稀土掺杂硅酸盐的发光性能及长余辉调控
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摘要
长余辉发光材料是能吸收能量然后把能量以发光的形式缓慢释放出来的一种材料。作为一种特殊的储能材料,近几年来,长余辉材料备受关注,其应用已扩展到交通,建筑、钟表、服饰等日常生活方面。目前,铝酸盐体系长余辉材料具有优异的发光性能,得到了广泛应用。不过,其耐水性较差,易潮解,遇水分解,影响其发光效率。由此,本文制备了系列硅酸盐体系长余辉材料,研究稀土掺杂硅酸盐的发光性能及其蓝、绿长余辉的调控。该材料稳定性高,耐水性好,因而可极大拓展长余辉材料的应用范围。
考虑硅酸盐长余辉材料的实际应用,提高其余辉强度,我们首先用高温固相法制备了系列P~(5+)掺杂蓝色长余辉材料Sr_2MgSi_2O_7:Eu~(2+),Dy~(3+),aB~(3+),bP~(5+),探索P~(5+)对其余辉强度的调制规律。随着P~(5+)的引入,我们观察到样品的余辉强度增加,而余辉时间(衰减时间)变短。这表明P~(5+)的引入能有效调节陷阱能级的深度,改变陷阱释放电子的速率。结果表明,通过P~(5+)的掺杂控制,可实现对Sr_2MgSi_2O_7:Eu~(2+),Dy~(3+)的余辉特性的调节。余辉的可调性有助于长余辉材料在不同的照明和显示行业上的应用。特别在弱光照明方面,余辉时间超过12个小时的长余辉材料将有很大的可调性,有更大的应用前景。
其次,用高温固相法合成了稀土(Tb, Sm, Ce, Dy, Nd)掺杂CaAl2Si2O8:Eu和CaAl2Si2O8:Eu,Mn等硅铝酸盐样品。该样品具有硅酸盐材料的稳定性,其长余辉性能接近铝酸盐材料。结果表明,共激活剂Dy~(3+), Nd~(3+)都能延长蓝色长余辉材料CaAl2Si2O8:Eu的余辉时间,并且Nd~(3+)的效果比Dy~(3+)更好。这是因为Nd~(3+)产生的陷阱深度要比Dy~(3+)产生的陷阱深度要深。此外,Ce~(3+), Tb~(3+)和Sm~(3+)掺杂对提高荧光材料Ca_(0.74)Al_2Si_2O_8:0.01Eu~(2+),0.25Mn~(2+)的白光显色性有帮助,其中Sm~(3+)离子效果最为明显。
此外,通过增加CaO, SrO, BaO等反应物,替代有毒的Cd2+掺杂方法,用高温固相法制备了无毒、环保的新型绿色稀土掺杂长余辉材料M(Ca, Sr, Ba) O·2ZnO·2SiO_2:Mn,RE。M=Sr时,样品具有较好的余辉特性,并且,Mn~(2+)的浓度为1mol%,其余辉特性最好。实验发现,样品的余辉特性优于同种条件下制备的Zn_2SiO_4:Mn样品,其原因归结为,在烧结过程中Sr~(2+)替代Zn~(2+),增加了Zn_2SiO_4中陷阱的数量,或加深了陷阱深度,导致了余辉性能的改进。在此基础上,进一步比较Sm~(3+), La~(3+), Tb~(3+)掺杂对样品余辉特性的影响。实验发现,引入Tb~(3+)时能延长余辉衰减时间。结果为寻找合适的发光和余辉敏化剂提供了借鉴。
Long lasting phosphor (LLP) is a kind of energy-storing material, which can store the absorbed energy then slowly release the energy as visible light. In the recent years, long afterglow phosphors are drawing more and more attention because of a constantly growing market for their applications in traffic signs, emergency signage, watches and clocks display, textile printing and so on. For its excellent luminescence properties, aluminate LLP holds a leading post in actual applications. However, it has worse water resistance, easy deliquescence, of which the luminous efficiency can be weaken by hydration. Here a series of silicate long lasting phosphors of high stability and good water resistance are prepared, of which luminescence properties are studied. Blue, green afterglow properties can be adjusted by doping, which have wider application prospects.
For the practical applications, firstly, we prepare long-lasting phosphor Sr_2MgSi_2O_7:Eu~(2+),Dy~(3+),aB~(3+),bP~(5+) by solid state reaction. To enhance its afterglow intensity, we have researched the adjustment of afterglow property with P~(5+) doping in the samples. It is observed that with P~(5+) doping, the afterglow intensity of the samples increases while its persistent time decreases, indicating that the P~(5+) doping can adjust the depth of the trap level and thus change the releasing rate of the trapped electrons. The adjustability of the afterglow properties is very helpful for different practical applications of illumination and displays, especially for long-lasting phosphor of more than 12 hours but relatively weak luminance.
Secondly, the samples of both CaAl2Si2O8:Eu~(2+) and CaAl2Si2O8:Eu~(2+),Mn~(2+) doped with rare earths (Tb, Sm, Ce, Dy, Nd) are prepared by solid state reaction. It is found that the samples have a good stability just as silicate but high afterglow strength approaching that of the aluminate LLP’s. The results indicate that the afterglow time of CaAl2Si2O8:Eu~(2+) can be lasted by both Dy~(3+) and Nd~(3+) doping, and the effect of Nd~(3+) doping is better than the Dy~(3+) doping. The reason is that the trap level of Nd~(3+) doping is deeper than Dy~(3+) doping. In addition, the white color rendering for Ca_(0.74)Al_2Si_2O_8:0.01Eu~(2+),0.25Mn~(2+) have been optimized by adjusting the Ce~(3+), Tb~(3+) or Sm~(3+) co-doping, of which Sm~(3+) co-doping is best of all.
In order to avoid the toxicity of Cd2+, thirdly, we prepared nontoxic, environmental protection and new green-emitting LLP materials M(Ca2+, Sr~(2+), Ba2+)O?2ZnO?2SiO_2:Mn,RE (Sm~(3+), La~(3+), Tb~(3+)) by introducing of CaO, SrO, and BaO composition to replace the Cd2+ doping. In the case of M=Sr, the sample has a good afterglow property, and the best afterglow performance is obtained at 1mol% Mn~(2+) concentration. The results indicate that the afterglow property of sample is better than Zn_2SiO_4:Mn~(2+), obtained under the same prepare condition. This is because Sr~(2+) ions can partly replace Zn~(2+) site in Zn_2SiO_4, which deepen the trap energy level and prolong the afterglow decay time. Furthermore, the effects of co-doping ions (Sm~(3+), La~(3+), Tb~(3+)) on afterglow property of sample have also been investigated. It is found that the afterglow can be improved only by Tb~(3+) co-doping. The investigation is helpful for finding sensitizing agent for LLP.
考虑硅酸盐长余辉材料的实际应用,提高其余辉强度,我们首先用高温固相法制备了系列P~(5+)掺杂蓝色长余辉材料Sr_2MgSi_2O_7:Eu~(2+),Dy~(3+),aB~(3+),bP~(5+),探索P~(5+)对其余辉强度的调制规律。随着P~(5+)的引入,我们观察到样品的余辉强度增加,而余辉时间(衰减时间)变短。这表明P~(5+)的引入能有效调节陷阱能级的深度,改变陷阱释放电子的速率。结果表明,通过P~(5+)的掺杂控制,可实现对Sr_2MgSi_2O_7:Eu~(2+),Dy~(3+)的余辉特性的调节。余辉的可调性有助于长余辉材料在不同的照明和显示行业上的应用。特别在弱光照明方面,余辉时间超过12个小时的长余辉材料将有很大的可调性,有更大的应用前景。
其次,用高温固相法合成了稀土(Tb, Sm, Ce, Dy, Nd)掺杂CaAl2Si2O8:Eu和CaAl2Si2O8:Eu,Mn等硅铝酸盐样品。该样品具有硅酸盐材料的稳定性,其长余辉性能接近铝酸盐材料。结果表明,共激活剂Dy~(3+), Nd~(3+)都能延长蓝色长余辉材料CaAl2Si2O8:Eu的余辉时间,并且Nd~(3+)的效果比Dy~(3+)更好。这是因为Nd~(3+)产生的陷阱深度要比Dy~(3+)产生的陷阱深度要深。此外,Ce~(3+), Tb~(3+)和Sm~(3+)掺杂对提高荧光材料Ca_(0.74)Al_2Si_2O_8:0.01Eu~(2+),0.25Mn~(2+)的白光显色性有帮助,其中Sm~(3+)离子效果最为明显。
此外,通过增加CaO, SrO, BaO等反应物,替代有毒的Cd2+掺杂方法,用高温固相法制备了无毒、环保的新型绿色稀土掺杂长余辉材料M(Ca, Sr, Ba) O·2ZnO·2SiO_2:Mn,RE。M=Sr时,样品具有较好的余辉特性,并且,Mn~(2+)的浓度为1mol%,其余辉特性最好。实验发现,样品的余辉特性优于同种条件下制备的Zn_2SiO_4:Mn样品,其原因归结为,在烧结过程中Sr~(2+)替代Zn~(2+),增加了Zn_2SiO_4中陷阱的数量,或加深了陷阱深度,导致了余辉性能的改进。在此基础上,进一步比较Sm~(3+), La~(3+), Tb~(3+)掺杂对样品余辉特性的影响。实验发现,引入Tb~(3+)时能延长余辉衰减时间。结果为寻找合适的发光和余辉敏化剂提供了借鉴。
Long lasting phosphor (LLP) is a kind of energy-storing material, which can store the absorbed energy then slowly release the energy as visible light. In the recent years, long afterglow phosphors are drawing more and more attention because of a constantly growing market for their applications in traffic signs, emergency signage, watches and clocks display, textile printing and so on. For its excellent luminescence properties, aluminate LLP holds a leading post in actual applications. However, it has worse water resistance, easy deliquescence, of which the luminous efficiency can be weaken by hydration. Here a series of silicate long lasting phosphors of high stability and good water resistance are prepared, of which luminescence properties are studied. Blue, green afterglow properties can be adjusted by doping, which have wider application prospects.
For the practical applications, firstly, we prepare long-lasting phosphor Sr_2MgSi_2O_7:Eu~(2+),Dy~(3+),aB~(3+),bP~(5+) by solid state reaction. To enhance its afterglow intensity, we have researched the adjustment of afterglow property with P~(5+) doping in the samples. It is observed that with P~(5+) doping, the afterglow intensity of the samples increases while its persistent time decreases, indicating that the P~(5+) doping can adjust the depth of the trap level and thus change the releasing rate of the trapped electrons. The adjustability of the afterglow properties is very helpful for different practical applications of illumination and displays, especially for long-lasting phosphor of more than 12 hours but relatively weak luminance.
Secondly, the samples of both CaAl2Si2O8:Eu~(2+) and CaAl2Si2O8:Eu~(2+),Mn~(2+) doped with rare earths (Tb, Sm, Ce, Dy, Nd) are prepared by solid state reaction. It is found that the samples have a good stability just as silicate but high afterglow strength approaching that of the aluminate LLP’s. The results indicate that the afterglow time of CaAl2Si2O8:Eu~(2+) can be lasted by both Dy~(3+) and Nd~(3+) doping, and the effect of Nd~(3+) doping is better than the Dy~(3+) doping. The reason is that the trap level of Nd~(3+) doping is deeper than Dy~(3+) doping. In addition, the white color rendering for Ca_(0.74)Al_2Si_2O_8:0.01Eu~(2+),0.25Mn~(2+) have been optimized by adjusting the Ce~(3+), Tb~(3+) or Sm~(3+) co-doping, of which Sm~(3+) co-doping is best of all.
In order to avoid the toxicity of Cd2+, thirdly, we prepared nontoxic, environmental protection and new green-emitting LLP materials M(Ca2+, Sr~(2+), Ba2+)O?2ZnO?2SiO_2:Mn,RE (Sm~(3+), La~(3+), Tb~(3+)) by introducing of CaO, SrO, and BaO composition to replace the Cd2+ doping. In the case of M=Sr, the sample has a good afterglow property, and the best afterglow performance is obtained at 1mol% Mn~(2+) concentration. The results indicate that the afterglow property of sample is better than Zn_2SiO_4:Mn~(2+), obtained under the same prepare condition. This is because Sr~(2+) ions can partly replace Zn~(2+) site in Zn_2SiO_4, which deepen the trap energy level and prolong the afterglow decay time. Furthermore, the effects of co-doping ions (Sm~(3+), La~(3+), Tb~(3+)) on afterglow property of sample have also been investigated. It is found that the afterglow can be improved only by Tb~(3+) co-doping. The investigation is helpful for finding sensitizing agent for LLP.
引文
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