Monochromic orange emission of Pr~(3+) ions in phosphate glass

Zinc strontium phosphate glasses doped with different trivalent praseodymium ion(Pr3t) concentrations are presented and their photoluminescence properties are investigated upon 442 nm excitation. With the Pr3tconcentration decreasing, the orange emission of Pr3t(1D2-3HJ) is enhanced steadily at the cost of its blue emission(3P1;0-3H4). Monochromic orange emission of Pr3tions is obtained when the Pr3tdoping is reduced to 0.05 mol.%. The mechanism controlling the monochromatic characteristic of Pr3temissions is supposed to be associated with the phonon-aided nonradiative relaxation process of Pr3t:3Pj→1D2, which depends on the Pr3tconcentration as well as the phonon energy of the glass matrix. Sodium zinc tellurite and barium gadolinium germinate glasses with the lower phonon energy are used as reference hosts to clarify this mechanism, and the results obtained support this suggestion.     

Theoretical studies on the one- and two-photon absorption properties of azulenylporphyrins and azulene-fused porphyrins

The electronic structures, one-photon absorption (OPA) and two-photon absorption (TPA) properties of the azulenylporphyrins and azulene-fused porphyrins have been comparatively studied by using DFT/B3LYP/6-31G(d) and the ZINDO/SDCI method. With the number of azulenyl groups increasing, the OPA wavelengths of all molecules are red-shifted in 400--600~nm and the two-photon absorption cross section is gradually enlarged. The azulene-fused structures facilitate an expanding conjugated area and increasing TPA cross section. The origin of TPA properties of studied compounds is studied with a two-level model. In summary, the azulene-fused porphyrins exhibit strong two-photon absorption.     

Nonlinear two-photon absorption properties induced by femtosecond laser with the films of two novel anthracene derivatives

Two novel anthracene derivatives containing 4-vinylpyridine (FPEA) and 2-vinylpyridine (TPEA) poly(methyl methacrylate) films are prepared on quartz glass substrates. Their nonlinear absorption properties are investigated by using a 120-fs, 800-nm Ti:sapphire femtosecond pulsed laser operating at a 1-kHz repetition rate. The unique nonlinear absorption properties of these new compounds are observed by utilizing a Z-scan system. These two-photon absorption (TPA) properties are proven by the two-photon fluorescence excited at 800 nm. The FPEA and TPEA films have nonlinear TPA coefficients of 0.164 and 0.148 cm/GW and the TPA cross sections of 3.345 × 10-48 and 3.081 × 10-48 cm4 ·s/photon, respectively. The influence of the chemical structures on the nonlinear TPA properties of the compounds is also discussed. The highly nonlinear TPA activities of the films implied that the new anthracene derivatives are suitable materials with promising applications in super-high-density three-dimensional data storage and nano- or microstructure fabrication.     

Two-Photon-Absorption Induced Superradiance of a New Organic Dye PSPS

The linear and nonlinear optical properties of a new two-photon absorption (TPA) dye,trans-4-(4‘-pyrrolidinyl styryl)-N-methyl pyridinium methyl sulfate (abbreviated as PSPS) is reported.Intense red superradiance with a peak located at 625nm can be observed from PSPS solution in benzyl alcohol when pumped by a focused picosecond laser beam operated at 1064nm.The lifetines of one-photon absorption (OPA) and TPA fluorescence were measured to be 370 and 384ps,respectively.The pulse widths of OPA and TPA superradiance were 60 and 58 ps,respectively.The highest net upconversion efficiency from the absorbed pump laser to the upconverted superradiance is 8.3% at the pump energy of 0.6 mJ.     

Broadband 1.5-um emission of erbium-doped TeO_2-WO_3-Nb_2O_5 glass for potential WDM amplifier

Erbium-doped glass showing the wider 1.5-um emission band is reported in a novel oxide system TeO2-WO3-Nb2O5 and their thermal stability and optical properties such as absorption, emission spectra, cross-sections and fluorescence lifetime were investigated. Compared with other glass hosts, the gain bandwidth properties of Er3+ in TWN glass is close to that of bismuth glasses, and larger than those of tellurite, germanate, silicate and phosphate glasses. The broad and flat 4I13/2-4I15/2 emission and the large stimulated emission cross-section of Er3+ ions around 1.5um can be used as host material for potential broadband optical amplifier in the wavelength-division-multiplexing (WDM) network system.     

Solvent effects on optical properties of a newly synthesized two-photon polymerization initiator： BPYPA

Time-dependent hybrid density functional theory in combination with polarized continuum model is applied to study the solvent effects on the geometrical and electronic structures as well as one- and two-photon absorption processes, of a newly synthesized asymmetrical charge-transfer organic molecule bis-（4-bromo-phenyl）-[4-（2-pyridin-4-yl-vinyl）phenyl]-amine （BPYPA）. There exist two charge-transfer states for the compound in visible region. The two-photon absorption cross section calculated by a three-state model and solvatochromic shift of the charge-transfer states are found to be solvent-dependent, where a nonmonotonic behaviour with respect to the polarity of the solvents is observed. The numerical results show that the organic molecule exhibits a rather large two-photon absorption cross section as compared with the compound 4-trans-[p-（N, N-Di-n-butylamino）-p-stilbenyl vinyl] pyridine （DBASVP） reported previously, and is predicted to be a good two-photon polymerization initiator. The hydrogen-bond effect is analysed. The computational results are in good agreement with the measurements.     

THz Generation by Optical Rectification and Competition with Other Nonlinear Processes

We present a study of the competition between tera-hertz （THz） generation by optical rectification in （110） ZnTe crystals, two-photon absorption, second harmonic generation and free-carrier absorption. The two-photon nonlinear absorption coefficient, second harmonic generation efficiency and free-carrier absorption coefficient in the THz range are measured independently. The incident pump field is shown to be depleted by two-photon absorption and the THz radiation is shown to be reduced, upon focusing, by free-carrier absorption. The reduction of the generated THz radiation upon tight focusing is explained, provided that one also takes into account diffraction effects from the sub-wavelength THz source.     

Two-Photon Absorption and Excited State Dynamics of Two Organic Molecules Containing Donor/Acceptor Moieties

Two new two-photon absorption （TPA） molecules, named SK-G1 and NT-G1, are synthesized and the photo- physical characteristics are investigated by using linear absorption spectra, one-photon fluorescence spectra and two-photon excited fluorescence spectra. Both the compounds exhibit TPA properties, and the TPA values determined by z-scan measurement are 10 GM and 39 GM for SK-G1 and NT-G1, respectively, at wavelength 80Ohm. Time-resolved spectroscopic techniques are employed to further explore the excited state dynamics of NT-G l with larger TPA cross section. The research results show that there is an ultrafast intraband energy transfer process （about 3ps） before the formation of charge transfer state with a relatively long lifetime.     

Two-Photon Fluorescence Property and Ultrafast Dynamics of Two Dipolar Compounds with Dipicolinate as Electron Acceptor

Linear and nonlinear photophysical properties of two novel dipolar compounds named as trans- dimethyl-4-[4＇-（N,N-dimethylamino）-styry1]-pyridin-2,6-dicarboxylate （Xiao-1） and trans-dimethyl-4-[4＇-（N,N-diphenylamino）-styry1]-pyridin-2,6-dicarboxylate （Xiao-2） are investigated by steady-state absorption and fluorescence spectroscopy, Z-scan and two-photon excited fluorescence measurements. Strong two-photon fluorescence emission and the pronounced positive solvatochromism are observed from two compounds. The two-photon absorption cross section of Xiao-2 is about 1.5 times larger than that of Xiao-1. One-color and two-color femtosecond pump-probe experiments are employed to investigate the excited state dynamics of two compounds. The relaxation lifetime of the intra-molecular charge transfer state is determined to be in the hundreds of picosecond domain for both the compounds in THF, and several tens of picosecond in DMSO solutions.     

Broadband 1.5-μm emission of erbium-doped TeO2-WO3-Nb2O5 glass for potential WDM amplifier

Erbium-doped glass showing the wider 1.5-/μm emission band is reported in a novel oxide system TeO2-WO3-Nb2O5 and their thermal stability and optical properties such as absorption,emission spectra,cross-sections and fluorescence lifetime were investigated.Compared with other glass hosts,the gain bandwidthproperties of Er3+ in TWN glass is close to that of bismuth glasses,and larger than those of tellurite,germanatc,silicate and phosphate glasses.The broad and flat 4I13/2 → 4I15/2 emission and the largestimulated emission cross-section of Er3+ ions around 1.5 μm can be used as host material for potentialbroadband optical amplifier in the wavelength-division-multiplexing(WDM)network system.     

Responsive mechanism and molecular design of di-2-picolylamine-based two-photon fluorescent probes for zinc ions

The properties of one-photon absorption(OPA), emission and two-photon absorption(TPA) of a di-2-picolylaminebased zinc ion sensor are investigated by employing the density functional theory in combination with response functions.The responsive mechanism is explored. It is found that the calculated OPA and TPA properties are quite consistent with experimental data. Because the intra-molecular charge transfer(ICT) increases upon zinc ion binding, the TPA intensity is enhanced dramatically. According to the model sensor, we design a series of zinc ion probes which differ by conjugation center, acceptor and donor moieties. The properties of OPA, emission and TPA of the designed molecules are calculated at the same computational level. Our results demonstrate that the OPA and emission wavelengths of the designed probes have large red-shifts after zinc ions have been bound. Comparing with the model sensor, the TPA intensities of the designed probes are enhanced significantly and the absorption positions are red-shifted to longer wavelength range. Furthermore, the TPA intensity can be improved greatly upon zinc ion binding due to the increased ICT mechanism. These compounds are potential excellent candidates for two-photon fluorescent zinc ion probes.     

Computational design of ratiometric two-photon fluorescent Zn2+ probes based on quinoline and di-2-picolylamine moieties

To improve two-photon absorption (TPA) response of a newly synthesized probe, a series of ratiometric two-photon fluorescent Zn²⁺ sensors based on quinoline and DPA moieties have been designed. The one-photon absorption, TPA, and emission properties of the experimental and designed probes before and after coordination with Zn²⁺ are investigated employing the density functional theory in combination with response functions. The design consists of two levels. In the first level of design, five probes are constructed through using several electron acceptors or donors to increase accepting or donating ability of the fluorophores. It shows that all the designed probes have stronger TPA intensities at longer wavelengths with respect to the experimental probe because of the increased intra-molecular charge transfer. Moreover, it is found that the probe 4 built by adding an acyl unit has the largest TPA cross section among the designed structures due to the form of longer conjugated length and more linear backbone. One dimethylamino terminal attached along the skeleton can improve TPA intensity more efficiently than two side amino groups. Therefore, in the second level of design, a new probe 7 is formed by both an acyl unit and a dimethylamino terminal. It exhibits that the TPA cross sections of probe 7 and its zinc complex increase dramatically. Furthermore, the fluorescence quantum yields of the designed probes 4 and 7 are calculated in a new way, which makes use of the relation between the computed difference of dipole moment and the measured fluorescence quantum yield. The result shows that our design also improves the fluorescence quantum yield considerably. All in all, the designed probes 4 and 7 not only possess enhanced TPA intensities but also have large differences of emission wavelength upon Zn²⁺ coordination and strong fluorescence intensity, which demonstrates that they are potential ratiometric two-photon fluorescent probes.     

Zn2+ responsive two-photon fluorescent probes based on branch structure: a computational investigation

A series of zinc ion fluorescent probes on the basis of multi-branched ligands were investigated in theory. The three-branched ligand TPPA (N,N,N′,N′-tetraphenyl-p-phenylenediamine) has better three-dimensional spatial localisation, which can detect zinc at the parts per million level. The complex coordinated with Zn²⁺ can show a significant improvement in two-photon absorption (TPA) cross-section in the near-infrared (NIR) excitation region. The calculated results reveal that the stability and sensitivity of Zn²⁺ complexes will be enhanced by increasing the number of branches. The selectivity of double phenyl-p-phenylenediamine (DPPA) ligand to Zn²⁺ will be better compared to Cd²⁺. With regard to the studied ligands single phenyl-p-phenylenediamine (SPPA), two connected single phenyl-p-phenylenediamine (2CSPPA), DPPA and TPPA, λ^EM_max shows a red-shift and ?^EM gets stronger upon the addition of Zn²⁺. Most of the molecules exhibit TPA peaks in the NIR region. The theoretical investigations demonstrate that DPPA-Zn²⁺ shows good TPA activity at a telecommunication wavelength.     

Isomerism and coordination mode effects on two-photon absorption of tris(picolyl)amine-based fluorescent probes for zinc ions

One-photon absorption and two-photon absorption(TPA) properties of three tris(picolyl)amine-based zinc ion sensors are investigated by employing the density functional response theory in combination with the polarizable continuum model.The different isomer and coordination geometry of each probe are taken into account. Special emphasis is placed on the effects of isomerism and the coordination mode on the optical properties. The intra-molecular charge transfer(ICT)properties are specified by natural bond orbital charge analysis. It is shown that the isomerism has non-negligible effects on TPA properties of free ligands. It is found that both the TPA wavelength and the cross section are highly dependent on the coordination mode. When the zinc ion connects with the picolyl unit in the middle of a ligand, the zinc complex has a large TPA intensity in a long wavelength range due to the increased ICT mechanism.     

Styryl Dyes as Two-Photon Excited Fluorescent Probes for DNA Detection and Two-Photon Laser Scanning Fluorescence Microscopy of Living Cells

Spectral-fluorescent properties of benzothiazole styryl monomer (Bos-3) and homodimer (DBos-21) dyes in presence of DNA were studied. The dyes enhance their fluorescence intensity in 2–3 orders of magnitude upon interaction with DNA. Studied styrylcyanines in DNA presence demonstrate rather high values of two-photon absorption (TPA) cross-section, which are comparable with the values of TPA cross section of the rhodamine dyes. An applicability of the styrylcyanines as probes for the fluorescence microscopy of living cells was studied. It was shown that both dyes are cell-permeable but homodimer dye DBos-21 produces noticeably brighter staining of HeLa cells comparing with monomer dye Bos-3. Molecules of DBos-21 initially bind to the nucleic acids- containing cell organelles (presumable mitochondria) and are able to penetrate into the cell nucleus. Thus, homodimer styryl DBos-21 dye is viewed as efficient stain for single-photon and two-photon excitation fluorescence imaging of living cells.     

Optical Properties of a New Two-photon Absorption Dye DEASPI

The two-photon absorption (TPA), TPA-induced frequency up-conversion emission, and two-photon pumped (TPP) frequency up-conversion lasing properties of a new synthesized dye Trans-4-［p-(N,N-diethylamino)styryl］-N-methylpyridinium iodide (DEASPI) were experimentally studied. This new dye has a moderate TPA cross-section of σ2=6.9×10-48 cm4*s/photon at 1064 nm, but exhibits a high lasing efficiency. The overall superradiant lasing conversion efficiency is as high as 10.7% at the pump energy of 2.14 mJ.     

Optical Properties of a New Two-photon Absorption Dye DEASPI

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The UV,blue and green up-conversion luminescence of PbF2+GeO2:Er2O3 pumped with 650 nm

A detailed study of the spectroscopic properties of the PbF₂+GeO₂:Er₂O₃ vitroceramic sample upon 650 nm excitation was investigated. The absorption, emission, excitation spectra, and time-resolved spectra have been measured. The up-conversion of red radiation (650 nm) into UV (368 nm and 379 nm), blue (406.8 nm) and green (522 nm and 540 nm) emissions is observed for Er³⁺ ions in the sample. The up-conversion process involves a two-photon absorption for the violet, blue, and green emission bands. A three-photon process happens for another violet (379 nm) band.     

两个新合成化合物EPVPC和OPVPC非线性光学特性的理论研究

在杂化密度泛函理论（DFT/B3LYP）的水平上，研究了最新实验室合成的两个化合物分子9-乙烷基-3-{2-[4-2-吡啶-4-乙烯基苯]-乙烯基}-9氢咔唑（EPVPC）和9-十八烷基-3-{2-[4-2-吡啶-4-乙烯基苯]-乙烯基}-9氢咔唑（OPVPC）的非线性光学特性。理论结果与现有的实验测量结果符合得的较好。利用扩展的少态模型方法计算了分子的双光子吸收截面，结果表明三态模型可以很好地描述它们的最大双光子吸收截面。数值模拟显示这两个化合物都具有较大的双光子吸收截面，并且，在低频范围内，OPVPC分子比EPVPC分子显示出较强的双光子吸收特性。