GdBO3：Pr3+，Yb3+中Pr3+到Yb3+的能量传递及发光性质

采用高温固相法制备了一系列单掺或双掺Pr3+和Yb3+的GdBO3材料,分别测试分析了材料的物相结构和发光性质。在446 nm蓝光( Pr3+：3 H4→3 P2)激发下,检测到Yb3+的近红外特征发射,表明样品中存在Pr3+到Yb3+的能量传递。 Pr3+的掺杂浓度一定时,样品的发光会随着Yb3+掺杂浓度的改变而发生变化。通过对比不同掺杂情况下Pr3+：3 P0能级的衰减曲线,发现随着Yb3+的掺杂浓度的增加,该能级的荧光寿命不断缩短;同时利用不同条件下的衰减特性计算得出不同 Yb3+掺杂浓度样品的能量传递效率。用 Inokuti-Hirayama模型分析表明Pr3+-Yb3+能量传递类型为偶极子-偶极子相互作用。     

Nd3+ → Yb3+ energy transfer in glasses with composition close to LiLnP4O12 metaphosphate (Ln = La,Nd, Yb)

In the course of an investigation of new luminescent solar concentrators (LSC) we report a kinetic stúdy of the Nd³⁺ → Yb³⁺ energy transfer for Yb doped glasses with compositions close to LiLnP₄O₁₂ (Ln = La, Nd, Yb). If the only doping ion present is neodymium, the glasses exhibit low self quenching of the Nd ⁴F_3/2→⁴I_11/2 emission. For Nd³⁺-Yb³⁺ codoped glasses, the energy migration over the donor array can be explained by a hopping mechanism. Supermigration arises for neodymium concentrations exceeding 2.8 × 10²¹ ions cm^-3. The large ytterbium lifetime limits the neodymium decay rate at low ytterbium concentration.     

The luminescence and energy transfer in Pr3+–Ce3+ co-doped Lu0.8Sc0.2BO3 crystals

Lu_0.8Sc_0.2BO₃ crystals doped with 1 at%Ce³⁺ and co-doped 0.1 at% and 0.5 at%Pr³⁺ were grown by the Czochralski method. The concentrations of Pr³⁺ and Ce³⁺ in crystals were measured by the ICP-AES method. Absorption spectra, VUV–UV spectra, fluorescence decay time and X-ray excitation luminescence spectra were investigated at room temperature. The excitation luminescence spectra of Ce³⁺ emission and decay curves from the lower excited state levels of the 4f¹5d¹ and 5d¹ electronic configurations of the Pr³⁺ and Ce³⁺ conspicuously indicated the non-radiative energy transfer from Pr³⁺ to Ce³⁺. The detailed pathways were shown in the energy level diagram of the respective Ce³⁺ and Pr³⁺ in Lu_0.8Sc_0.2BO₃ host. In addition, the scintillation efficiency data indicated that the energy transfer effect is directly associated with the Pr³⁺ concentration.     

Driving the resonant quantum kicked rotor via extended initial?conditions

We study the resonances of the quantum kicked rotor subjected to an extended initial distribution. For the primary resonances we obtain the dispersion relation for the map of this system. We find an analytical dependence of the statistical moments on the shape of the initial distribution. For the secondary resonances we obtain numerically a similar dependence. This allows us to devise an extended initial condition which produces an average angular momentum pointing in a preset direction which increases with time with a preset ratio.     

Förster energy transfer from a semiconductor quantum well to an organic material overlayer

We predict an efficient electronic energy transfer from an excited semiconductor quantum well to optically active organic molecules of the nearby medium (substrate and/or overlayer). The energy transfer mechanism is of the F?rster type and, at semiconductor-organic distances of about 50 ?, can easily be as fast as 10-100 ps, which is about an order of magnitude shorter than the effective exciton lifetime in an isolated quantum well. In such conditions, the Wannier-Mott exciton luminescence is quenched and the organic luminescence is efficiently turned on. We consider both free as well as localized quantum well excitons discussing the dependence of the energy transfer rate on temperature and localization length. A similar mechanism for the non-radiative energy transfer to the organic overlayer molecules from unbound electron-hole pairs excited in the 2D continuum is shown to be much less competitive with respect to other relaxation channels inside the inorganic quantum well (in particular, 2D exciton formation). Received 20 July 1998     

Intense 974 nm emission from ErxYb2−xSi2O7 films through efficient energy transfer up-conversion from Er3+ to Yb3+ for Si solar cell

The optical properties of the Er_xYb_2?xSi₂O₇ thin films were investigated by photoluminescence measurements and the intense 974 nm light emission was observed. The 974 nm emission was mainly from the transition ²F_5/2 to ²F_7/2 level of Yb³⁺ upon exploring energy-transfer via up-conversion at Er^{3+ 4}I_13/2 level. Under 972 nm excitation, the lifetime at Er^{3+ 4}I_13/2 level reaches up to 4 ms for film containing 2 at% Er³⁺, while decreases to about 20 μs as the film is pumped by 488 nm. This confirmed that the energy transfer up-conversion process was the dominant transition at Er^{3+ 4}I_13/2 level. This may be of interest to improve the solar cells′ efficiency by placing this film at the rear of cell, converting the near-infrared photons between 1480 nm and 1580 nm to just above the Si bandgap.     

Time-resolved spectroscopy and energy transfer in Pr3+-doped Gd2(SO4)3·8H2O

The luminescence of Pr³⁺ in gadolinium sulfate hydrate is reported for 195 nm laser excitation. the Pr³⁺ ion acts as a sensitizer of the host lattice emission. The Pr³⁺Gd³⁺ energy transfer occurs in two different ways. In the octahydrate the transfer occurs from the lowest component of the 4f5d configuration of Pr³⁺, but in the samples with less water there is energy transfer from the¹ S _o level of Pr³⁺ to several Gd³⁺ levels. The Pr³⁺ emission in the two modifications is, of course, also strikingly different.Deceased 24 December 1994     

Broadband near infrared quantum cutting in Bi–Yb codoped Y2O3 transparent films on crystalline silicon

By a pulsed laser deposition technique the efficient broadband near-infrared downconversion Bi–Yb codoped crystallization Y₂O₃ transparent films have been grown successfully on Si (1 0 0) substrates. Upon excitation of ultraviolet photon varying from 300 to 400 nm, the near infrared quantum cutting has been obtained, which is originated from the transitions of the transition-metal Bi^{3+ 3}P₁ level to Yb^{3+ 2}F_5/2 level. The downconversion quantum efficiency of films is estimated to be 152%. The transparent Y₂O₃ films may have potential application in enhancing the conversion efficiency of crystalline Si solar cells.     

Near-infrared broadband luminescence and energy transfer in Bi–Tm–Er co-doped lanthanum aluminosilicate glasses

The Bi–Tm–Er co-doped SiO₂–Al₂O₃–La₂O₃ (SAL) glasses, which exhibited a broadband near-infrared (NIR) emission, were investigated by the optical absorption and photoluminescence spectra. A super broadband NIR emission extending from 0.95 to 1.6 μm with a full-width at half-maximum (FWHM) of 430 nm which covered the whole O, E, S, C and L bands, was observed in Bi–Tm–Er co-doped samples under 808 nm excitation, as a result of the overlap of the Bi-related emission band (centered at 1270 nm) and the emission from Tm^{3+ 3}H₄→³F₄ transition (1450 nm) as well as Er^{3+ 4}I_13/2→⁴I_15/2 transition (1545 nm). In addition, a super broadband emission with amplitude relatively flat from 0.95 to 2.1 μm has been observed. The possible energy transfer between Bi-related centers, Tm³⁺ ions and Er³⁺ ions was proposed.     

Resonance energy transfer in a dense array of II–VI quantum dots

Förster resonance energy transfer in inhomogeneous dense arrays of epitaxial CdSe/ZnSe quantum dots is demonstrated by time- and space-resolved photoluminescence spectroscopy. The specific feature of this process is the dipole–dipole interaction between the ground exciton levels of small quantum dots and the excited levels of large dots. This interaction brings efficient energy collection and spectral selection of a limited number of emitters. Results of theoretical modeling of optical transitions in spheroidal quantum dots with a Gaussian potential profile agree with the observed features of optical spectra induced by the change of the dominant energy transfer mechanism.     

Sensitized deep-ultraviolet up-conversion emissions of Gd3+ via Tm3+ and Yb3+ in hexagonal NaYF4 nanorods

Deep-ultraviolet (UV) up-conversion (UC) emissions in the region of 270～330 nm of Gd³⁺ under the excitation of a 980 nm laser diode in hexagonal Yb³⁺-Tm³⁺-Gd³⁺ triply doped NaYF₄ nanorods synthesized using a hydrothermal method are reported. Spectral analyses indicate that the UV UC emissions originate from highly efficient energy transfer from Yb³⁺ to Tm³⁺, then to Gd³⁺ions, and the intensity of the emission as well as the ratios of the emission peaks are strongly dependent on the doping concentrations and pump power. The materials are envisioned to have potential applications in anti-counterfeiting, optical and magnetic dual modal nanoprobes for biomedicine, solution-based scintillator materials and UV compact solid-state lasers.     

Energy transfer and frequency upconversion in Yb3+–Er3+-doped PbO-GeO2 glass containing silver nanoparticles

We report the infrared-to-visible frequency upconversion in Er³⁺–Yb³⁺-codoped PbO-GeO₂ glass containing silver nanoparticles (NPs). The optical excitation is made with a laser at 980 nm in resonance with the ²F_5/2→²F_7/2 transition of Yb³⁺ ions. Intense emission bands centered at 525, 550, and 662 nm were observed corresponding to Er³⁺ transitions. The simultaneous influence of the Yb³⁺→Er³⁺ energy transfer and the contribution of the intensified local field effect due to the silver NPs give origin to the enhancement of the whole frequency upconversion spectra.     

Selective enhancement of green upconversion emissions of Er3+:Yb3Al5O12 nanocrystals by high excited state energy transfer with Yb3+–Mn2+ dimer sensitizing

An innovative upconversion (UC) emissions route of Er³⁺ by Yb³⁺–Mn²⁺ dimer sensitizing in Er³⁺–Mn²⁺:Yb₃Al₅O₁₂ (YbAG) nanocrystals is reported here, which resulted in the selective enhancement of green UC emission and suppression of red UC emission by a 976 nm laser diode excitation. By codoping of Mn²⁺, the green UC emission intensity increased about 260 times, while the red UC emission intensity decreased about 20 times than that of Er³⁺:YbAG nanocrystals. It indicates that the green enhancement and red suppression arise from the high excited state energy transfer with |²F_7/2, ⁴T_1g> (Yb³⁺–Mn²⁺ dimer) to the ⁴F_7/2 (Er³⁺), which partly decreases the nonradiative processes happened in the lower levels of Er³⁺. The proposed sensitizing route here may constitute a promising step to realize high-efficient UC emissions of rare-earth ions doped oxides and significantly extend their scope of applications.     

Space-time curvature due to quantum vacuum fluctuations: An alternative to dark energy?

It is pointed out that quantum vacuum fluctuations may give rise to a curvature of space-time equivalent to the curvature currently attributed to dark energy. A simple calculation is made, involving plausible assumptions within the framework of quantized gravity, which suggests that the value of the dark energy density is roughly given by the product of Newton's constant times the quantity m⁶c⁴?−4, m being a typical mass of elementary particles. The estimate is compatible with observations.     

Near-infrared downconversion in Eu2＋ and Pr3＋ co-doped KSrPO4 phosphor

A novel near-infrared (NIR) downconversion (DC) phosphor KSrPO4 :Eu2+ , Pr3+ is synthesized by the conventional high temperature solid-state reaction. The Eu2+ acts as an efficient sensitizer for Pr3+ in the KSrPO4 host. With broad-band near-ultraviolet light excitation induced by the 4f→5d transition of Eu2+ , the characteristic NIR emission of Pr3+ , peaking at 974 nm and 1019 nm due to 3P0 → 1G4 and 1G4 → 3H4 transitions, is generated as a result of the energy transfer from Eu2+ to Pr3+ . The luminescence spectra in both the visible and the NIR regions and the decay lifetime curves of Eu2+ prove the energy transfer from Eu2+ to Pr3+ . This Eu2+ and Pr3+ co-doped KSrPO4 phosphor may be a promising candidate to modify the spectral mismatch behavior of crystalline solar cells and sunlight.     

Theoretical study of fluorescence resonant energy transfer dynamics in individual semiconductor nanocrystal–DNA–dye conjugates

Motivated by recent experimental studies of fluorescence resonant energy transfer (FRET), we consider the influence of the temperature-dependent microscopic spectral overlap and relative orientation of the transition dipoles of fluorophores on the nanosecond dynamics of photon statistics and energy transfer efficiency in semiconductor nanocrystal–DNA–organic dye conjugates using Monte-Carlo simulations. Our calculated mean energy transfer efficiencies are found to be well consistent with those measured in experiment at low temperatures. For the higher temperatures, our results demonstrate that the use of Förster radius estimated from the isotropic dynamic average value of 2/3 for the orientation parameter term may lead to overestimation of energy transfer efficiency for the cases of the rigid arrangement of fluorophore transition moments, and thereby deteriorate the precision of the analysis of donor–acceptor distances. Our theoretical results here underline the importance of a detailed understanding of the microscopic picture of FRET for exploiting this spectroscopic technique in various nano- and bio-applications.     

Ultraviolet to near-infrared downconversion in Yb3+–Na+ codoped Sr2CaWO6

This study investigated photoluminescent properties of Sr₂CaWO₆:Yb³⁺, Na⁺ phosphor. The samples were successfully synthesized via a solid-state reaction method with various doping concentrations. The phosphor can efficiently absorb ultraviolet photons of 250–350 nm and transfer its absorbed photon energy to Yb³⁺ ions. Then subsequent quantum cutting between WO₆ groups and Yb³⁺ ions takes place, down-converting an absorbed ultraviolet photon into two photons of 1007 nm radiations. Analyses of decay curves of different samples reveal an efficient energy transfer from WO₆ groups to Yb³⁺ ions. Cooperative energy transfer from host to Yb³⁺ ions is responsible for downconversion via lifetime analysis. Quantum efficiencies were calculated, and estimated maximum efficiency reached 190%. These phosphors combine wide wavelength absorption in the ultraviolet range with high quantum efficiency, enabling potential application of efficiency enhancement of Si solar cell.     

Determination of energy constants for Yb3＋/Er3＋ transfer and upconversion codoped phosphate glass

The energy transfer and cooperation upconversion processes are investigated in Yb3＋/Er3＋ codoped phos- phate glass. Based on the measured curves of output power versus incident power, the laser and spectroscopic parameters of the glass are fitted and analyzed. We focus on the resonant energy transfer constant k from Yb3＋ to Er3＋ as well as the cooperation upconversion coefficient Cup from 4113/2 of Era＋. The fitted k and Cup can give almost the same results for different thicknesses of glass disk with the same dop- ing concentrations. The determination of these parameters is helpful for the development of Yb3＋/Er3＋ codoped laser glass.     

Down-conversion process in Tb3+–Yb3+ co-doped Calibo glasses

The down-conversion process in Tb³⁺–Yb³⁺ co-doped Calibo glasses was studied. The emission, excitation and time-resolved measurements indicated the existence of an energy conversion through the excitation of Tb³⁺ ions to near-infrared emission by Yb³⁺ ions. The emission intensity dependence on excitation power confirms that the one-photon process is responsible for the Yb³⁺ emission. An enhanced Yb³⁺ emission was observed with Yb³⁺ doping and an optimal energy transfer efficiency of 32% was obtained before reaching near-infrared emission quenching. The mechanism of the non-resonant energy transfer from Tb³⁺ to Yb³⁺ is discussed in terms of the Tb³⁺–Yb³⁺ cross-relaxation and multiphonon decay processes.