电子俘获透明玻璃陶瓷的可控制备与光激励发光研究

The advent of “big data” era poses unprecedented challenges to information storage. Developing low cost and high energy efficiency optical storage mode and material are extremely urgent. The electron-trapped optical storage technique has long-term received researchers’ attention since 1980s, owing to the admirable merits of high storage capacity, fast access speed, and information multiplexing. However, the conventionally-used electron-trapped material, i.e., the electron-trapped powder and organic resin compound, ages easily, possesses low data-security and limited storage dimension, which hinder the practical application of this technique. In this project, the electron-trapped transparent glass ceramic embedded with solid-solution nanocrystals is proposed to solve these problems, hopefully increasing the service lifetime, improving the data security, and realizing the spatial-dimension optical storage. Systematical studies will be performed on the influence of glass composition on glass network and phase-separation behavior, as well as the solid-solution nanophase crystallization dynamics in glass. HRBE model will be constructed to reveal physical mechanism of the electron-trapped processes that are influenced by the manipulation of host bandgap structure. The impact of spatial distribution of rare earth ions on the photostimulated luminescence property will be explored. Thereupon, the relationship of composition-microstructure-property will be established, which can feedback to the microstructure manipulation and property optimization. Based on the above fundamental investigations, the validation experiments will be carried out to evaluate the application feasibility of the electron-trapped glass ceramic for optical-storage.

“大数据”时代的到来对信息存储提出了空前挑战，低成本、高能效的新型光存储模式与光存储材料的研发迫在眉睫。上世纪80年代兴起的电子俘获光存储技术具有存储密度高、存取速度快、可实现光信号多路复用等优势，自问世以来受到广泛关注，但由于所用材料为电子俘获粉体-有机物复合膜，在实际应用时面临着易老化、数据安全性和存储维度受限等难题。为了研发安全性高、寿命长、可实现空间维度光存储的新型光存储材料，本项目拟研究电子俘获透明玻璃陶瓷：系统分析玻璃组分对玻璃网络结构、玻璃分相与晶粒成核长大行为的影响，优化玻璃组分，实现特定石榴石结构固溶体纳米晶的可控晶化；揭示晶化相能带结构改变影响电子俘获过程的物理机制；构建HRBE模型，选择可产生深陷阱能级的辅助离子；探明玻璃陶瓷微结构和稀土离子分布对其光激励发光性能的影响，进而指导结构调控，改善材料性能；在此基础上，对电子俘获玻璃陶瓷的光存储应用的可行性进行实验验证。

“大数据”时代的到来对信息存储提出了空前挑战，低成本、高能效的新型光存储模式与光存储材料的研发意义重大。本项目聚焦于研究电子俘获型光存储材料，致力于探索材料组分设计、晶化机理、显微结构调控、缺陷性质及电子俘获机制。项目执行期间，研发了多种新型光激励发光玻璃陶瓷和光致变色玻璃/玻璃陶瓷，细致地研究了玻璃网络结构对玻璃可控晶化的影响、玻璃与微晶低温共烧过程中的热侵蚀效应、掺杂激活离子在非晶/微晶不同局域配位环境下的光谱特性、非晶/微晶的缺陷特性及其电子俘获机制、玻璃网络结构限域环境下金属团簇的形成及其受激结构/价态演变规律等。其中，BaSi2O5: Eu2+, Nd3+光激励发光玻璃陶瓷实现了图像、条形码、二维码、二进制数据的紫外光编码和热/近红外光解码，并展现了比以往光激励发光材料更优越的存储光信号稳定性和持久性。通过玻璃可控热处理晶化，首次获得了纳米结构的LiGa5O8:Mn2+光激励发光玻璃陶瓷，突破了目前光激励发光材料难以实现纳米尺度分辨率的瓶颈问题，并验证了该材料在三维光存储应用的可行性，所研制材料兼具强度/光频复用、高安全性和鲁棒性。研究了新型Ag掺杂TZN-x玻璃和V掺杂BNN玻璃，它们均具有较优的辐照响应能力，可通过便携式低功率蓝光激光器直接在透明玻璃体内写入光信息，在经济性上相比于以往飞秒激光直写技术有较大优势。研制了具有可快速自漂白特性的Bi1.5ZnNb1.5O7光致变色荧光粉，并将之与低熔点玻璃复合形成块材，发现其在多模式、高安全等级光存储防伪方面具有独特的优越性。理论上，揭示了该材料在亚带隙激发条件下，缺陷和色心之间通过直接电子转移进行状态交换的光致变色新机制。此外，作为项目拓展，我们还研究了一系列性能优异、可望应用于激光照明/显示和力敏传感技术的新型稀土掺杂荧光玻璃陶瓷材料。.项目成果在Light Sci. Appl.、Laser Photon. Rev.、J. Adv. Ceram.、Adv. Funct. Mater.、Nano Res.、J. Mater. Chem. C、Nanoscale、Opt. Lett.等国内外重要刊物发表论文30篇；申请中国发明专利6项（获授权2项）；培养（毕业）硕、博士研究生13名。