Preparation and Luminescent Properties of Ti‐Activated Zirconia
Preparation and Luminescent Properties of Ti‐Activated Zirconia
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DOI：
10.1149/1.2423883
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发表时间：
1966-02
影响因子：
3.9
通讯作者：
J. F. Sarver
中科院分区：
文献类型：
--
作者：
J. F. Sarver
用0.08%Ti4+活化重结晶的氧氯化锆制备了高纯的单斜晶系的氧化锆，对2537A和阴极激发有很好的响应。在2537A激发下，获得了相对于MgWO4约70%的室温量子效率。发射带从4000以下延伸到6500A以上，在4800A处达到峰值。这种荧光粉具有广泛的激发光谱，对2100到2600A之间的波长响应几乎同样好。在20℃时，对2537A激发的响应约为-60℃时最大响应的82%。初始衰减是指数型的，速率常数为~z 1.5×105秒-1，但肉眼可检测到的持续时间为几分钟。这种长余辉与发现在20℃以上的发光峰有关。在此之前，作者观察到几种商业来源的单斜氧化锆对2537A和阴极射线的激发做出了响应，产生了蓝白色的长余辉发光。国家铅公司钛合金制造部门生产的一种纯度相对较高的锆化合物--水合碳酸锆的实验样品制备的二氧化锆似乎只有微弱的发光。以前的文献(1，2)中也提到过类似的观察结果。哈里森、梅拉米德和苏巴拉奥(2)的一篇论文激发了人们对这一现象的进一步兴趣，他们准备了几种具有相同广义式的化合物。特别感兴趣的是具有通式R22+ZrR25+09的一系列等结构化合物，其中R2+是Sr2+、Ba2+或Pb2+，R5+是P5+或As5+。这些化合物对2537A的激发有响应，表现出较宽的发射带，峰值波长在4840-4920A之间。他们还发现，在制备三元化合物时使用的单斜晶氧化锆也有类似的发射。这些同型化合物的吸收光谱、激发光谱和发射光谱与ZrO2的吸收光谱、激发光谱和发射光谱的显著相似性表明，这些荧光粉是自激活型的，某些钨酸盐和钼酸盐化合物也是如此。他们认为，这种发光可能与氧原子在Zr4+离子上的不对称配位有关。单斜晶系的氧化锆中的氧配位确实是不对称的和不寻常的。根据麦卡洛和特鲁布拉德(3)的说法，齐尔-
Very pure monoclinic ZrO2 prepared from recrystallized zirconium oxychloride and activated with 0.08% Ti 4+ responds well to 2537A and cathoderay excitation. A room temperature quantum efficiency of 70%, relative to MgWO4, has been attained with 2537A excitation. The emission band extends from below 4000 to above 6500A, peaking at 4800A. The phosphor has a broad excitation spectrum and responds almost equally well to wavelengths between 2100 and 2600A. At 20~ the response to 2537A excitation is about 82% of the maximum response which occurs at about--60~ The initial decay is exponential with rate constant~ z 1.5 x 105 sec-1, but the visually detectable persistence lasts several minutes. The long persistence is associated with glow peaks which were found to exist above 20~ Additional stronger glow peaks occur at lower temperatures.Prior to this investigation it was observed by the author that several commercial sources of monoclinic zirconia responded to 2537A and cathode-ray excitation, yielding a blue-white luminescence with a long persistence. ZrO2 prepared from an experimental sample of hydrous zirconium carbonate, which is a relatively high purity zirconium compound manufactured by the Titanium Alloy Manufacturing Division of the National Lead Company, appeared to be only weakly luminescent. Similar observations have been mentioned previously in the literature (1, 2). Further interest in this phenomenon was stimulated by a paper of Harrison, Melamed, and Subbarao (2) who prepared several compounds having the same generalized formula. Of special interest was a series of isostructural compounds having the generalized formula R22+ ZrR25+ 09 where R 2+ is Sr 2+, Ba 2+, or Pb 2+, and R 5+ is p5+ or As 5+. These compounds responded to 2537A excitation and exhibited broad emission bands with peak wavelengths between 4840 and 4920A. They also found a similar emission for the monoclinic ZrO2 used in the preparation of the ternary compounds. The marked similarity in the absorption, excitation, and emission spectra of these isotypic compounds and of ZrO2 suggested to the authors that the phosphors were of the self-activated type, as are certain tungstate and molybdate compounds. They suggested the possibility that the luminescence is related to an asymmetric coordination of oxygens about the Zr 4+ ions. The oxygen coordination of zirconium in monoclinic ZrO2 is indeed asymmetric and unusual. According to McCullough and Trueblood (3), the zir-