Enhancement of three-photon absorption cross-sections in a novel class of symmetrical charge transfer fluorene-based molecules

The three-photon absorption effect (3PA) of two novel symmetrical charge transfer fluorene-based molecules (abbreviated as BASF and BMOSF) has been determined by using a Q-switched Nd:YAG laser pumped with 38 ps pulses at 1064 nm in DMF. The measured 3PA cross-sections are 84 x 10(-78) and 114 x 10(-78) cm(6) s(2), respectively. The geometries and electronic excitations of these two molecules are systematically studied by PM3 and ZINDO/S methods. The relationships between 3PA cross-sections and intramolecular charge transfer are discussed micromechanically. The experimental and theoretical results have shown that the larger intramolecular charge transfer, which was characterized by the charge density difference between the ground state (SO) and the first excited state (S-I), the greater enhancement of the 3PA cross-sections. (c) 2005 Elsevier B.V. All rights reserved.

Large three-photon absorption cross-section in a novel class of bis-(N-carbazolyl) fluorene derivatives

Two novel symmetrical charge transfer fluorene derivatives (abbreviated as BCZF and BVCZF) with carbazole end-group as the donor moieties have been synthesized. Three-photon absorption cross-sections of these two compounds have been determined by using a Q-switched Nd:YAG laser pumped with 38 ps pulses at 1064 nm in DMF. The measured 3PA cross-sections are 140 x 10(-78) and 400 x 10(-78) cm(6) s(2) for BCZF and BVCZF, respectively. The geometries, electronic structures and electronic spectra of these two compounds are systematically studied by AM1 and ZINDO/S methods. On the basis of correct UV-vis spectra, the influence of different molecular structure on three-photon absorption cross-sections is discussed micromechanically. (C) 2005 Elsevier B.V. All rights reserved.

Large three-photon absorption and intramolecular charge transfer of the bis-donor fluorene-based molecules

Three-photon absorption (3PA) of two fluorene-based molecules with D-pi-D structural motifs (abbreviated as BPAF and BCZF) has been determined by using a Q-switched Nd: YAG laser pumped with 38 ps pulses at 1064 nm in DMF. The measured 3PA cross-sections are 222 and 140 x 10(-78) cm(6) s(2) for BPAF and BCZF, respectively. AM1 calculations show that attaching different donors changes the charge density distribution of the fluorene skeleton, and it is observed that the 3PA cross-section can be enhanced with increasing intramolecular charge transfer character, measured by the parameter Delta p(1)/Delta p(2)/Delta p(1)'. (c) 2005 Elsevier B.V. All fights reserved.

Two- and three-photon absorption in a novel fluorene-based compound

A novel symmetrical charge transfer fluorene-based compound 2,7-bis (4-methoxystyryl)-9, 9-bis (2-ethylhexyl)-9H-fluorene (abbreviated as BMOSF) was synthesized and its nonlinear absorption was investigated using two different laser systems: a 140-fs, 800-nm Ti:sapphire laser operating at 1-kHz repetition rate and a 38-ps, 1064-nm Nd:YAG pulsed laser operating at 10-Hz repetition rate, respectively. Unique nonlinear absorption properties in this new compound were observed that rise from multiphoton absorption. The nonlinear absorption coefficients were measured to be 6.02

Thiophene-fluorene derivatives with high three-photon absorption activities and their application to optical power limiting

The three-photon absorption (3PA) properties of two thiophene-fluorene derivatives (abbreviated as MOTFTBr and ATFTBr) have been determined by using a Q-switched Nd:YAG laser pumped wish 38ps pulses at 1064nm in DMF. The measured 3PA cross-sections are 152x10(-78)cm(6)s(2) and 139x10(-78)cm(6)s(2), respectively. The optimized structures were obtained by AM1 calculations and the results indicate that these two molecules show nonplanar structures, and attaching different donors has different effects on the molecular structure. The charge density distributions during the excitation were also systematically studied by using AM1 method. In addition, an obvious optical power limiting effect induced by 3PA has been demonstrated for both derivatives.

一种新的芴类衍生物的三光子吸收诱导荧光和光限幅效应研究

通过对新合成的芴的一种具有对称性衍生物4-2-（7-（4-氨基苯乙烯基）-9，9-二（2-乙基己基）-9H-芴-2-）乙烯基）苯胺（BASF）的DMF溶液的研究，发现其具有很强三光子吸收频率上转换荧光发射特性，实验测出上转换荧光的波长范围是456-775nm，在510nm处的荧光强度与入射光强的三次方成正比．在0．03mol／L的浓度下就有明显的三光子吸收诱导的光限幅效应．非线性吸收系数和吸收截面分别为y=4．34×10^20 cm^3／W^2和σ3=2．4×10^-39 cm^6／W^2．

A new strategy of enhancing two-photon absorption in benzothiazole-containing fluorene molecules: Introduction of auxiliary donor-acceptor effects

A series of benzothiazole-containing fluorene molecules have been designed and their one- and two-photon absorption properties have been investigated theoretically by using the ZINDO method. The effects of electron-excessive/deficient heterocyclic bridges as auxiliary donors (auxD)/acceptors (auxA) on TPA cross-sections were studied. The results show that the molecules with D-pi-auxA-A, D-aux D-pi-A, or D-auxD-pi-auxA-A structure types have large TPA cross-section, which can be a valuable strategy in the design of two-photon absorption materials. Also, a linear relationship between the first hyperpolarizability and the TPA cross-section is observed. (c) 2006 Elsevier B.V. All rights reserved.

Theoretical investigation on the one- and two-photon absorption properties for a series of symmetrical charge transfer fluorene-phenylene and fluorene-thiophene derivatives

One- and two-photon absorption properties of a series of fluorene derivatives with symmetrical charge transfer D-IT-D and A-IT-A structural motifs have been theoretically investigated with ZINDO/S method. The optimized structures and the characterization of frontier molecular orbitals were obtained by using AMI calculations. Two-photon absorption properties of molecules have been studied using three-state model. The calculation results have shown that fluorene-thiophene derivatives exhibit larger two-photon absorption cross-section as compared with other studied molecules. To illustrate the results, the crucial effects of thiophene ring on fluorenethiophene derivatives and the net charge changes on the pi-conjugated bridges are analyzed theoretically. (c) 2006 Elsevier B.V. All rights reserved.

Near infrared broadband emission from bismuth-dysprosium codoped chalcohalide glasses

We investigate the broadband infrared emission of bismuth doped and bismuth/dysprosium codoped chalcohalide glasses. It is found that the bismuth/dysprosium codoping can drastically enhance the fluorescence as compared with either bismuth or dysprosium doped glasses. Meanwhile, the full width at half maximum of bismuth/dysprosium codoped glasses is over 170 nm, which is the largest value among all the reported rare-earth doped chalcohalide glasses. An ideal way for energy consumption between bismuth and dysprosium ions is supposed. Such improved gain spectra of both bismuth and dysprosium ions may have potential applications in developing broadband fibre amplifiers.

Broadband near-infrared emission from transparent Ni2+-doped silicate glass ceramics

Transparent Ni2+-doped MgO-Al2O3-TiO2-SiO2 glass ceramics were prepared, and the optical properties of Ni2+-doped glass ceramics were investigated. Broadband emission centered at 1320 nm was observed by 980 nm excitation. The longer wavelength luminescence compared with Ni2+-doped Li2O-Ga2O3-SiO2 glass ceramics is ascribed to the low crystal field hold by Ni2+ in MgO-Al2O3-TiO2-SiO2 glass ceramics. The change in optical signals at the telecommunication bands with or without 980 nm excitation was also measured when the seed beam passes through the bulk gain host.(C) 2007 American Institute of Physics.

Spectroscopic properties of neodymium doped high silica glass and aluminum codoping effects on the enhancement of fluorescence emission

Nd3+ -codoped and Al3+-Nd3+-codoped high silica glasses have been prepared by sintering nanoporous glasses impregnated with Nd3+ stop and Al3+ ions. The Judd-Ofelt intensity parameters Omega(2,4,6) of Nd3+-doped high silica glasses were obtained and used to analyze aluminum codoping effects. Fluorescence properties of Nd3+-doped high silica glasses strongly depend on the Al3+ concentration. While Nd3+ ion absorption and emission intensities of obviously increase when aluminum is added to Nd3+-doped high silica glasses, fluorescence lifetimes decrease and aluminum codoping has almost no influence on the radiative quantum efficiencies. This indicates that aluminum codoping is responsible for an anti-quenching effect through a local modification of rare-earth environments rather than through physical cluster dispersion.

Cooperative downconversion in GdAl3(BO3)(4): RE3+,Yb3+ (RE=Pr, Tb, and Tm)

An efficient near-infrared (NIR) quantum cutting (QC) in GdAl3(BO3)(4):RE3+,Yb3+ (RE=Pr, Tb, and Tm) phosphors has been demonstrated, which involves the conversion of the visible photon into the NIR emission with an optimal quantum efficiency approaching 200%, by exploring the cooperative downconversion mechanism from RE3+ (RE=Pr, Tb, and Tm) excitons to the two activator ions, Yb3+. The development of NIR QC phosphors could open up a new approach in achieving high efficiency silicon-based solar cells by means of downconversion in the visible part of the solar spectrum to similar to 1000 nm photons with a twofold increase in the photon number. (c) 2007 American Institute of Physics.

Er3+离子浓度对Er3+/Yb3+共掺磷酸盐玻璃上转换 发光的影响

The upconversion emission of Er³⁺/Yb³⁺ codoped phosphate glass with 980 nm excitation was investigated. In the glass Er³⁺ concentration has a great influence on the intensity and the ratio of green and red light upconversion. The slope of the green luminenscence intensity as a function of pumping power ranges from 2.52 to 3.27, is the evidence of the three photon excitation process. The three photon process can also be concluded from excitation spectra when emission wavelength is 545 nm. The effect of Er³⁺ concentration is also discussed.

Energy transfer and infrared-to-visible upconversion luminescence of Er3+/Yb3+-codoped halide modified tellurite glasses

We report on the energy transfer and frequency upconversion spectroscopic properties of Er3+-doped and Er3+/Yb3+-codoped TeO2-ZnO-Na2O-PbCl2 halide modified tellurite glasses upon excitation with 808 and 978 nm laser diode. Three intense emissions centered at around 529, 546 and 657 nm, alongwith a very weak blue emission at 4 10 nm have clearly been observed for the Er3+/Yb3+-codoped halide modified tellurite glasses upon excitation at 978 nm and the involved mechanisms are explained. The quadratic dependence of fluorescence on excitation laser power confirms the fact that the two-photon contribute to the infrared to green-red upconversion emissions. And the blue upconversion at 410 nm involved a sequential three-photon absorption process. (c) 2005 Elsevier Ltd. All rights reserved.