【作者】 罗岚；

【导师】 周浪；

【作者基本信息】 南昌大学 ， 材料物理化学， 2008， 博士

【摘要】 组合材料芯片技术是功能材料开发研究的全新方法,能够高效、快速地筛选/优化新材料。我们利用这一技术对新型稀土掺杂钆铝酸盐发光材料进行了研究,以期建立钆铝酸盐基发光材料数据库,为发光材料设计提供科学依据。本研究以国内第一个普适性组合技术研究平台—IM100离子束材料芯片沉积仪为主要实验设备,采用离子束顺序沉积技术设计、制备了一系列稀土掺杂钆铝酸盐发光材料芯片。我们针对发光材料体系中影响发光性能的主要因素:基体、发光中心种类、发光中心掺杂浓度、敏化中心种类等,进行了系统地研究;作为开展这一研究的实验基础,我们还进行了稀土掺杂钆铝酸盐发光材料粉体的制备技术研究。主要研究内容和结果如下:1、稀土掺杂钆铝酸盐发光材料发光性能的研究。凭借芯片技术实现该类发光材料的基体材料和稀土掺杂元素相关光学性能数据的迅速积累,并以第一性原理为研究手段探讨稀土掺杂钆铝酸盐材料的发光共性和规律。实验中以扫描电镜（SEM）、X射线相分析（XRD）、荧光发射和激发谱（PL）、紫外激发发光照相记录等分析方法来表征材料芯片和同步粉体样品。通过组合芯片筛选:发现GdAlO₃（GAP）是一种高效发光基体;完成了Ce、Pr、Sm、Eu、Tb、Dy等稀土离子的单掺杂和共掺杂光谱特性数据的积累;并从众多的稀土掺杂钆铝酸盐发光材料中优选出Eu、Tb离子主掺杂的线索材料。2、钆铝酸盐薄膜制备工艺研究。按化学计量比顺序沉积晶相薄膜各组元,通过低温扩散过程和高温晶化的两步热处理得到均质单相薄膜。热处理时考虑单层薄膜厚度、温度、时间等条件对薄膜的扩散均匀性的影响,以及在不同烧成温度下薄膜结晶状况。根据扫描电镜二次电子像（SEM）、X射线衍射谱（XRD）、俄歇深度剖析谱（AES）结果发现:当组元单层不大于500（?）时,钆铝酸盐前驱薄膜经低温扩散（400℃/120h）后,再经过高温晶化(Gd₄Al₂O₉（GAM）及GdAlO₃（GAP）在1300℃/4h、Gd₃Al₅O₁₂（GAG）在1200℃/4h的条件下),可得到单相晶化薄膜。3、稀土掺杂钆铝酸盐基发光材料粉体的制备技术研究。实验以X射线相分析（XRD）、热重-差热（TG-DSC）和计算热力学为分析手段,得到如下实验结果:柠檬酸盐-硝酸盐法制备稀土掺杂钆铝酸盐粉体时,≥900℃/2h可得到GdAlO₃、Gd₄Al₂O₉单相粉末,随着煅烧温度的升高,晶粒发育越完整;Gd₃Al₅O₁₂需要在900℃附近快速煅烧得到,900℃/1h是比较好的煅烧条件,低于或高于此温度都很难得到Gd₃Al₅O₁₂单相粉末。采用醋酸盐—硝酸盐法很难制备Gd₄Al₂O₉单相粉末,而GdAlO₃的单相粉末≥1100℃/2h即可得到;Gd₃Al₅O₁₂这一晶相粉体则需要850℃/2h保温后再900℃/1h煅烧得到。更多还原

【Abstract】 The combinatorial materials chip method is an excellent innovation for inorganic function material research.The technique is capable of efficiently discovering and screening new materials.In present work,a new luminescence material system, Gadolinium aluminate doped with rare earth ions,was investigated,and a database of this material system was set up.Some major issues associated with luminescence materials,such as host materials,activator and activator/sensitizer concentrations,were well taken into consideration in the process of materials chip design.With the utilization of IM100 ion beam deposition system,which is the first platform for combinatorial materials chip synthesis in China,a series of gadolinium aluminate luminescence materials chips were fabricated.Powder synthesis methods were also studied as the experimental basis.The main content and results of this research work are listed as follows:1) Gadolinium aluminate luminescence material doped with rare earth ions was studied by combinatorial method,including data collection of the luminescent properties and rule derivation with the first principle calculation.Scanning electron microscopy （SEM）,X-ray diffraction phase analysis（XRD）,Auger electron spectroscopy（AES） emission and excitation photoluminescence spectra（PL）,photoluminescence photos techniques were used as analysis methods.Based on experiments,GdAlO₃（GAP） was selected as the optimal host material in the gadolinium aluminate;luminescence spectra data of rare earth ions（RE=Ce,Pr,Sm,Eu,Tb,Dy） doped gadolinium aluminate were gathered;It was found that the Eu or Tb ion doped gadolinium aluminate can emit strong visible photoluminescence under UV excitation.2) The most suitable annealing condition for gadolinium aluminate single phase film synthesis was investigated.The stoichiometric gadolinium aluminate multiplayer thinfilm precursors（single layer thickness was less than 500A） were treated at 400℃/120 h+1300℃/4 h,and final products of GdAlO₃（GAP） and Gd₄Al₂O₉（GAM） single phase films were formed.For Gd₃Al₅O₁₂（GAG） phase stoichiometric precursor,the high temperature crystallization should be 1200℃/4h while the low temperature diffusion was the same.The XRD,AES analysis indicated that such two-step annealing processes would form pure single phase films,and the SEM analysis further proved that uniform and dense films were obtained.3) Powder synthesis for gadolinium aluminate luminescence materials.XRD,TGDSC and thermodynamics calculation were used as analysis methods.After obtaining the precursor powder from citrate-nitrate combustion process,≥900℃/2h annealing could form GAP,GAM single phase powder,the annealing condition should be changed to 900℃/1h（the temperature should be kept precisely at 900℃） when fabricating GAG. Acetate-nitrate combustion was also used to synthesis the gadolinium aluminate luminescence powder.It was found that 1100℃/2h for GAP,and 850℃/2h+900°/1h for GAG were the suitable heat treatment conditions.However,GAM single powder could not be obtained by this method.更多还原