.1)陶瓷材料在405nm辐照与200℃热处理交替作用下调控率R随测试循环次数N的变化关系。十次循环测试，调控率R的平均值分别为64.9％(x＝0.005)，73.5％(x＝0.02)，63.2％(x＝0.05)，58.5％(x＝0.1)。可以看出200℃热处理(时间1分钟)能基本擦除辐照效应，使SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料上转换发光恢复辐照前的初态，并且SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料的上转换调控展现出很好的重复性。
Claims (6)
1.一种基于光致变色效应的上转换发光可逆调控材料，其特征在于：所述上转换发光可逆调控材料是化学式为SrBi3.9-xHoxYb0.1Ti4O15的陶瓷材料，其中，x＝0.02；
所述基于光致变色效应的上转换发光可逆调控材料的制备方法是以SrCO3、Bi2O3、Yb2O3、Ho2O3和TiO2作为原料，将上述原料按比例进行混合，以无水乙醇作为溶剂，在球磨机中研磨成混合均匀的粉末，之后将粉末进行干燥，并于1050℃下进行预烧，所述的预烧时间为5小时；然后将预烧后的粉末再次进行研磨，加入粘合剂并造粒，压片后在1100℃下进行烧结，所述的烧结时间为3小时，冷却到室温，经碳化硅表面抛光减薄后，获得基于光致变色效应的上转换发光可逆调控SrBi3.9-xHoxYb0.1Ti4O15陶瓷材料，其中，x＝0.02。
2.一种如权利要求1所述基于光致变色效应的上转换发光可逆调控材料的制备方法，其特征在于：所述的制备方法是以SrCO3、Bi2O3、Yb2O3、Ho2O3和TiO2作为原料，将上述原料按比例进行混合，以无水乙醇作为溶剂，在球磨机中研磨成混合均匀的粉末，之后将粉末进行干燥，并于1050℃下进行预烧，所述的预烧时间为5小时；然后将预烧后的粉末再次进行研磨，加入粘合剂并造粒，压片后在1100℃下进行烧结，所述的烧结时间为3小时，冷却到室温，经碳化硅表面抛光减薄后，获得基于光致变色效应的上转换发光可逆调控SrBi3.9- xHoxYb0.1Ti4O15陶瓷材料，其中，x＝0.02。
3.根据权利要求2所述的基于光致变色效应的上转换发光可逆调控材料的制备方法，其特征在于：所述的SrCO3、Bi2O3、Yb2O3、Ho2O3和TiO2的质量比如下：
当x＝0.02时，质量比为1/6.1234/0.0254/0.1322/2.1641。
4.根据权利要求2所述的基于光致变色效应的上转换发光可逆调控材料的制备方法，其特征在于：所述的球磨机采用行星式球磨机。
5.根据权利要求2所述的基于光致变色效应的上转换发光可逆调控材料的制备方法，其特征在于：所述的球磨机中的研磨时间为24h。
6.根据权利要求2所述的基于光致变色效应的上转换发光可逆调控材料的制备方法，其特征在于：所述的粘合剂采用聚乙烯醇缩丁醛酯。
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