用脉冲激光溅射法制备的Yb^3＋和Er^3＋共掺杂氟化物薄膜的上转换发光

脉冲激光溅射法（PLD），作为一种制备高质量薄膜的方法，被广泛地用于制备超导、铁电等薄膜。用PLD法制备的Yb^3 和Er^3 共掺杂氟化物薄膜的上转换发光性质。在978nm LD激发下，薄膜发出强烈的橙色光，用日立－F4500光谱仪测量了其上转换发光光谱，观测到了Er^3 很强的^2H9/2→^4I15/2(408nm),^2H11/2→^4I15/2(520nm),^4S3/2→^4I15/2(550nm)和^4F9/2→^4I15/2(650nm)跃迁发射峰。给出了上转换发光强度随激发强度的关系，分析了其上转换发光机制及紫色上转换发光增强的原因。     

一种新型铒镱共掺碲硅酸盐玻璃的光谱性质及荧光俘获效应研究

用高温熔制法制备了系列Er^3＋／Yb^3＋共掺碲硅酸盐玻璃样品，测试和分析了玻璃样品的吸收光谱、荧光光谱、上转换发光光谱及热稳定性。结果表明：这种玻璃具有较宽的荧光半高宽、较大的受激发射截面，较好的热稳定性。970nm泵浦下该系列玻璃在可见光525，546和658nm这3处存在明显的上转换现象，它们分别由Er^3＋离子^2H11/2→^4 I15/2，4S3/2→^4 I15/2和^4 F9/2→^4 I15/2辐射跃迁产生。另外，测试和讨论了在不同样品厚度下玻璃的光谱特性，如荧光光谱、荧光寿命和上转换发光光谱等。结果表明，荧光俘获效应对Er^3＋离子1．5μm波段荧光及上转换发光都有着较大的影响，并随着玻璃厚度的增加而增大，导致测量值与实际值产生较大的偏差。     

ZnWO4:Er3+,Yb3+纳米棒的制备及发光性能

采用水热法以聚乙二醇为分散剂合成了Er3+,Yb3+共掺的ZnWO4纳米棒.X射线衍射、透射电子显微镜分析结果表明:所得产物为直径约20 nm的ZnWO4纳米棒.在激发波长为980 nm的半导体激光器做光源激发下,确定样品的3个发射峰的发光中心位于532、553和656 nm,分别对应于铒离子2H11/2→4I15/2,4S3/2→4I15/2和4F9/2→4I15/2的跃迁.     

稀土离子掺杂Ba2GdF7纳米颗粒的合成及其上转换发光性质研究

采用热分解法制备了稀土离子掺杂的立方相Ba2GdF7上转换发光纳米粒子。利用X射线衍射(XRD)技术测定了样品的物相,通过透射电子显微镜(TEM)和荧光分光光度计分别分析了样品的形貌、尺寸和上转换发射光谱。实验结果表明:合成的样品为单分散的、其平均尺寸为14 nm,立方相结构的Ba2GdF7纳米颗粒。在980 nm红外光激发下Ba2GdF7:Yb0.2Er0.04纳米颗粒分别发射来自于Er3+离子2H11/2→4I15/2,4S3/2→4I15/2光跃迁的绿光和4F9/2→4I15/2光跃迁的红光发射。     

Yb3+,Er3+掺杂的NaGd(MoO4)2纳米晶的制备及发光性能

采用水热合成技术成功制备了一种新型的上转换发光纳米晶体NaGd(MoO4)2:Yb3+,Er3+.采用X射线粉末衍射分析、透射电镜和光谱分析对不同条件下所得样品的结构和发光性能进行了表征.NaGd(MoO4)2:Yb3+,Er3+和NaGd(MoO4)2具有相同的晶体结构,属于四方晶系;透射电镜观察表明,所得晶体为直径约为20 nm的纳米棒;在980 nm红外激光器的激发下,观察到了3个明显的上转换发射峰,发光中心分别位于531,552和656 nm,分别对应于Er3+2H11/2→I15/2,4S3/2→I15/2和4F9/2→4I15/2的跃迁.     

Li+掺杂对TeO2:Tm3+/Er3+/Yb3+纳米材料上转换发光的增强作用

采用水热法制备了发白光的Li+掺杂α-TeO2∶Tm3+/Er3+/Yb3+和β-TeO2∶Tm3+/Er3+/Yb3+纳米上转换发光材料。采用X射线衍射、透射电镜和上转换发光光谱对制备的TeO2∶Tm3+/Er3+/Yb3+/Li+纳米材料进行表征,结果显示:Li+的掺入基本不改变纳米材料的晶型和结构;在980 nm近红外光的激发下,纳米材料发射出中心波长476 nm的蓝光,525 nm及545 nm的绿光和659 nm及675nm的红光,分别对应于Tm3+的1G4→3H6能级跃迁,Er3+的2H11/2→4I15/2和4S3/2→4I15/2能级跃迁,Er3+的4F9/2→4I15/2能级跃迁和Tm3+的3F2→3H6能级跃迁;Li+的掺入能够增大白光体系的发光强度,基本不改变纳米材料的白光颜色。此外,探讨了纳米材料的上转换发光机理。     

一种上转换白光荧光粉的制备与发光性能研究

采用高温固相法制备了上转换白光荧光粉AlF3-YbF3:Er3+/Tm3+。通过XRD物相分析可知:上转换白光荧光粉AlF3-YbF3:Er3+/Tm3+是由三方AlF3相和正交YbF3相组成;利用发射光谱研究了该荧光粉的上转换发光性能,并且分析了当固定Er3+离子掺杂浓度时,Tm3+离子掺杂浓度对上转换白光荧光粉AlF3-YbF3:Er3+/Tm3+色度的影响,进而提出其上转换能量传递机制。结果表明:在980 nm激光激发下,波长为410 nm的紫光峰、550 nm的绿光峰和660 nm的红光峰分别对应于荧光粉中Er3+离子的2H9/2→4I15/2,4S3/2→4I15/2和4F9/2→4I15/2能级的跃迁,而波长为360 nm的紫外光峰、450 nm的蓝光峰、700 nm的红光峰,分别对应于荧光粉中Tm3+离子的1D2→3H6,1G4→3H6和1G4→3F4能级的跃迁,Er3+离子发出的光与Tm3+离子发出的光最终混合成色坐标为x=0.32,y=0.36的白光。此外,通过980 nm半导体激光器和EPM 2000 Dual-channel Joulemeter/Power meter测得该荧光粉最大上转换效率为6.90%。     

GdF3∶Er3+，Yb3+的合成和上转换发光特性

采用水热法制备了Er3 离子浓度为3%,yb3 离子浓度分别为10%,20%的GdF3:Er3 ,Yb3 .XRD结果表明:合成的样品均为正交结构的GdF3,Cd0.87Yb0.10Er0.03F3和Gd0.77Yb0.20Er0.03F3样品的晶粒尺寸分别为28和26 nm.研究了980 nm红外光激发的上转换发射光谱.结果表明:红光和绿光发射分别来自于Er3 离子的2H11/2,4S3/2→4I15/2和4F9/2→4I15/2跃迁.样品的绿光发射强度较红光发射强.但绿光和红光发射的相对强度比例与Yb3 离子浓度有关.对Gd0.87Yb0.10Er0.03F3和Gd0.77Yb0.20Er0.03F3样品中可能的上转换发光机制进行了讨论.     

Na(Y1.5Na0.5)F6:Yb3+/Er3+纳米棒的制备及其上转换发光特性

采用水热合成法,使用油酸作为乳化剂制备了Yb3+/Er3+共掺杂六角相Na(Y1.5Na0.5)F6纳米棒。通过X射线衍射(XRD)、扫描电子显微镜(SEM)以及荧光光谱等测试手段对所制备的样品进行表征。测试结果表明,Na(Y1.5Na0.5)F6纳米晶的晶格常数为a=b=0.600 nm,c=0.352 nm。在980 nm红外光激发下,Yb3+/Er3+共掺杂Na(Y1.5Na0.5)F6纳米棒发出从红光到近紫外的上转换荧光,其中红光、绿光和近紫外光分别对应于Er3+离子4F9/2→4I15/2,(2H11/2,4S3/2)→4I15/2和(2G11/2/2H9/2)→4I15/2的能级跃迁。详细讨论和分析了各荧光波段的上转换发射过程。     

用脉冲激光溅射法制备的Yb~(3 )和Er~(3 )共掺杂氟化物薄膜的上转换发光

脉冲激光溅射法 (PLD) ,作为一种制备高质量薄膜的方法 ,被广泛地用于制备超导、铁电等薄膜。用PLD法制备的Yb3 和Er3 共掺杂氟化物薄膜的上转换发光性质。在 978nmLD激发下 ,薄膜发出强烈的橙色光 ,用日立 -F45 0 0光谱仪测量了其上转换发光光谱 ,观测到了Er3 很强的2 H9/2 →4 I1 5/2 (4 0 8nm) ,2 H1 1 /2 →4 I1 5/2 (5 2 0nm) ,4 S3/2 →4 I1 5/2 (5 5 0nm)和4 F9/2 →4 I1 5/2 (65 0nm)跃迁发射峰。给出了上转换发光强度随激发强度的关系 ,分析了其上转换发光机制及紫色上转换发光增强的原因。     

Strong blue emission from Pr3+ ions through energy transfer process from Nd3+ to Pr3+ via Yb3+ in tellurite glass

Energy transfer excited upconversion emission in Nd3+/Pr3+-codped tellurite glass have been studied on pumping with 800 nm wavelength. The upconversion emission bands from Pr3+ ion are observed at the 488, 524, 546, 612, 647, 672, 708 and 723 nm due to the (3P0 + 3P1)-->3H4, 3P1-->3H5, 3P0-->3H5, 3P0-->3H6, 3P0-->3F2, 3P1-->3F3, 3P0-->3F3 and 3P0-->3F4 transitions, respectively. The addition of ytterbium ions (Yb3+) on the upconversion emission intensity is also studied and result shows an eight times enhancement in the upconversion intensity at 488 nm from Pr3+ ions. The pump power and concentration dependence studies are also made. It is found that Yb3+ ions transfer its excitation energy to Nd3+ from which it goes to Pr3+. No direct transfer to Pr3+ is seen. This is verified by codoping Nd3+ and Pr3+ into the host.     

LD激发的ZnWO4:Er3+晶体上转换发光

采用Czochralski法生长出ZnWO₄:Er³⁺(Er=0.02mol)单晶,测量了吸收光谱和激发光谱。在波长966nm功率500mW的激光二极管(LD)激发下观察到上转换发光。强度最大的发射峰位于547和558nm,发射光谱分析表明,上转换激发过程与双光子步进吸收有关。     

Yb~(3 )对Tm~(3 )间接敏化与基质晶格关系

Yb3 敏化Tm3 有两种方式 ,一种是直接敏化上转换 ,另一种是间接敏化上转换。前种直接采用 980nm激光激发 ,而后者可用 80 7nm激光激发 ,无疑后者有利于提高上转换发光的量子效率。由于基质晶格的晶体场强度不同 ,对称性有高有低 ,造成的稀土离子的能级分裂不同 ,通过分析双掺BaY2 F8,Cs3Yb2 Cl9等材料的光谱资料并结合生长的双掺Yb3 ,Tm3 ∶ZnWO4 单晶光谱的实际测试与分析 ,提出了Yb3 和Tm3 间的间接敏化共振能量传输的新观点 ,并具体分析了能形成这一上转换机制的条件。与间接敏化非共振能量传输不同 ,一是Yb3 的2 F5/2 →2 F7/2 的跃迁应与Tm3 3H4 →1 G4 能级间隔尽可能接近 ;二是Yb3 激发态能级2 F5/2 与Tm3 的3H4 能级尽可能接近。这要求基质材料的晶体场场强要弱 ,对称性要低。间接敏化共振能量传输极有可能引起光子雪崩上转换 ,这将为探索实用上转换激光晶体提供有益经验。     

Study of upconversion fluorescence property of novel Er3+/Yb3+ co-doped tellurite glasses

Er3+/Yb3+ co-doped TeO2-B2O3-Nb2O5-ZnO (TBN) glasses were prepared. The absorption spectra and upconversion luminescence spectra of TBN glasses were measured and analyzed. The upconversion emission bands centered at 530, 546 and 658 nm were observed under the excitation at 975 nm, corresponding to the transitions of 2H11/2-->4I15/2, 4S3/2-->4I15/2 and 4F9/2-->4I15/2 respectively. The ratio of red emission to green emission increases with an increasing of Yb3+ ions concentration. According to the quadratic dependence on excitation power, the possible upconversion mechanisms and processes were discussed.     

Long-lived room temperature deep-red/near-IR emissive intraligand triplet excited state (3IL) of naphthalimide in cyclometalated platinum(II) complexes and its application in upconversion

[C(^)NPt(acac)] (C(^)N = cyclometalating ligand; acac = acetylacetonato) complexes in which the naphthalimide (NI) moiety is directly cyclometalated (NI as the C donor of the C-Pt bond) were synthesized. With 4-pyrazolylnaphthalimide, isomers with five-membered (Pt-2) and six-membered (Pt-3) chelate rings were obtained. With 4-pyridinylnaphthalimide, only the complex with a five-membered chelate ring (Pt-4) was isolated. A model complex with 1-phenylpyrazole as the C(^)N ligand was prepared (Pt-1). Strong absorption of visible light (ε = 21,900 M(-1) cm(-1) at 443 nm for Pt-3) and room temperature (RT) phosphorescence at 630 nm (Pt-2 and Pt-3) or 674 nm (Pt-4) were observed. Long-lived phosphorescences were observed for Pt-2 (τ(P) = 12.8 μs) and Pt-3 (τ(P) = 61.9 μs). Pt-1 is nonphosphorescent at RT in solution because of the acac-localized T(1) excited state [based on density functional theory (DFT) calculations and spin density analysis], but a structured emission band centered at 415 nm was observed at 77 K. Time-resolved transient absorption spectra and spin density analysis indicated a NI-localized intraligand triplet excited state ((3)IL) for complexes Pt-2, Pt-3, and Pt-4. DFT calculations on the transient absorption spectra (T(1) → T(n) transitions, n > 1) also support the (3)IL assignment of the T(1) excited states of Pt-2, Pt-3, and Pt-4. The complexes were used as triplet sensitizers for triplet-triplet-annihilation (TTA) based upconversion, and the results show that Pt-3 is an efficient sensitizer with an upconversion quantum yield of up to 14.1%, despite its low phosphorescence quantum yield of 5.2%. Thus, we propose that the sensitizer molecules at the triplet excited state that are otherwise nonphosphorescent were involved in the TTA upconversion process, indicating that weakly phosphorescent or nonphosphorescent transition-metal complexes can be used as triplet sensitizers for TTA upconversion.     

Effect of ZnX (X=F2 and Cl2) as modifier on luminescence properties of Ho3+/Yb3+ doped tellurite glasses

Optical absorption and photoluminescent properties of Ho(3+)/Yb(3+) co-doped tellurite and zinc halide tellurite glasses are investigated. The effect of zinc halides as modifier on the luminescence properties of above mentioned samples has been explored. Two intense upconversion emission bands centered at 546 ((5)F(4), (5)S(2)→(5)I(8)) and 660 ((5)F(5)→(5)I(8)) nm are observed when samples are excited by 976 nm radiation. Zinc halides act as quencher when 976 nm excitation source is used. The up and downconversion emission spectra are recorded with 532 nm excitation source also. In this case also, zinc halides do not show any improvement. The dependence of upconversion intensities on excitation power and temperature is discussed. The power dependence study shows a quadratic dependence of fluorescence intensity on the excitation power while decrement in emission intensity of different transitions at different rates is observed in temperature dependence study. The possible upconversion mechanisms are also discussed in order to understand the energy transfer between Yb(3+) and Ho(3+) ions.     

Enhancement of luminescence properties in Er3+ doped TeO2-Na2O-PbX (X=O and F) ternary glasses

An enhancement of luminescence properties in Er3+ doped ternary glasses is observed on the addition of PbO/PbF2. The infrared to visible upconversion emission bands are observed at 410, 525, 550 and 658 nm, due to the 2H9/2-->4I15/2, 2H11/2-->4I15/2, 4S3/2-->4I15/2, 4F9/2-->4I15/2 transitions respectively, on excitation with 797 nm laser line. A detailed study reveals that the 2H9/2-->4I15/2 transition arises due to three step upconversion process while other transitions arise due to two step absorption. On excitation with 532 nm radiation, ultraviolet and violet upconversion bands centered at 380, 404, 410 and 475 nm wavelengths are observed along with one photon luminescence bands at 525, 550, 658 and 843 nm wavelengths. These bands are found due to the 4G11/2-->4I15/2, 2P3/2-->4I13/2, 2H9/2-->4I15/2, 2P3/2-->4I11/2, 2H11/2-->4I15/2, 4S3/2-->4I15/2, 4F9/2-->4I15/2 and 4S3/2-->4I13/2 transitions, respectively. Though incorporation of PbO and PbF2 both enhances fluorescence intensities however, PbF2 content has an important influence on upconversion luminescence emission. The incorporation of PbF2 enhances the red emission (658 nm) intensity by 1.5 times and the violet emission (410 nm) intensity by 2.0 times. A concentration dependence study of fluorescence reveals the rapid increase in the red (4F9/2-->4I15/2) emission intensity relative to the green (4S3/2-->4I15/2) emission with increase in the Er3+ ion concentration. This behaviour has been explained in terms of an energy transfer by relaxation between excited ions.     

Designing Upconversion Nanocrystals Capable of 745 nm Sensitization and 803 nm Emission for Deep‐Tissue Imaging

A crystal design strategy is described that generates hexagonal‐phased NaYF₄:Nd/Yb@NaYF₄:Yb/Tm luminescent nanocrystals with the ability to emit light at 803 nm when illuminated at 745 nm. This is accomplished by taking advantage of the large absorption cross‐section of Nd³⁺ between 720 and 760 nm plus efficient spatial energy transfer and migration through Nd³⁺→Yb³⁺→Yb³⁺→Tm³⁺. Mechanistic investigations suggest that a cascaded two‐photon energy transfer upconversion process underlies the emission mechanism. This protocol enables deep‐tissue imaging to be achieved while mitigating the attenuation effect associated with the visible emission and the overheating constraint imposed by conventional 980 nm excitation.     

Host dependent frequency upconversion of Er3+/Yb3+-codoped bismuth-germanate glasses

The absorption and upconversion fluorescence spectra of a series of Er3+/Yb3+-codoped xBi(2)O(3)-(90-x)GeO2-10Na(2)O (BGN x, x=31, 36, 41, 46 and 51 mol%) glasses have been studied. Intense green and red emission bands at around 533, 548 and 659 nm, corresponding to the 2H(11/2)-->4I(15/2), 4S(3/2)-->4I(15/2) and 4F(9/2)-->4I(15/2) transitions of Er3+, respectively, were simultaneously observed at room temperature. The dependence of intensities of upconversion emission on excitation power and possible upconversion mechanisms were evaluated and analyzed. The important role of Bi(2)O(3) in upconversion intensity is observed and its influence on the green (533 and 548 nm) and red (659 nm) emissions is compared and discussed. The influence of Bi(2)O(3) on the upconversion emissions has been investigated based on the IR spectra.