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1. 中国科学技术大学物理系
2. 中国科学院激发态物理开放实验室 长春,130021
3. 中国科学技术大学结构分析开放实验室,安徽 合肥,230026
收稿日期:2000-11-20,
修回日期:2001-03-16,
纸质出版日期:2001-08-30
移动端阅览
郭常新, 李碧琳. 纳米荧光粉的余辉研究[J]. 发光学报, 2001,22(3): 223-226
GUO Chang-xin, LI Bi-lin. Luminescent Decay of Nanocrystal ZnS:Mn Phosphor[J]. Chinese Journal of Luminescence, 2001,22(3): 223-226
用无机材料在室温下通过溶胶法制成了纳米ZnS:Mn荧光粉
立方晶形
平均粒径为3nm
它的橙色发光(峰值608nm
半宽75nm)亮度与同晶型(立方)的体ZnS:Mn荧光粉的亮度相同
而余辉缩短。在Nd:YAG四倍频266nm脉冲激光激发下
仔细对立方纳米、纯立方微米、纯六角微米ZnS:Mn荧光粉进行了余辉的对比测量。它们的余辉主要遵循指数衰减规律
其1/e余辉时间的结果如下:(1)纯立方纳米ZnS:Mn:两个指数衰减
余辉时间分别为186μs和1078μs
其幅度比为4:1
前者是主要的
决定了1/e余辉时间
(2)纯立方微米体ZnS:Mn:944μs
(3)纯六角微米体ZnS:Mn:1.2ms(还有幅度很小的极长余辉成分)。结果表明纳米ZnS:Mn荧光粉的光致发光余辉的确比对应的体材料(不管是六角还是立方)都短
但余辉仅缩短了几倍
而不是五个数量级。
Nanocrystal ZnS:Mn phosphor has been prepared by sol method using inorganic materials at room temperature. The nanocrystal phosphor of ZnS:Mn has cubic crystal structure with average 3nm of particle size
emitting bright orange light at peak wavelength 608nm with the full width of half maximum 75nm under UV 365nm excitation
and the brightness as high as the corresponding bulk pure cubic ZnS:Mn phosphor. According to the results reported by R.N.Bhargava
in comparison with the bulk ZnS:Mn phosphor the nanocrystal ZnS:Mn has nearly high luminescent efficiency with its luminescent decay time at least 5 orders of magnitude faster. It means that the oscillator intensity of luminescent centers in nanocrystal ZnS:Mn enhances at least 5 orders of magnitude than that in corresponding bulk ZnS:Mn. The discovery of high luminescent efficiency nanocrystal phosphor ZnS:Mn aroused the great interest to lots of researchers in the world. But these results are difficult to explain according to the normal concept. So checking these results by experiment has very important meaning in theory and experiment. In this paper the main purpose is to make a luminescent decay comparison between the nanocrystal and normal bulk crystal (particle size in micrometer) ZnS:Mn phosphors. In this comparison we controlled two factors:(1) The nanometer and bulk ones need have same crystal structure. A commercial bulk ZnS:Mn phosphor usually has mixed structure of cubic and hexagonal crystal which mainly depends on the sintering temperature and the doping concentration of luminescent activator Mn
2+
. In our experiments
under two different sintering conditions we prepared the bulk phosphors in two pure structures
cubic and hexagonal
respectively. These bulk crystal ZnS:Mn phosphors have the average particle size in micrometer order of magnitude. (2) Luminescent decay will sensitively depend upon the excitation condition
such as excitation intensity and mode like photoluminescence (PL) and cathodeluminescence (CL). In general
high intensity excitation will cause faster decay and CL will also cause faster decay than PL for the same phosphors. So in our experiments
the photoluminescent decay comparison between nanocrystal and bulk crystal ZnS:Mn was made in the same excitation condition. Under the excitation of the fourfold frequency pulse laser of Nd:YAG at 266nm (pulse width:9ns
pulse repeat frequency:3~30Hz
single pulse energy in 1.064μm:750 mJ)
we have carefully investigated the decay time of nanocrystal cubic ZnS:Mn phosphor in comparison with that of pure cubic and pure hexagonal microcrystal bulk ZnS:Mn phosphors. The 1/e luminescent decay times of these phosphors are as follows:(1) Pure cubic nanocrystal ZnS:Mn has two distinct exponential decays. The two decay time constants are 186 and 1 078μs and its amplitude ratio is 4:1; so the former is major one
which determines the 1/e decay time. (2) For pure cubic bulk crystal ZnS:Mn
there is only one exponential decay
the decay time constant is 944μs. (3) For pure hexagonal bulk ZnS:Mn
one exponential decay time constant is 1.2ms and a small amplitude hyperbolic component having extremely long decay time. These results show that the nanocrystal ZnS:Mn phosphor do have shorter photoluminescent decay time than the corresponding bulk crystal ZnS:Mn phosphors (no matter hexagonal or cubic one)
but the shortened rate is only several times
not 5 orders of magnitude.
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