稀土离子掺杂的Gd_2O_2SO_4和Gd_2O_2S发光材料的合成、结构及性能
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摘要
稀土发光材料已成为信息显示、照明工程、X射线增感屏、X射线断层扫描、光电二极管、生物标记和诊断、上转换激光器等领域的支柱材料。近年来,稀土发光材料的研究热点主要有探索新型的发光基质和将传统的稀土发光材料超细化。本文开发了一种新型的Gd2O2SO4：Eu3+红色发光材料,研究了固-液法、均相沉淀法和共沉淀法来合成不同粒径的Gd2O2SO4：Eu3+发光粉的工艺,并对其晶体结构、电子结构和光学性能进行了研究。发现Gd2O2SO4：Eu3+发光粉不但具有良好的热稳定性,而且主发射峰波长为618nm,是最理想的红光,在高分辨的红色发光显示领域具有很好的应用前景。另外,研究了还原法、均相沉淀法和共沉淀法来合成不同粒径的Gd2O2S：Pr3+发光粉,并对其晶体结构、电子结构和光学性能进行了研究。该粉体有望在“水窗”软X射线探测、X射线显微镜等领域得到应用。最后通过无压反应烧结法制备了Gd2O2S：Pr3+闪烁陶瓷,并对其发光性能进行了研究。
采用Gd2O3、Eu2O3和H2SO4为实验原料,通过固-液法合成了微米Gd2O2SO4：Eu3+发光粉。针对目前Gd2O2SO4晶体结构数据不全和电子结构数据缺乏的问题,根据Gd2O2SO4的X射线粉末衍射数据计算了Gd2O2SO4的晶体结构,在此基础上计算了其电子结构。研究表明：Gd2O2SO4属于正交晶系结构,空间群为PMNB(No.62),晶胞参数为a=12.996A,b=8.117A,c=4.184A,并确定了晶胞中原子的位置和各原子间距离和角度。Gd202S04是具有间接带隙特征的绝缘体,计算的带隙值为4.9eV,比估算值8.4eV小。在270nm的紫外光激发下,(Gd0.95,Eu0.05)2O2SO4的主发射峰位于618nm,归属于Eu3+离子的5D0→7F2电偶极跃迁。
采用Gd2O3、Eu2O3、H2SO4、尿素为实验原料,通过均相沉淀法合成了亚微米Gd2O2SO4：Eu3+发光粉。研究表明：在900℃煅烧温度下,通过控制尿素与Gd2(SO4)3的摩尔比(M)可以合成单相Gd2O2SO4,最佳的尿素与Gd2(S04)3的摩尔比M为10,此时所合成的Gd2O2SO4粉体颗粒呈球形,大小为300-500nm。在270nm的紫外光激发下,(Gd1_x,Eux)2O2SO4亚微米发光粉的主发射峰位于618nm,归属于Eu3+离子的5D0→7F2电偶极跃迁,其猝灭浓度为5mol%,猝灭机理是电偶极与电偶极之间的相互作用,Eu3+离子5D0→7F2跃迁呈现e的单指数衰减行为。
采用Gd2O3、Eu2O3、H2SO4和NaOH为实验原料,通过共沉淀法合成了纳米Gd2O2SO4：Eu3+发光粉。研究表明:NaOH和Gd2(SO4)3的摩尔比m对前驱体的成分影响很大。当m<4时,所合成的前驱体成分为非晶的Gd2(OH)4SO4·nH2O,但产率较低；当m>4时,所合成的前驱体成分偏离Gd2(OH)4SO4·nH2O,其高温煅烧产物中含有Gd2O3相；最佳的m值为4。此时合成的前驱体在空气气氛下900℃煅烧2小时后可转化为高产率的单相Gd2O2SO4,所合成粉体颗粒呈准球形,大小为30-50nm,分散性良好。在270nm紫外光激发下,(Gd1-x,EUx)2O2SO4纳米发光粉的主发射峰位于618nm,归属于Eu3+离子的5Do→7F2电偶极跃迁,其猝灭浓度为10mol%,猝灭机理是Eu3+-Eu3+之间的交换相互作用,Eu3+离子5Do→7F2跃迁也呈现e的单指数衰减行为。但其发光强度和发光寿命均小于(Gd1-x,Eux)2O2SO4亚微米发光粉的发光强度和发光寿命。
采用固-液法合成的Gd2O2SO4：Pr微粉为实验原料,通过还原法合成了微米(Gd1-x,Prx)2O2S发光粉。研究了Gd2O2S的电子结构和光学性能。研究表明Gd2O2S是具有间接带隙特征的半导体,计算带隙值为2.57eV,比实测光学带隙值4.37eV小。在303nm的紫外光激发下,(Gd1-x,Prx)2O2S的主发射峰位于515nm,归属于Pr3+离子的3p0→3H4跃迁,其猝灭浓度为1mol%。
采用上述均相沉淀法和共沉淀法合成的Pr3+离子掺杂的前驱体为实验原料,分别合成亚微米和纳米Gd2O2S：Pr3+发光粉。研究表明：在流动氢气气氛下,两种方法合成的前驱体在700℃以上均能被还原成单相的Gd2O2S。前者合成的粉体颗粒呈球形,大小为300-500nm,后者合成的粉体颗粒呈准球形,大小为20-40nm。在303nm和300nm的紫外光激发下,(Gd0.99,Pr0.01)2O2S亚微米和纳米发光粉的主发射峰分别位于515nm和512nm,两者均归属于Pr3+离子的3P0→3H4跃迁,且该跃迁呈现e单指数衰减行为。随着煅烧温度的升高,两者的发光强度和发光寿命均增加,但前者的发光强度和发光寿命均大于后者。
采用固-液法合成的Gd2O2SO4：Pr微粉为实验原料,通过在氢气气氛下1750℃无压反应烧结法制备出相对密度大于99%的Gd2O2S：Pr3+闪烁陶瓷,并具有一定的发光性能。
综上,本工作所合成的Gd2O2SO4：Eu3+和Gd2O2S：Pr3+发光材料具有良好的发光性能,并且合成工艺简单,易于控制,成本低廉,具有很好的实际应用前景。
Rare earth luminescent materials have become the main materials in many different technological areas, including information display, illumination engineering, X-ray intensifying screen, X-ray computed tomography(X-CT), light emitting diodes, biological labeling and diagnostics, and upconversion lasers. Nearly, the hotspots in the research fields of rare earth luminescent materials mainly include exploration of new luminescent material systems and synthesis of highly dispersed ultrafine phosphors. In the present work, a new Gd2O2SO4:Eu3+ red luminescent material was developed. Gd2O2SO4:Eu3+ phosphors with various sizes were synthesized using a solid-liquid method, a homogenous precipitation method, and a co-precipitation method, and their crystal structure, electronic structure and optical properties were studied. It was found that the Gd2O2SO4:Eu3+ phosphors not only have good thermal stability, but also ideal red light emission performance with peak emission at 618nm, making them suitable candidates in the field of high resolution red light emission. Moreover, Gd2O2S:Pr3+ phosphors with various sizes were synthesized using a reduction method, a homogenous precipitation method, and a co-precipitation method, and their crystal structure, electronic structure and optical properties were studied. The Gd2O2S:Pr3+ phosphors are prospective in the fields of soft X-ray detection for "water window", X-ray microscopy and upconversion luminescence. Finally, Gd2O2S:Pr3+ scintillation ceramic was fabricated by pressureless reaction sintering method, and their luminescent properties were studied.
Gd2O2SO4 phosphors in micrometer scale were synthesized by a solid-liquid method from the commercially available Gd2O3, Eu2O3,and H2SO4 starting materials. Since there are no complete data on crystal structure and electronic structure of the Gd2O2SO4 system, crystal structure of Gd2O2SO4 was calculated from the X-ray diffraction data, and electronic structure was calculated on this basis. The results show that the crystal structure of Gd2O2SO4 belongs to orthorhombic system with a space group PMNB (No.62):a=12.996A, b=8.117A, c=4.184A. The atom positions, distances and angles between different atoms of Gd2O2SO4 crystal cell were also determined. The Gd2O2SO4 is an indirect-gap insulator with the indirect band gap energy of 4.9eV, which is lower than estimated value 8.4eV. The emission spectrum of (Gd0.95,Eu0.0)2O2SO4 under 270nm UV light excitation demonstrates the strongest emission peak located at 618nm, attributing to the electric dipole 5D0→7F2 transition of Eu3+ions.
Gd2O2SO4:Eu3+submircrometer phosphors were synthesized by a homogeneous method from the commercially available Gd2O3, Eu2O3, H2SO4 and urea starting materials. The results reveal that single phase Gd2O2SO4 phosphors can be synthesized at 900℃by controlling the molar ratio (M) of precipitant to Gd2(SO4)3. The optimal M value is found to be 10, and the produced particles are spherical in shape with a particle size of 300-500nm. Under 270nm UV light excitation, the strongest emission peak of the (Gd1-x,Eux)2O2SO4 submircrometer phosphor is located at 618nm, attributing to the electric dipole 5D0→7F2 transition of Eu3+ions. The quenching concentration of Eu3+ ions for the phosphor is 5mol%, and the concentration quenching mechanism is the electric dipole-dipole interactions. The decay study reveals that the 5D0→7F2 transition of Eu3+ ions has a single exponential decay behavior.
Gd2O2SO4:Eu3+ nano-sized phosphors were synthesized by a co-precipitation method from the commercially available Gd2O3, Eu2O3; H2SO4, and NaOH starting materials. The results reveal that molar ratio (m) of NaOH to Gd2(SO4)3 has great effect on the composition of precursor. If m<4, the precursor is amorphous Gd2(OH)4SO4·nH2O, but the productivity is low. If m>4, the composition of precursor is away from Gd2(OH)4SO4·nH2O, with the existence of Gd2O3 after the later calcination. The optimum m is found to be 4, and pure phase can be obtained by calcining the precursor in air at 900℃for 2 hours. The particles are nearly spherical and well dispersed, with a particle size of 30-50nm. Under 270nm UV light excitation, the strongest emission peak of the (Gd1-x,Eux)2O2SO4 nano-sized phosphor is located at 618nm, attributing to the electric dipole 5D0→7F2 transition of Eu3+ ions. The quenching concentration of Eu3+ ions is 10mol%, the concentration quenching mechanism is the exchange interaction among the Eu3+ions. The decay study reveals that the 5D0→7F2 transition of Eu3+ ions has also a single exponential decay behavior. However, its luminescent intensity and lifetime of the 5D0→7F2 transition is smaller than those of the submicrometer phosphors.
(Gd1-x,Prx)2O2S micrometer phosphors were synthesized by reduction method from the Gd2O2SO4:Pr micrometer phosphors synthesized by solid-liquid method. Its crystal structure, electronic structure and optical properties were studied. The results show that Gd2O2S is an indirect-gap semiconductor with the indirect band gap energy of 2.57eV, which is lower than the experimental value 4.37eV. The emission spectrum of (Gd1-x,Prx)2O2S under 303nm UV light excitation demonstrates the strongest emission peak located at 515nm, attributing to the 3P0→3H4 transition of Pr3+ions. The quenching concentration of Pr3+ ions for (Gd1-x,Prx)2O2S micrometer phosphors is 1mol%.
The Gd2O2S:Pr3+ submircrometer phosphors and the Gd2O2S:Pr3+ nano-sized phosphors were produced from the precursors synthesized by a homogeneous and a co-precipitation method, respectively. The results show single phase Gd2O2S can be synthesized by calcining the precursors at temperature higher than 700℃for 1 hour in flowing hydrogen. The former particles are spherical and 300-500nm in size, and the latter particles are 20-40nm in size, with a near spherical shape. Under 303nm and 300nm UV light excitation, the strongest emission peaks of the (Gd1-x,Prx)2O2S submircrometer and nanometer phosphors are located at 515nm and 512nm, respectively, attributing to the 3P0→3H4 transition of Pr3+ ions. The 3P0→3H4 transition of Pr3+ ions has a single exponential decay behavior. The luminescent intensity and lifetime of 3P0→3H4 transition increase with increasing calcination temperature for Gd2O2S:Pr3+ submircrometer and nano-sized phosphors and the former has higher luminescent intensity and longer lifetime compared with the latter.
Gd2O2S:Pr3+ scintillation ceramic was fabricated by sintering at 1750℃in a hydrogen atmosphere from the Gd2O2SO4:Pr powder synthesized by solid-liquid method. The fabricated scintillation ceramic has a relative density higher than 99%, with certain luminescent properties.
In summary, the synthesized Gd2O2SO4:Eu3+ and Gd2O2S:Pr3+ luminescent materials have high luminescent performance and the preparation conditions are simple, easy to control and low cost, with good potential of practical applications.
采用Gd2O3、Eu2O3和H2SO4为实验原料,通过固-液法合成了微米Gd2O2SO4：Eu3+发光粉。针对目前Gd2O2SO4晶体结构数据不全和电子结构数据缺乏的问题,根据Gd2O2SO4的X射线粉末衍射数据计算了Gd2O2SO4的晶体结构,在此基础上计算了其电子结构。研究表明：Gd2O2SO4属于正交晶系结构,空间群为PMNB(No.62),晶胞参数为a=12.996A,b=8.117A,c=4.184A,并确定了晶胞中原子的位置和各原子间距离和角度。Gd202S04是具有间接带隙特征的绝缘体,计算的带隙值为4.9eV,比估算值8.4eV小。在270nm的紫外光激发下,(Gd0.95,Eu0.05)2O2SO4的主发射峰位于618nm,归属于Eu3+离子的5D0→7F2电偶极跃迁。
采用Gd2O3、Eu2O3、H2SO4、尿素为实验原料,通过均相沉淀法合成了亚微米Gd2O2SO4：Eu3+发光粉。研究表明：在900℃煅烧温度下,通过控制尿素与Gd2(SO4)3的摩尔比(M)可以合成单相Gd2O2SO4,最佳的尿素与Gd2(S04)3的摩尔比M为10,此时所合成的Gd2O2SO4粉体颗粒呈球形,大小为300-500nm。在270nm的紫外光激发下,(Gd1_x,Eux)2O2SO4亚微米发光粉的主发射峰位于618nm,归属于Eu3+离子的5D0→7F2电偶极跃迁,其猝灭浓度为5mol%,猝灭机理是电偶极与电偶极之间的相互作用,Eu3+离子5D0→7F2跃迁呈现e的单指数衰减行为。
采用Gd2O3、Eu2O3、H2SO4和NaOH为实验原料,通过共沉淀法合成了纳米Gd2O2SO4：Eu3+发光粉。研究表明:NaOH和Gd2(SO4)3的摩尔比m对前驱体的成分影响很大。当m<4时,所合成的前驱体成分为非晶的Gd2(OH)4SO4·nH2O,但产率较低；当m>4时,所合成的前驱体成分偏离Gd2(OH)4SO4·nH2O,其高温煅烧产物中含有Gd2O3相；最佳的m值为4。此时合成的前驱体在空气气氛下900℃煅烧2小时后可转化为高产率的单相Gd2O2SO4,所合成粉体颗粒呈准球形,大小为30-50nm,分散性良好。在270nm紫外光激发下,(Gd1-x,EUx)2O2SO4纳米发光粉的主发射峰位于618nm,归属于Eu3+离子的5Do→7F2电偶极跃迁,其猝灭浓度为10mol%,猝灭机理是Eu3+-Eu3+之间的交换相互作用,Eu3+离子5Do→7F2跃迁也呈现e的单指数衰减行为。但其发光强度和发光寿命均小于(Gd1-x,Eux)2O2SO4亚微米发光粉的发光强度和发光寿命。
采用固-液法合成的Gd2O2SO4：Pr微粉为实验原料,通过还原法合成了微米(Gd1-x,Prx)2O2S发光粉。研究了Gd2O2S的电子结构和光学性能。研究表明Gd2O2S是具有间接带隙特征的半导体,计算带隙值为2.57eV,比实测光学带隙值4.37eV小。在303nm的紫外光激发下,(Gd1-x,Prx)2O2S的主发射峰位于515nm,归属于Pr3+离子的3p0→3H4跃迁,其猝灭浓度为1mol%。
采用上述均相沉淀法和共沉淀法合成的Pr3+离子掺杂的前驱体为实验原料,分别合成亚微米和纳米Gd2O2S：Pr3+发光粉。研究表明：在流动氢气气氛下,两种方法合成的前驱体在700℃以上均能被还原成单相的Gd2O2S。前者合成的粉体颗粒呈球形,大小为300-500nm,后者合成的粉体颗粒呈准球形,大小为20-40nm。在303nm和300nm的紫外光激发下,(Gd0.99,Pr0.01)2O2S亚微米和纳米发光粉的主发射峰分别位于515nm和512nm,两者均归属于Pr3+离子的3P0→3H4跃迁,且该跃迁呈现e单指数衰减行为。随着煅烧温度的升高,两者的发光强度和发光寿命均增加,但前者的发光强度和发光寿命均大于后者。
采用固-液法合成的Gd2O2SO4：Pr微粉为实验原料,通过在氢气气氛下1750℃无压反应烧结法制备出相对密度大于99%的Gd2O2S：Pr3+闪烁陶瓷,并具有一定的发光性能。
综上,本工作所合成的Gd2O2SO4：Eu3+和Gd2O2S：Pr3+发光材料具有良好的发光性能,并且合成工艺简单,易于控制,成本低廉,具有很好的实际应用前景。
Rare earth luminescent materials have become the main materials in many different technological areas, including information display, illumination engineering, X-ray intensifying screen, X-ray computed tomography(X-CT), light emitting diodes, biological labeling and diagnostics, and upconversion lasers. Nearly, the hotspots in the research fields of rare earth luminescent materials mainly include exploration of new luminescent material systems and synthesis of highly dispersed ultrafine phosphors. In the present work, a new Gd2O2SO4:Eu3+ red luminescent material was developed. Gd2O2SO4:Eu3+ phosphors with various sizes were synthesized using a solid-liquid method, a homogenous precipitation method, and a co-precipitation method, and their crystal structure, electronic structure and optical properties were studied. It was found that the Gd2O2SO4:Eu3+ phosphors not only have good thermal stability, but also ideal red light emission performance with peak emission at 618nm, making them suitable candidates in the field of high resolution red light emission. Moreover, Gd2O2S:Pr3+ phosphors with various sizes were synthesized using a reduction method, a homogenous precipitation method, and a co-precipitation method, and their crystal structure, electronic structure and optical properties were studied. The Gd2O2S:Pr3+ phosphors are prospective in the fields of soft X-ray detection for "water window", X-ray microscopy and upconversion luminescence. Finally, Gd2O2S:Pr3+ scintillation ceramic was fabricated by pressureless reaction sintering method, and their luminescent properties were studied.
Gd2O2SO4 phosphors in micrometer scale were synthesized by a solid-liquid method from the commercially available Gd2O3, Eu2O3,and H2SO4 starting materials. Since there are no complete data on crystal structure and electronic structure of the Gd2O2SO4 system, crystal structure of Gd2O2SO4 was calculated from the X-ray diffraction data, and electronic structure was calculated on this basis. The results show that the crystal structure of Gd2O2SO4 belongs to orthorhombic system with a space group PMNB (No.62):a=12.996A, b=8.117A, c=4.184A. The atom positions, distances and angles between different atoms of Gd2O2SO4 crystal cell were also determined. The Gd2O2SO4 is an indirect-gap insulator with the indirect band gap energy of 4.9eV, which is lower than estimated value 8.4eV. The emission spectrum of (Gd0.95,Eu0.0)2O2SO4 under 270nm UV light excitation demonstrates the strongest emission peak located at 618nm, attributing to the electric dipole 5D0→7F2 transition of Eu3+ions.
Gd2O2SO4:Eu3+submircrometer phosphors were synthesized by a homogeneous method from the commercially available Gd2O3, Eu2O3, H2SO4 and urea starting materials. The results reveal that single phase Gd2O2SO4 phosphors can be synthesized at 900℃by controlling the molar ratio (M) of precipitant to Gd2(SO4)3. The optimal M value is found to be 10, and the produced particles are spherical in shape with a particle size of 300-500nm. Under 270nm UV light excitation, the strongest emission peak of the (Gd1-x,Eux)2O2SO4 submircrometer phosphor is located at 618nm, attributing to the electric dipole 5D0→7F2 transition of Eu3+ions. The quenching concentration of Eu3+ ions for the phosphor is 5mol%, and the concentration quenching mechanism is the electric dipole-dipole interactions. The decay study reveals that the 5D0→7F2 transition of Eu3+ ions has a single exponential decay behavior.
Gd2O2SO4:Eu3+ nano-sized phosphors were synthesized by a co-precipitation method from the commercially available Gd2O3, Eu2O3; H2SO4, and NaOH starting materials. The results reveal that molar ratio (m) of NaOH to Gd2(SO4)3 has great effect on the composition of precursor. If m<4, the precursor is amorphous Gd2(OH)4SO4·nH2O, but the productivity is low. If m>4, the composition of precursor is away from Gd2(OH)4SO4·nH2O, with the existence of Gd2O3 after the later calcination. The optimum m is found to be 4, and pure phase can be obtained by calcining the precursor in air at 900℃for 2 hours. The particles are nearly spherical and well dispersed, with a particle size of 30-50nm. Under 270nm UV light excitation, the strongest emission peak of the (Gd1-x,Eux)2O2SO4 nano-sized phosphor is located at 618nm, attributing to the electric dipole 5D0→7F2 transition of Eu3+ ions. The quenching concentration of Eu3+ ions is 10mol%, the concentration quenching mechanism is the exchange interaction among the Eu3+ions. The decay study reveals that the 5D0→7F2 transition of Eu3+ ions has also a single exponential decay behavior. However, its luminescent intensity and lifetime of the 5D0→7F2 transition is smaller than those of the submicrometer phosphors.
(Gd1-x,Prx)2O2S micrometer phosphors were synthesized by reduction method from the Gd2O2SO4:Pr micrometer phosphors synthesized by solid-liquid method. Its crystal structure, electronic structure and optical properties were studied. The results show that Gd2O2S is an indirect-gap semiconductor with the indirect band gap energy of 2.57eV, which is lower than the experimental value 4.37eV. The emission spectrum of (Gd1-x,Prx)2O2S under 303nm UV light excitation demonstrates the strongest emission peak located at 515nm, attributing to the 3P0→3H4 transition of Pr3+ions. The quenching concentration of Pr3+ ions for (Gd1-x,Prx)2O2S micrometer phosphors is 1mol%.
The Gd2O2S:Pr3+ submircrometer phosphors and the Gd2O2S:Pr3+ nano-sized phosphors were produced from the precursors synthesized by a homogeneous and a co-precipitation method, respectively. The results show single phase Gd2O2S can be synthesized by calcining the precursors at temperature higher than 700℃for 1 hour in flowing hydrogen. The former particles are spherical and 300-500nm in size, and the latter particles are 20-40nm in size, with a near spherical shape. Under 303nm and 300nm UV light excitation, the strongest emission peaks of the (Gd1-x,Prx)2O2S submircrometer and nanometer phosphors are located at 515nm and 512nm, respectively, attributing to the 3P0→3H4 transition of Pr3+ ions. The 3P0→3H4 transition of Pr3+ ions has a single exponential decay behavior. The luminescent intensity and lifetime of 3P0→3H4 transition increase with increasing calcination temperature for Gd2O2S:Pr3+ submircrometer and nano-sized phosphors and the former has higher luminescent intensity and longer lifetime compared with the latter.
Gd2O2S:Pr3+ scintillation ceramic was fabricated by sintering at 1750℃in a hydrogen atmosphere from the Gd2O2SO4:Pr powder synthesized by solid-liquid method. The fabricated scintillation ceramic has a relative density higher than 99%, with certain luminescent properties.
In summary, the synthesized Gd2O2SO4:Eu3+ and Gd2O2S:Pr3+ luminescent materials have high luminescent performance and the preparation conditions are simple, easy to control and low cost, with good potential of practical applications.
引文
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