Yb~(3+),Er~(3+)掺杂Y_2Ti_2O_7荧光粉的制备与上转换发光机理

采用溶胶-凝胶法制备合成了(Y_(0.98-x)Yb_xEr_(0.02))_2Ti_2O_7(x=0, 0.02, 0.04,…,0.10)荧光粉,分别采用XRD和荧光光谱仪对样品的结构和上转换发光性能进行了表征.研究了Yb~(3+)掺杂浓度对样品上转换发光性能的影响,并对样品的发光机理进行了研究.结果表明,所得样品为面心立方结构的烧绿石相.在980 nm激发下,样品展现出很强的上转换荧光发射并且发光颜色可以通过Yb~(3+)掺杂浓度来调节.样品上转换绿光和红光发射均为双光子过程并且交叉弛豫过程在上转换红光发射过程中占据主导作用.     

纳米Gd_2O_3:Tb~(3+)的多元醇法制备及发光特性

以DEG为溶剂,分别配置一定比例的GdCl_3, TbCl_3作为前驱液,利用多元醇法合成可用于生物探针的Gd_2O_3:Tb~(3+)纳米晶;将一定量的APTES和TEOS加入制备好的溶液中,使得纳米晶Gd_2O_3:Tb~(3+)的表面包裹聚硅氧烷层。本实验通过马尔文粒度仪、 X射线衍射仪(XRD)、场发射扫描电镜(SEM)、透射电镜(TEM)、荧光分光光度计等检测方法研究不同煅烧温度和不同Tb~(3+)掺杂浓度对纳米晶Gd_2O_3的粒径、物相结构、和发光性能的影响。将真空干燥过的纳米晶Gd_2O_3:Tb~(3+)置于马弗炉中分别以600, 800, 1000℃进行煅烧,得到的样品经XRD表征后发现:当煅烧温度为800℃时,得到立方相结构的纳米Gd_2O_3:Tb~(3+)。通过研究不同Tb~(3+)离子掺杂浓度下纳米晶Gd_2O_3:Tb~(3+)的荧光强度表明:当Tb~(3+)离子浓度为5.0%时,纳米晶Gd_2O_3:Tb~(3+)的发射强度最强,尤其是在主发射峰545 nm附近Tb~(3+)的~5D_4→~7F_5能级跃迁峰,其峰值强度比掺杂浓度为2.5%时提高了39%; Tb~(3+)掺杂浓度升高至7.5%时,样品发生了浓度猝灭导致光谱强度下降。     

Er~(3+)/Yb~(3+)掺杂NaY(MoO_4)_2荧光粉的制备及其上转换发光性能研究

采用高温固相法合成了一系列Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺NaY(MoO_4)_2荧光粉样品。通过X射线衍射仪、扫描电子显微镜、激光粒度仪和荧光光谱仪分别对样品的相纯度、微观形貌、粒径分布和上转换发光性能进行了表征。在980 nm激光激发下,Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺样品的发射光谱中均能观测到中心波长位于536 nm、560 nm的上转换绿光发射和位于660 nm的红光发射,分别归因于Er~(3+)的~2H~(11/2)→~4I_(15/2)、~4S_(3/2)→~4I_(15/2)和~4F_(9/2)→4I_(15/2)能级跃迁。在Er~(3+)单掺体系中共掺Yb~(3+),可以轻松实现由上转换绿光到红光的转变。NaY_(1-x-y)(MoO_4)_2∶x Er~(3+),y Yb~(3+)样品中最优的Er~(3+)/Yb~(3+)掺杂浓度和最佳的烧结温度为x=0.04、y=0.5、T=850℃。基于泵浦依赖和能级图,在Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺体系上转换发光过程中所涉及的能量转移机制被详细讨论。     

镧系离子掺杂NaLuF_4纳米晶的可控合成及上转换发光性质研究

采用水热法制备了镧系离子Gd~(3+)/Yb~(3+)/Tm~(3+)和Dy~(3+)/Yb~(3+)/Tm~(3+)掺杂的NaLuF_4纳米晶。对样品进行了X-射线衍射分析(XRD)和上转换光谱分析。XRD结果显示所制备的NaLuF_4纳米晶的晶相结构、尺寸可通过简单的Gd~(3+)、Dy~(3+)掺杂方法来调控,随着Gd~(3+)、Dy~(3+)掺杂浓度的增加NaLuF_4纳米晶倾向于形成六角相结构,说明高的Gd~(3+)、Dy~(3+)浓度能够促进立方相向六角相的转变,有利于六角相结构的形成,为制备结构精确可控的纳米晶提供了一种简单的方法。在980 nm激光激发下,所制备的Gd~(3+)/Yb~(3+)/Tm~(3+)共掺的NaLuF_4纳米晶具有强的476 nm的蓝光发射,并且随着Gd~(3+)浓度的增加上转换发光强度逐渐减弱。     

Eu~(3+)掺杂ZnS纳米晶的制备及其表面修饰

通过水相法合成Eu~(3+)掺杂ZnS纳米晶(ZnS:Eu),合成的ZnS:Eu纳米晶具有立方晶形结构,粒径约为2 nm~4 nm,荧光谱图中可以检测到Eu~(3+)的5D0-7FJ(J=0,1,2)的特征吸收峰,这是由于在ZnS:Eu纳米晶内Eu~(3+)周围存在电荷缺陷和晶格缺陷导致的。为了实现ZnS:Eu纳米晶的功能性和可加工性,通过新颖的方法配体交换法合成了5-(2-甲基丙烯酰乙氧基甲基)-8-羟基喹啉(MQ)表面修饰的ZnS:Eu纳米晶(MQ-ZnS:Eu),表面修饰后的MQ-ZnS:Eu纳米晶与ZnS:Eu纳米晶相比较发光效率显著提高,且发射峰发生蓝移,蓝移约80 nm~90 nm,这可能是MQ与ZnS:Eu纳米晶之间协同作用导致的。     

用于物品安全的Yb~(3+)单掺纳米颗粒的制备与表征

为了提高稀土荧光防伪系统的防伪力度,采用沉淀法制备了用于物品安全的Yb~(3+)单掺杂NaYF_4纳米颗粒。利用FT-IR分析了制备过程中间产物的化学组成。利用XRD和TEM对产物的形貌结构进行表征,并结合吸收光谱和发射光谱图,分析了不同掺杂浓度NaYF_4∶Yb~(3+)纳米颗粒发光特性。实验结果表明,Yb~(3+)与苯甲酸钠反应生成了多齿配合物,验证了苯甲酸钠在制备过程中起络合作用。在N_2氛围中经400℃煅烧4 h得到β-NaYF_4∶Yb~(3+)纳米颗粒,平均粒径为86 nm。该纳米颗粒在900 nm光的激发下具有930 nm～1080 nm的不可见红外发射(归属于Yb~(3+)的~2F_(7/2)→~2F_(5/2)),980 nm激发下具有475 nm的蓝色可见发射(归属于Yb~(3+)对的合作上转换发光),最大红外发射和蓝色上转换发射的样品掺杂浓度分别为5%和20%。研究结果表明NaYF_4∶Yb~(3+)纳米颗粒在物品追踪领域具有良好的应用前景。     

白光LED用LaF_3:Eu~(3+)红色荧光粉的制备与表征

采用水热法制备具有单一相六方晶系的LaF_3:Eu~(3+)纳米荧光粉.通过X射线粉末衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、光致发光光谱(PL)和荧光衰减曲线对LaF_3:Eu~(3+)纳米荧光粉进行表征. LaF_3:Eu~(3+)荧光粉的激发光谱主要由250 nm处的宽带(O2-→Eu3+的电荷转移跃迁)和一些尖峰(Eu3+f-f跃迁)构成,其中位于近紫外区396 nm处有一较强的激发峰.通过发射光谱探测Eu3+在LaF3晶体中的局部晶场环境.在298 K下激发光谱和发射光谱可知,在六方晶系的LaF3纳米晶体中的Eu3+晶格位置从D4h降至到C2v,这是由于晶格变化所造成的.在396 nm激发下,观测到较优掺杂浓度为10%的LaF_3:Eu~(3+)荧光粉在591 nm(5D0→7F1跃迁)处有强烈的红色发射峰.其发光性能表明,LaF_3:Eu~(3+)红色荧光粉在近紫外发光二极管领域具有潜在的应用价值.     

Ho~(3+)-Yb~(3+)掺杂β-NaYF_4纳米晶的近红外荧光与能量传递

用共沉淀法制备了Ho~(3+),Yb~(3+)掺杂的β-NaYF_4纳米晶,测量并分析了不同Yb~(3+)掺杂浓度下NaYF_4∶Ho~(3+),Yb~(3+)的荧光光谱与荧光衰减曲线。结果表明,在447 nm泵浦光激发下,较强的近红外光发射主要来源于Ho~(3+)-Yb~(3+)之间高效的能量传递过程。被泵浦光激发的Ho~(3+)通过~5F_4,~5S_2能级与~5F_5能级将能量传递给Yb~(3+),使Yb~(3+)从基态~2F_(7/2)能级跃迁到~2F_(5/2)能级。同时,处于~2F_(5/2)能级的Yb~(3+)可以将能量再传递给Ho~(3+)的~5I_6能级从而增强Ho~(3+)离子~5I_6→~5I_8的跃迁发光。在所研究的样品中,NaYF_4∶3%Ho~(3+),3%Yb~(3+)表现出最强的近红外荧光发射,其980 nm附近的荧光强度是NaYF_4∶3%Ho~(3+)样品的18倍。较强的近红外光发射使得NaYF_4∶Ho~(3+),Yb~(3+)材料在提高太阳能电池的光电转换效率以及进行荧光标记等方面有潜在的应用价值。     

Eu~(3+)/Sm~(3+)共掺K_2Gd(WO_4)(PO_4)荧光粉的发光性能及热稳定性研究

采用高温固相法制备了K_2Gd_(1-x-y)(PO_4)(WO_4):x Sm~(3+),y Eu~(3+)新型红色荧光材料,通过利用X射线衍射谱(XRD)、荧光光谱对其结构及发光性能进行了研究。结果表明,稀土离子S~(3+)的掺入没有改变荧光粉的晶相;样品的激发光谱在394 nm有很强的激发峰,与近紫外LED芯片匹配,且Eu~(3+)的~5D_0→~7F_2电偶极跃迁表现出616 nm有较好的红光发射,Eu~(3+)的最佳掺杂量(摩尔分数)为y=0.3;Sm~(3+)进入晶格后,激发峰明显增强和变宽,表明Sm~(3+)对Eu~(3+)的发光起到敏化作用;K_2Gd_(0.68)(PO_4)(WO_4)∶0.3Eu~(3+),0.02Sm~(3+)样品在150℃时发光强度仍为初始温度的78%,具有良好的热稳定性且色纯度高,是一种潜在的白光LED用荧光粉。     

一维四棱柱状Bi_2O_3纳米棒的微乳法合成及光性能

纳米氧化铋是一种重要的功能材料,其可控制备一直是研究的热点。以TritonX-100/正庚烷/正戊醇/水为微乳液体系,采用反相微乳法合成了一维四棱柱状Bi_2O_3纳米棒。采用X射线衍射(XRD)和扫描电镜(SEM)表征了煅烧温度和煅烧时间对Bi_2O_3样品晶型和微观形貌的影响。表征结果表明,随煅烧温度增加,产物由四方相β-Bi_2O_3向单斜相α-Bi_2O_3转变,样品为一维四棱柱状纳米棒,其直径为50～100 nm,长为300～600 nm。对前驱体的形成机制进行分析发现,定向附着、自组织和奥斯瓦尔德熟化在微乳体系合成纳米材料的过程中起到了重要作用。紫外-可见光谱(UV-Vis)分析表明,亚稳相β-Bi_2O_3(550 nm)相比稳定相α-Bi_2O_3(460 nm)具有更宽的可见光响应范围和更窄的禁带宽度(分别为2.30和2.74 eV),属于电子从价带跃迁到导带引起的吸收,为Bi_2O_3的直接带隙吸收。荧光光谱(PL)表明β-Bi_2O_3在400～600nm具有宽的发射谱带,466 nm处的强蓝带发射归属于Bi~(3+)的~3P_1→~1S_0跃迁和O~(2-)→Bi~(3+)荷移跃迁,562 nm处绿峰归属于晶体表面氧空位和生长过程中形成的缺陷。     

Na_2WO_4:Eu~(3+),Tb~(3+)光致发光材料的发光性质和能量传递

利用溶胶-凝胶法,将激活离子Eu~(3+)和Tb~(3+)以单一或混合的形式掺入体系得到了光致发光材料.分别研究了材料中激活离子Eu~(3+)和Tb~(3+)的含量及其离子之间的能量传递关系.主要利用材料的三维荧光光谱,激发光谱和发射光谱对其的发光性质进行了分析;结果发现,材料中有两个发光中心,分别为Eu~(3+)和Tb~(3+),在不同的波长光的激发下得到的材料的红绿色发光强度不同,而且Eu~(3+)和Tb~(3+)的掺杂浓度比对发光色度影响很大.所以可以根据选择最适合的Eu~(3+)和Tb~(3+)的浓度比来控制材料的发光色,也可以通过不同的激发波长对材料的色度进行微调.     

Recent progress of energy transfer and luminescence intensity boosting mechanism in Nd~(3+)-sensitized upconversion nanoparticles

Rare earth doped upconversion nanoparticles can be considered as the spice of research in the field of luminescence nanomaterials due to their unique optical properties such as near-infrared excitation.Enormous works have been reported about biomedical applications of 980 nm excited and Yb~(3+)-sensitized upconversion nanoparticles.However,980 nm excitation wavelength overlaps with the absorption band of water molecules in the biological environment,leading to overheating effect that can induce thermal damages of normal cells and tissues.Recently,Nd~(3+)-sensitized upconversion nanoparticles which can be excited with 808 nm has been widely investigated as alternative nanoparticles that can surmount this issue of overheating effect.Even though Nd~(3+)-sensitized upconversion nanoparticles can reduce the overheating effect by 20 fold as compared to Yb~(3+)-sensitized counterpart,there are several factors that reduce the upconversion luminescence intensity.In this review article,photon energy harvesting and transferring mechanisms in Nd~(3+),Yb~(3+)and emitter ions co-doped upconversion nanoparticles under 808 nm excitation are briefly discussed.Factors that affect upconversion luminescence intensity and quantum yield of Nd~(3+)-sensitized upconversion nanoparticles are also addressed.Besides,some of the important strategies that have been recently utilized to boost upconversion luminescence intensity of Nd~(3+)sensitized upco nversion nanoparticles are tho roughly summarized.Lastly,the future challenges in the area and our perspectives are in sight.     

Synthesis of YAG:Ce3+ Phosphor by Polyacrylamide Gel Method and Promoting Action of α-Al2O3 Seed Crystal on Phase Formation

YAG:Ce3 phosphor particles were prepared using polyacrylamide gel method. The structure evolution of powders during annealing process was followed by X-ray diffraction determination. It is found that some intermediate phases, including θ-Al2O3, YAM and YAP, are formed when calcining polyacrylamide gel, however, the pure YAG phase can be formed directly when calcining polyacrylamide gel with α-Al2O3 as seed crystal. These facts show that the existence of α-Al2O3 seed crystal can block the formation of θ-Al2O3, YAM and YAP, and accelerate its reaction with Y2O3 to form YAG phase directly at lower temperature. The emission peak of prepared YAG:Ce3 phosphor is wide with maximum at 550 nm and the exitation band has two peaks, the major one is around at 460 nm, which matches the blue emission of GaN LED and is suitable for the assemble of white LED. Some fluxes can enhance the photoluminescence intensity of phosphor particles, that can be attributed both to the improvement of crystallization processes of YAG and to the stabilization of trivalence cerium ion in YAG:Ce3 .     

Ultra-high sensitivity of rhodamine B sensing based on NaGdF4:Yb3+,Er3+@NaGdF4 core-shell upconversion nanoparticles

A series of mono-dispersed hexagon NaGdF_4:Yb~(3+),Er~(3+)@NaGdF_4 core-shell nanoparticles with different shell thickness were synthesized via a co-precipitation method. Nanoparticles with high upconversion fluorescent emissions result in large signal-to-noise ratio, which guarantees the accuracy of the sensitivity. Besides, the maximum sensitivity of these NPs as detection film increases first and then decreases with the shell thickness increasing. When the shell thickness is 2.3 nm(NaGdF_4-2), the maximum sensitivity(0.69959 ppm~(-1)) is reached. A large degree of overlap between the rhodamine B absorption band and the Er~(3+) green emission bands ensures that the NaGdF_4:Yb~(3+),Er~(3+)@NaGdF_4 nanoparticles can be used as fluorescent probe to detect the concentration of rhodamine B based on fluorescent intensity ratio technology. The linear relationship between the rhodamine B concentration and the intensity ratio(R) of green and red emission intensity(I_(S+H) and I_F) were studied systematically. The result shows that the maximum sensitivity can be obtained in low concentration rhodamine B(4 ppm), which is lower than the reported minimum detection concentration. Thus, the ultra-high sensitivity detection by NaGdF_4:Yb~(3+),Er~(3+)@NaGdF_4 core-shell upconversion nanoparticles in low concentration can be realized,which provides promising applications in bio-detection filed.     

Tunable luminescence,energy transfer and excellent thermal stability of SrMg_2(PO_4)_2:Ce~(3+),Tb~(3+) phosphors for LEDs

A series of novel SrMg_2(PO_4)_2:Ce~(3+),Tb~(3+)(SMP:Ce~(3+),Tb~(3+)) phosphors with tunable emission spectra were produced via high temperature solid phase method.XRD,fluorescence spectrum and fluorescence lifetime for SMP:Ce~(3+),Tb~(3+)were studied in detail.Under the excitation at 308 nm,SMP:Ce~(3+),Tb~(3+) samples can emit high efficiency tunable blue-green light by controlling the proportion of dopant concentration.Through the spectral overlap and the regular change of fluorescence lifetime,it is proved that there is a significant energy transfer between Ce~(3+) and Tb~(3+) in SMP matrix and the energy transfer mechanism is determined to be an electric dipole-dipole interaction with energy transmission efficiency of 55%.In additional,Commission International de L'Eclairage(CIE) color coordinates and thermal stability were studied.All above findings suggest that SMP:Ce~(3+),Tb~(3+)can be regarded as the potential bluish green phosphor for LED applications.     

Luminescence characteristics of Ca_4YO(BO_3)_3 doped with Bi~(3+),Dy~(3+) and Pr~(3+) ions

The photoluminescence(PL) properties of Ca4YO(BO3)3 doped with Bi3+,Dy3+,and Pr3+ ions were investigated.These compounds were prepared using a typical solid-state reaction.The excitation and emission spectra were measured using a spectrofluorometer.For Ca4YO(BO3)3:Bi3+,the excitation spectrum showed the bands at about 228,309,and 370 nm which correspond to the 1S0→1P1 transition and the 1S0→3P1 transition of Bi3+ ions.The emission band at 390 nm corresponded to the 3P1→1S0 transition of Bi3+ ions.For Ca4YO(BO3)3:Bi3+,Dy3+,energy transfer occurred from Bi3+ to Dy3+ somewhat.In Ca4YO(BO3)3:Bi3+,Dy3+,Pr3+,the excitation band at 367 nm was enhanced obviously due to the energy migration from Bi3+ to Pr3+,which converted efficiently the emission of semiconductor InGaN based light-emitting diode(LED).Therefore,the emission of Dy3+ ions was enhanced due to the energy migration from the process of Bi3+→Pr3+→Dy3+.It resulted in the good color rendering.     

Broadband Cr~(3+)-sensitized upconversion luminescence of LiScSi_2O_6:Cr~(3+)/Er~(3+)

Broadband sensitization is an effective strategy to enhance the upconversion luminescence(UCL) of lanthanide ions.Herein,novel UC materials LiScSi_2 O_6:Cr~(3+)/Er~(3+)(LSS:Cr~(3+)/Er~(3+)) were synthesized by high-temperature solid state reaction and their luminescent properties were investigated.LSS:Cr~(3+)/Er~(3+)has the broadband absorption in the spectral range of 600-800 nm,and meanwhile shows green UC emissions of Er~(3+)upon pumping Cr~(3+) by the 690 nm laser.The UCL of LSS:Cr~(3+)/Er~(3+)belongs to the twophoton process and is attributed to the energy transfer upconversion mechanism.The effects of the Cr~(3+)and Er~(3+)concentration as well as the Yb~(3+)introduction were also studied.LSS:Cr~(3+)/Yb~(3+)/Er~(3+) exhibits the interesting dual-mode UCL,capable of generating the UCL of Cr~(3+) upon pumping Yb~(3+)ions and the UCL of upon pumping Cr~(3+) ions.This research might promote the development of novel broadband Cr~(3+)-sensitized UC materials.     

Synthesis and characterization of NaYF_4:Yb~(3+),Er~(3+)@silica-N=folic acid nanocomplex for bioimaginable detecting MCF-7 breast cancer cells

Upconversion nanophosphors are new promising nanomaterials to be used as biolabels for detection and imaging of cancer cells.These nanophosphors absorb long-wavelength excitation radiation in the infrared or near infrared region and emit shorter wavelength,higher energy radiation from ultraviolet to infrared.In this paper,we studied the hydrothermal method and optical properties of the functionalized NaYF_4:Yb~(3+),Er~(3+)for biomedical application.After synthesis,these NaYF_4:Yb~(3+),Er~(3+)nanophosphors were functionalized with aminosilanes and folic acid.Folic acid binds to the folate receptor on the surface of MCF-7 breast cancer cells and this binding promotes internalization of the nanophosphors via endocytosis.The sizes of the functionalized NaYF_4:Yb~(3+),Er~(3+)@silica-N=FA(folic acid) nanophosphors can be controlled with length of the rod about 300-800 nm and diameter of the rod about 100-200 nm.Phase structure of NaYF_4:Yb~(3+),Er~(3+)is in hexagonal crystal system.The photo luminescence(PL) spectra of the functionalized NaYF_4:Yb~(3+),Er~(3+)@silica-N=FA nanophosphors were measured.These nanophosphors emit in red color with the strongest band at 650 nm under 980 nm excitation.This result can provide NaYF_4:Er~(3+),Yb~(3+)@silica-N=FA complex for developing fluorescence label and image tool in cancer biology and medicine.     

Preparation and upconversion luminescence of YAG（Y3Al5O12）：Yb^3＋,Ho^3＋ nanocrystals

Cubic YAG: Yb3+, Ho3+ pure phase nanocrystals were synthesized by using coprecipition nitrate and ammonium hydrogen carbonate as raw materials. After calcining the precipitates at 800 ℃, the resultant YAG: Yb3+, Ho3+ nanocrystals were nearly spheric and the particle size was about 40 nm. Intense upconversion spectra were observed on the powder compact pumped by a 980 nm continuous wave diode laser, and green emission centered at 549 nm, red emission centered at 667 nm, and NIR centered at 760 nm were all due to two photons process, which originated from 5S2 (5F4)→5I8, 5F5→5I8, and 5S2 (5F4)→5I7 transitions, respectively.     

Broadband near-infrared luminescence and energy transfer of Cr~(3+),Ce~(3+) co-doped Ca_2LuHf_2Al_3O_(12) phosphors

Broadband near-infrared phosphors are highly desirable for food testing.Targeted Ca₂LuHf₂Al₃O₁₂:Cr³⁺(CLHA:Cr³⁺) and Ca₂LuHf₂Al₃O₁₂:Ce³⁺,Cr³⁺(CLHA:Ce³⁺,Cr^(³⁺)) phosphors were synthesized by the conventional high-temperature solid state reaction.The CLHA:Cr³⁺phosphor,with a good thermal stability,shows a red shift owing to radiation reabsorption and non-radiative transition with increasing Cr³⁺content.For co-doped sample,the emission intensity of Cr³⁺can be enhanced by three times due to the energy transfer from Ce³⁺to Cr³⁺,which can be evidenced by a significant overlap between the PLE of Cr³⁺single-doped phosphor and the PL of Ce³⁺single-doped phosphor.In addition,the mechanism of energy transfer is identified as a quadrupole-quadrupole interaction according to decay Lifetime and Dexter’s energy transfer formula.The broadband NIR emission peaked at 775 nm of CLHA:Cr³⁺,Ce³⁺phosphor shows a bright prospect in nondestructive quality-control analysis systems for food.