氟氧化物纳米相玻璃陶瓷Tb(0.7)Yb(5)∶FOV的合作下转换发光

报道了氟氧化物纳米相玻璃陶瓷Tb(0.7)Yb(5)∶FOV的红外量子剪裁研究,测量了从可见到红外的荧光发光光谱、激发谱、和荧光寿命,分析了{1([5 D4→7 F6](Tb3+),2([2 F7/2→2 F5/2] (Yb3+)}的红外量子剪裁现象,发现了487.0nm光激发5 D4能级和378.0nm光激发(5 D3,5 G6)能级的理论量子剪裁效率ηx％Yb依次分别为121.35％和136.27％.首次发现了一种新颖的合作(共协)下转换发光现象{2([(5 D3,5 G6)→5 D4](Tb3+),1([2 F7/2→2 F/2](Yb+)},即首次发现施主Tb3+离子释放两个小能量光子[(5 D3,5 G6)→5 D4]的能量,导致出现一个受主Yb3+的[2 F5/2→2 F7/2]的中等能量的光子.     

氟氧化物纳米相玻璃陶瓷Tb(0.7)Yb(5):FOV的合作下转换发光

报道了氟氧化物纳米相玻璃陶瓷Tb(0.7)Yb(5)∶FOV的红外量子剪裁研究,测量了从可见到红外的荧光发光光谱、激发谱、和荧光寿命,分析了{1([5 D4→7 F6](Tb3+),2([2 F7/2→2 F5/2](Yb3+)}的红外量子剪裁现象,发现了487.0nm光激发5 D4能级和378.0nm光激发(5 D3,5 G6)能级的理论量子剪裁效率ηx%Yb依次分别为121.35%和136.27%。首次发现了一种新颖的合作(共协)下转换发光现象{2([(5 D3,5 G6)→5 D4](Tb3+),1([2 F7/2→2 F5/2](Yb3+)},即首次发现施主Tb3+离子释放两个小能量光子[(5 D3,5 G6)→5 D4]的能量,导致出现一个受主Yb3+的[2 F5/2→2 F7/2]的中等能量的光子。     

纳米相氟氧化物玻璃陶瓷Tm（0.35）Yb（5）∶FOV的上转换发光

研究了纳米相氟氧化物玻璃陶瓷Tm(0.35)Yb(5)∶FOV在975nm半导体激光激发下的上转换发光。发现了位于363.6,(462.6,477.0),648.7,(699.7,680.7)和(777.6,800.7nm)的几条上转换发光线,它们是Tm3 离子的1D2→3H6,1G4→3H6,1G4→3F4,3F3→3H6和3H4→3H6的荧光跃迁。为了确认它们的上转换机理,还测量了上转换发光强度F随975nm泵浦激光功率P改变的双对数曲线,结果证实了1D2能级的上转换发光部分是五光子上转换发光,而1G4能级和3H4能级的上转换发光则是三光子和双光子上转换发光。     

纳米相氟氧化物玻璃陶瓷Tm(0.35)Yb(5):FOV的上转换发光

研究了纳米相氟氧化物玻璃陶瓷Tm(0.35)Yb(5):FOV在975 nm半导体激光激发下的上转换发光.发现了位于363.6,(462.6,477.0),648.7,(699.7,680.7)和(777.6,800.7 nm)的几条上转换发光线,它们是Tm3 离子的1D2→H6,1G→H6,1G4→F4,3F3→H6和3H4→H6的荧光跃迁.为了确认它们的上转换机理,还测量了上转换发光强度F随975 am泵浦激光功率P改变的双对数曲线,结果证实了1D2能级的上转换发光部分是五光子上转换发光,而1G4能级和H4能级的上转换发光则是三光子和双光子上转换发光.     

掺铒的纳米相氟氧化物玻璃陶瓷的多光子红外量子剪裁

研究了掺铒的纳米相氟氧化物玻璃陶瓷(Er(3):FOV)的红外量子剪裁现象,测量了红外和可见的Er(3):FOV的荧光光谱.结果发现光激发²H_11/2能级的⁴ I_13/2→⁴I_15/2荧光跃迁的近似量子剪裁效率已达约186.28%.计算了有关的无辐射弛豫速率、自发辐射速率和能量传递速率,分析了有关的能量传递动力学过程,发现     

Ho(0.5)Yb(5)氟氧化物玻璃的直接上转换增敏发光

本文研究了HoYb共掺氟氧化物玻璃的直接上转换增敏发光现象。发现了位于 (5 4 4 5nm ,1836 5cm- 1 )和 (6 5 8 5nm ,15 186cm- 1 )的两条很强的上转换发光 ,它们是 5S2 → 5I8和5F5→ 5I8的荧光跃迁。还有其他的一些上转换发光5F3→ 5I8,5S2 → 5I7和5I4 → 5I8的跃迁。还发现存在一种特征的饱和现象 ,即所有上转换发光随激光功率变化的F P双对数关系曲线都是一条相当好的直线 ,其斜率会随着光斑的增大而增大 ,由分析得知这是由能量扩能散造成的。     

Tm(0.1)Yb(10.9)氟氧化物玻璃陶瓷的直接上转换敏化发光

本文首次研究了掺杂Ｔｍ（０．１）Ｙｂ（１０．９）氟氧化物玻璃陶次居９６６ｎｍ半导体激光激发下的直接上转换敏化发光现象。测量艰现存在很强的＾１Ｇ４→＾３Ｈ６的４７７ｎｍ的三光子和＾３Ｆ４→＾３Ｈ６的７９９．５ｎｍ双光子上转换荧光以及较弱的＾１Ｄ２→＾３Ｈ６的３６１ｎｍ,＾１Ｄ２→＾３Ｈ４的４４９．５ｎｍ,＾１Ｇ４→＾３Ｆ４的６４７．０ｎｍ和＾３Ｆ３→＾３Ｈ６的多个上转换发光。     

掺钬镱离子的氟氧化物玻璃陶瓷的一级和二级红外量子剪裁的研究

本文报道了掺钬镱离子的氟氧化物玻璃陶瓷的一级和二级红外量子剪裁的比较研究．研究发现当0G5能级到0＆能级及之间的能级被激发的时候,大多数的粒子数容易无辐射弛豫到（5F4^5S2）能级．在（0F40＆）能级,由很强的ET7-ETaYb{5F4（Ho）→5I6（Ho）,2F7／2（Yb）→2F5/2（Yb））交叉能量传递渠道,导致Ho3＋离子的粒子数被无损耗的交叉能量传递到5I6能级,同时Yb3＋离子从基态2F7／2能级被激发到2F5/2能级,它导致了两个能被晶体硅有效吸收的红外光子,即一个（1153am,1188am）的红外光子和另一个（973．0nm,1002．0nm）的红外光子,因此出现了显著的双光子一级红外量子剪裁．最后,该文计算了Ho（0．5）Yb（1）：FOV和Ho（0．5）Yb（10．5）：FOV的交叉能量传递效率为ηtr,1％Yb（5FS2）=29．2％,‰,10．5％Yb（5F4^5S2）=99．2％和它们的共合作能量传递效率为ηtr,1％Yb（5F3）=4．18％,ηtr,10．5％Yb（5F3）=75．3％;而它们的双光子量子剪裁效率的理论上限值依次为ηCR,1％Yb（5F4^5S2）=129．2％,ηCR,10．5％Yb（5F4^5S2）=199．2％和ηCO,1％Yb（5F3）=104．18％,ηCO,10.5％Yb（5F3）=175．3％．因此发现了一级红外量子剪裁有比二级红外量子剪裁高较多的概率．该项研究对太阳能电池效率的提高很有意义．     

纳米相氟氧化物玻璃陶瓷中Er3+Yb3+离子对的量子剪裁发光造成的强的光谱调制

研究了纳米相氟氧化物玻璃陶瓷中Er3+Yb3+离子对的量子剪裁发光造成的强的光谱调制现象。测量了Er3+Yb3+双掺纳米相氟氧化物玻璃陶瓷的X射线衍射谱、表面形貌、激发光谱、吸收光谱、和发光光谱;而且也与Tb3+Yb3+双掺纳米相氟氧化物玻璃陶瓷的相对应的光谱参数进行了比较。发现378 nm光激发样品(A) Er(1%)Yb(8.0%)∶FOV和样品(B) Er(0.5%)Yb(3.0%)∶FOV所导致的652.0 nm红色发光强度为522 nm光激发时的680.85倍和303.80倍;我们还发现378 nm光激发所导致的样品(A) Er(1%)Yb(8.0%)∶FOV和样品(B) Er(0.5%)Yb(3.0%)∶FOV的 652.0 nm红色发光强度为样品(C) Er(0.5%)∶FOV 的491.05和184.12倍。我们还发现在378 nm光激发时的样品(A) Er(1%)Yb(8.0%)∶FOV和样品(B) Er(0.5%)Yb(3.0%)∶FOV的{978.0和1 012.0 nm}红外发光强度依次分别为样品(C) Er(0.5%)∶FOV 的{58.00和293.62}倍和{25.11和 67.50}倍。更进一步,对于652.0 nm波长发光的激发谱,发现(A) Er(1%)Yb(8.0%)∶FOV和(B) Er(0.5%)Yb(3.0%)∶FOV的378.5 nm激发谱峰强度是(C) Er(0.5%)∶FOV的大约606.02和199.83倍。同时,也发现样品(A) Er(1%)Yb(8.0%)∶FOV和样品(B) Er(0.5%)Yb(3.0%)∶FOV的一级量子剪裁红外1 012或978 nm发光强度为样品(D) Tb(0.7%)Yb(5.0%)∶FOV的二级量子剪裁红外976 nm发光强度的101.38和29.19倍。发现的该量子剪裁是目前所报道的最强的量子剪裁。因此,相信所发现的氟氧化物纳米玻璃陶瓷中Er3+Yb3+离子对的一级量子剪裁发光是强的可以作为量子剪裁层应用到提高晶硅太阳能电池的发电效率。研究结果也能加速对目前国际热点的下一代环保的光谱调制太阳能电池的探索。     

Tm(0.1)Yb(10.9)氟氧化物玻璃的直接上转换敏化发光

本文首次研究了Tm(0.1)Yb(10.9)氟氧化物玻璃在966nm半导体激光激发下的直接上转换敏化发光现象。测量发现存在很强的^1G4→^3H6的474nm三光子和较弱的^1D2→^3H6的362nm,^1D2→^3F4的452nm,^1G4→^3F4的650nm三光子以及^3F3→^3H6的681nm二光子上转换发光。并对他们的上转换机理做了简要的讨论分析。     

Ultraviolet and visible upconversion luminescence of Tm(0.1)Yb(5):FOV oxyfluoride nanophase vitroceramics

The ultraviolet upconversion luminescence of Tm³⁺ ions sensitized by Yb³⁺ ions in oxyfluoride nanophase vitroceramics when excited by a 975 nm diode laser was studied. An ultraviolet upconversion luminescence line positioned at 363.6 nm was found. It was attributed to the fluorescence transition of ¹D₂→³H₆ of Tm³⁺ ion. Several visible upconversion luminescence lines at 450.7 nm, (477.0 nm, 462.5 nm), 648.5 nm, (680.5 nm, 699.5 nm) and (777.2 nm, 800.7 nm) were also found, which result respectively from the fluorescence transitions of ¹D₂→³F₄, ¹G₄→³H₆, ¹G₄→³F₄, ³F₃→³H₆ and ³H₄→³H₆ of Tm³⁺ ion. The careful measurement and analysis of the variation of upconversion luminescence intensity F as a function of the 975 nm pumping laser power P prove that the upconversion luminescence of ¹D₂ state is partly a five-photon upconversion luminescence, and the upconversion luminescence of ¹G₄ state and ³H₄ state are respectively the three-photon and two-photon upconversion luminescence. The theoretical analysis suggested that the upconversion mechanism of the 363.6 nm ¹D₂→³H₆ upconversion luminescence is partly the cross energy transfer of {³H₄(Tm³⁺), ³F₄(Tm³⁺), ¹G₄(Tm³⁺)→¹D₂(Tm³⁺)} and {¹G₄(Tm³⁺)→³F₄(Tm³⁺), ³H₄(Tm³⁺)→¹D₂(Tm³⁺)} between Tm³⁺ ions. In addition, the upconversion luminescence of ¹G₄ and ³H₄ state results respectively from the sequential energy transfer {²F_5/2(Yb³⁺)→²F_7/2(Yb³⁺), ³H₄(Tm³⁺)→¹G₄(Tm³⁺)} and {²F_5/2(Yb³⁺) →²F_7/2(Yb³⁺), ³F₄(Tm³⁺)→³F₂(Tm³⁺)} from Yb³⁺ ions to Tm³⁺ ions. Supported by the National Natural Science Foundation of China (Grant No. 10674019)     

Experimental study on a nonlinear photonics process of Er(0.5)Yb(3):FOV oxyfluoride nanophase vitroceramics

We study the nonlinear photonics of rare-earth-doped oxyfluoride nanophase vitroceramics (FOV), oxyfluoride glass (FOG), and ZBLAN fluoride glass. We found that an interesting fluorescence intensity inversion phenomenon between red and green fluorescence occurs from Er(0.5)Yb(3):FOV. The dynamic range summation operator of the intensity inversion between red and green fluorescence of Er(0.5)Yb(3):FOV is about 5.753 x 10(2), which is 100 to 1000 times larger than those of other materials. One of the applications of this phenomenon is double-wavelength fluorescence falsification-preventing technology, which is proved to possess the novel antifriction loss and antiscribble properties.     

Infrared quantum cutting conversion luminescence of Tb(0.7)Yb(3):FOV

The infrared quantum cutting of oxyfluoride nanophase vitroceramics Tb(0.7)Yb(3):FOV has been studied in the present paper. The actual quantum cutting efficiency formula calculated from integral fluorescence intensity is extended to the case of Tb(0.7)Yb(3):FOV. The visible and the infrared fluorescence spectra and their integral fluorescence intensities are measured from static fluorescence experiment. Lifetime curve is measured from dynamic fluorescence experiment. It is found that the total actual quantum cutting efficiency η of the excited ⁵D₄ level is about 93.7%, and that of excited (⁵D₃, ⁵G₆) levels is 93.5%. It is also found that the total theoretical quantum cutting efficiency upper limit η_x%Yb of the 485.5 nm excited <⁵D₄ level is about 121.7%, and that of 378.5 nm excited (⁵D₃, ⁵G₆) levels is 137.2%.     

Experiments and analysis of infrared quantum cutting luminescence phenomena of Ho/Yb codoped nanophase oxyfluoride vitroceramics

The infrared quantum cutting phenomenon, which is an international hot research field, of Ho³⁺Yb³⁺: oxyfluoride vitroceramics (FOV) was studied in the present paper. It was found from the fluorescence spectroscopy experiments that the excitation spectrum of 973.0 nm fluorescence of Yb³⁺ ion is very similar to the absorption and excitation spectra of Ho³⁺ ion. It suggests that the energy transfer from Ho³⁺ ion to Yb³⁺ ion is very efficient. Then, all the possible important energy transfer passages were analyzed. It was found that the energy transfers {⁵G₄(Ho³⁺)→⁵F₅(Ho³⁺), ²F_7/2(Yb³⁺)→²F_5/2(Yb³⁺)} and {⁵F₅(Ho³⁺)→⁵I₇(Ho³⁺), ²F_7/2(Yb³⁺)→²F_5/2(Yb³⁺)} result in the effective two-photon quantum cutting 973.0 nm fluorescence of Yb³⁺ ion when ⁵G₄ or ³K₇ or the above energy level of Ho³⁺ ion are excited. Finally, the quantum efficiency η_QE,1%Yb=43.0% and η_QE,5%Yb=171.7% of two-photon quantum cutting was calculated for Ho(0.5)Yb(1):FOV and Ho(0.5)Yb(5):FOV respectively. This research would be beneficial for the enhancement of solar cell efficiency.     

Improved anti-Stokes energy transfer between rare earth ions in Er（0.5）Yb（9.5）：FOV oxyfluoride vitroceramics explains the strong color reversal

The widely used energy transfer theory is a foundation of luminescence,in which the rates of Stokes and antiStokes processes have the same calculation formula.An improvement on the anti-Stokes energy transfer to explain the fluorescence intensity reversal between the red and green fluorescence of Er(0.5)Yb(9.5):FOV is reported in the present article.The range of the intensity reversal Σ was measured to be 877.Dynamic processes for 16 levels were simulated.A coefficient,the improvement factor of the intensity ratio of Stokes to anti-Stokes processes in quantum Raman theory compared to classical Raman theory,is introduced to successfully describe the anti-Stokes energy transfer.A new method to calculate the distance between the rare earth ions,which is critical for the energy transfer calculation,is proposed.The validity of these important improvements is also proved by experiment.     

Yb:YAG晶体的合作发光现象

研究了Yb：YAG晶体的合作发光现象。当用940nm的近红外光激发时,Yb:YAG晶体有明显的上转换蓝色发光。实验发现498 nm的蓝色发光强度与激发功率的平方成正比,而且Yb3+掺杂浓度越高,蓝色发光越强。分析表明这是Yb3+间强的相互作用导致的合作发光,是由于Yb3+在共价性的YAG基质中,它的4f13电子易于与近邻离子发生相互作用导致的。     

DIRECT UPCONVERSION SENSITIZATION LUMINESCENCE OF Ho(0.1)Yb(5):OXYFLUORIDE VITROCERAMICS

This paper studies the upconversion luminescence phenomenon of the Ho,Yb co-doped oxyfluoride vitroceramics. There is one group of strong upconversion luminescence lines positioned at 536.5nm, 18639cm^-1; 540.5nm, 18501cm^-1; 544.0nm, 18399cm^-1, which is easily identified as the transitions of ⁵S₂→⁵I₈. There are other splendid upconversion luminescence lines, which are ⁵S₂→⁵I₇,⁵F₅→⁵I₈,⁵G₆→⁵I₈, (⁵G³G)₅ →⁵I₈,(³F³H⁵G)₄→⁵I₇,⁵G₄→⁵I₈ and (⁵G³H)₅→⁵I₈. It is also found that an interesting kind of upconversion cooperative radiation fluorescence comes from a kind of coupling state of clusters consisting of two Yb³⁺ ions.     

Quantum cutting mechanism in NaYF4:Tb3+, Yb3+

A quantum cutting mechanism for the sublinear near-IR power dependence property in Tb3+-Yb3+ codoped NaYF4 powders were investigated both experimentally and theoretically. The slopes of Yb3+ luminescence intensity versus excitation power were fitted to be between 0.5 and 1. We have developed a quantum cutting rate equation model to explain the anomalous sublinear phenomenon and an assessment factor was introduced to help understand the physical mechanism. Experimental results showed that the linear downconversion process combined with second-order nonlinear process induced the sublinear power dependence property with the latter to be the dominant process.