Two- and three-photon absorption and frequency upconverted emission of silicon quantum dots

In this communication, we present the experimental results of two- and three-photon excitation studies on silicon quantum dots (QDs) in chloroform (as well as in water) by using femtosecond laser pulses with wavelengths of 778 and 1335 nm and a pulse duration approximately 160 fs. The photoluminescence spectral distributions are nearly the same upon one-, two-, and three-photon excitation. With one- and two-photon excitation, the temporal relaxation measurements of photoluminescence emission manifest the same multiexponential decay behavior in the time range from 0.05 ns to 15 mus, characterized by three successive decay constants: 0.75 ns, 300 ns, and 5 mus, respectively. Finally, the two-photon absorption spectrum in the spectral range of 650-900 nm and the three-photon absorption spectrum in the spectral range of 1150-1400 nm have been measured.     

Giant two-photon absorption in bilayer graphene

We present a quantum perturbation theory on two-photon absorption (2PA) in monolayer and bilayer graphene which is Bernal-stacked. The theory shows that 2PA is significantly greater in bilayer graphene than monolayer graphene in the visible and infrared spectrum (up to 3 μm) with a resonant 2PA coefficient of up to ～0.2 cm/W located at half of the bandgap energy, γ(1) = 0.4 eV. In the visible and terahertz region, 2PA exhibits a light frequency dependence of ω(-3) in bilayer graphene, while it is proportional to ω(-4) for monolayer graphene at all photon energies. Within the same order of magnitude, the 2PA theory is in agreement with our Z-scan measurements on high-quality epitaxial bilayer graphene deposited on SiC substrate at light wavelength of 780 and 1100 nm.     

CdTe量子点的微波合成及其在双光子显微成像中的应用

采用微波辐射加热的方法,以亚碲酸钠(Na2TeO3)作碲源,以谷胱甘肽(GSH)作稳定剂,在水相中合成出高质量的CdTe量子点。所合成量子点的发射波长从515～630nm可调,荧光量子产率(PLQYs)最高达95%。利用X射线粉末衍射(XRD)、高分辨透射电镜(HRTEM)、紫外-可见吸收光谱(UV-Vis)和荧光发射光谱(PL)等技术表征产物的物相结构和光学性质。用双光子激发荧光法研究CdTe量子点的双光子吸收性质。用双光子激发荧光成像技术,以发红光的CdTe量子点作为双光子荧光探针成功标记了人肺腺癌细胞(A549)。     

Novel triphenylamine-cored two-photon absorbing dyes for labeling of biomolecules

Two novel, V-shaped and Y-shaped dipicolinate derivatives branched from triphenylamine, {4-[(E)-2-(2,6-dimethoxycarbonylpyridin-4-yl)vinyl]}-N-phenyl-N-{4-[(E)-2-(2,6-dimethoxycarbonylpyridin-4-yl)vinylphenyl]}aniline (1) and {4-[(E)-2-(2,6-dimethoxycarbonylpyridin-4-yl) vinyl]}-N,N-bis {4-[(E)-2-(2,6-dimethoxycarbonyl pyridin-4-yl)vinylphenyl]}aniline (2) were synthesized. These compounds were designed for large two-photon absorption and in particular for labeling of biomolecules. Their linear absorption, fluorescence properties and their two-photon absorption properties as well as two-photon fluorescence cell imaging were examined. When excited at 800 nm, the two-photon absorption cross-section values of chromophores 1 and 2 in THF were 208 GM, 376 GM, respectively. These two-photon absorbing dyes possess reasonable water solubility, strong chelating ability and display a large set of reactivity for coupling to biomolecules, which are apparently due to the two methoxycarbonyl groups in pyridine ring. This work suggests that chromophores 1 and 2 are promising labels potentially applicable for the tracking of biomolecules using two-photon scanning microscopy.     

Optimization of band structure and quantum-size-effect tuning for two-photon absorption enhancement in quantum dots

The two-photon absorption, 2PA, cross sections of PbS quantum dots, QDs, are theoretically and experimentally investigated and are shown to be enhanced with increasing quantum confinement. This is in contrast to our previous results for CdSe and CdTe QDs where the reduced density of states dominated and resulted in a decrease in 2PA with a decrease in QD size. Qualitatively this trend can be understood by the highly symmetric distribution of conduction and valence band states in PbS that results in an accumulation of allowed 2PA transitions in certain spectral regions. We also measure the frequency nondegenerate 2PA cross sections that are up to five times larger than for the degenerate case. We use a k·p four-band envelope function formalism to model the increasing trend of the two-photon cross sections due to quantum confinement and also due to resonance enhancement in the nondegenerate case.     

Synthesis and two-photon absorption property of new π-conjugated dendritic fluorophores containing styrylpyridyl moieties

Four new multi-branched two-photon absorption chromophores, namely 1-(4-bromobenzal)-3,5-bis(4-((E)-2-(pyridin-4-yl)vinyl)phenyl)benzene (4), tris(4-((E)-2-(pyridin-4-yl)vinyl)phenyl)-benzene (5), 6-chloro-N²,N⁴-bis(4-((E)-2-(pyridin-4-yl)vinyl)phenyl)-1,3,5-triazine-2,4-diamine (6), tris-[4-(2-pyridin-4-yl-vinyl)-phenyl]-amine (7), have been synthesized and characterized. One-photon fluorescence, fluorescent quantum yields and two-photon fluorescence have been investigated. The experimental two-photon absorption cross-sections of 4–7 in DMF are 6, 11, 13 GM (pumped by 740 nm laser) and 19 GM (pumped by 800 nm laser), respectively. The calculated two-photon absorption cross-sections of 4–7 are 5.41, 7.67, 9.57 and 76.14 GM, respectively. The two-photon induced fluorescent peak wavelengths of 4–7 in DMF are 421, 425, 474 and 534 nm pumped by 680, 680, 740 and 800 nm laser, respectively. The results show that molecule 7 is a good two-photon absorption fluorophore possessing long two-photon fluorescent lifetime, good fluorescent quantum yield and large two-photon absorption cross-section. The two-photon absorption peak wavelength of molecule 7 is at 800 nm, which is favourable for initiating two-photon photopolymerization.     

Limitations arising from two-photon absorption of solvent in pulsed-laser thermal lens detection: determination of the two-photon absorption coefficient of ethanol at 266 nm

Two-photon absorption of the solvent under pulsed-laser excitation at 266 nm produces a high background thermal lens signal interfering with the analyte signal. Discrimination of both solvent and analyte signals along with calibration of the photothermal response has allowed the determination of the two-photon absorption coefficient of ethanol. The obtained value, 3.0x10(-10) cm W-1, is close to the literature values obtained from transmittance measurements using picosecond or femtosecond laser pulses.     

The empirical correlation between size and two-photon absorption cross section of CdSe and CdTe quantum dots

The tuning of CdSe quantum dot (QDs) sizes, and consequently their corresponding two-photon absorption (TPA) cross section, has been systematically investigated. As the size (diameter) of the quantum dots increases, the TPA cross section is found to be empirically related via a power-law proportionality of 3.5+/-0.5 and 5.6+/-0.7 to the diameters of CdSe and CdTe QDs, respectively. The results are tentatively rationalized via a theoretical model of two-photon excitation properties in a system incorporating excitons and defects.     

Stimulated photoluminescence and optical limiting in CdI2

High quality single crystal of cadmium iodide (CdI₂) grown from the melt by the refining method was studied under ruby laser excitation. The low temperature (LNT) emission spectrum of the crystal was recorded by using a spectrofluorometer. The spectrum appeared a structureless emission with its peak in the green spectral region. Analysis of photoluminescence (PL) measurements in the crystal showed a quadratic dependence of the PL peak intensity on incident laser power. This might be explained with the existence of self-trapped excitons in the crystal. In the desired energy ranges of interest, the emission intensity of CdI₂ was found to depend on the square of the laser power, indicating the biphotonic process of two-photon excitation, i.e., the nonlinear response is due to a second-order process, or two-photon absorption (2PA) process. The optical limiting properties of CdI₂ were studied using 7 ns pulses from the laser. This investigation leads to the conclusion that apart from the 2PA reverse saturable absorption (RSA) is another mechanism for optical limiting in CdI₂.     

Excited-state absorption and anisotropy properties of two-photon absorbing fluorene derivatives

The electronic structure of fluorene derivatives N-(7-benzothiazol-2-yl-9,9-bis-decyl-9H-fluoren-2-yl)-acetamide (1); 9,9-didecyl-2,7-bis-(N,N-benzothiazoyl)fluorene (2); 4,4'-{[9,9-bis(ethyl)-9H-fluorene-2,7-diyl]di-2,1-ethenediyl}bis(N,N-diphenyl)benzeneamine (3); and 4,4',4"{[9,9-bis(ethyl)-9H-fluorene-2,4,7-triyl]tri-2,1-ethenediyl}tris(N,N-diphenyl)benzeneamine (4) were investigated by a steady-state spectral technique, quantum-chemical calculations, and a picosecond pump-probe method. These derivatives are of interest for their relatively high two-photon absorption. The steady-state excitation anisotropy spectra reveal the nature of the ground-state absorption bands. Semiempirical quantum-chemical calculations of the fluorene derivatives (AM1, ZINDO/S) show good agreement with experimental data. The spectral positions and alignment of various electronic transitions of derivatives 1-4 were estimated from their excited-state absorption and anisotropy spectra.     

Two-photon absorption in diazobenzene compounds

An investigation is made into molecular design strategies to enhance the two-photon absorption (2PA) of organic materials by measuring the 2PA cross-section of diazoaromatic compounds with the femtosecond pulses Z-scan technique at 775 nm. These diazo dyes exhibit a moderate 2PA cross-section, of the order of 300 GM, comparable to those of regular azoaromatic compounds. The increase in the π-electron bridge in the diazoaromatic compounds does not bring, therefore, substantial increase to the measured 2PA intensities, while the main factor to enhance the 2PA cross-section is the presence of charge donor and acceptor groups. It is concluded that current molecular design strategies are unlikely to produce azoaromatic compounds that are useful for applications requiring very high 2PA coefficients.     

含杂芴与噁二唑分子的p-n结与分子双光子吸收性能关系的研究

研究了若干个含杂芴与噁二唑分子的线性和非线性光谱性能.分别在飞秒钛宝石激光器泵浦下,通过开孔Z-scan技术和双光子荧光法研究了分子的双光子吸收性能;结合理论计算考察分子基态与激发态分子内电荷转移、分子p-n结对双光子吸收的影响.     

Frequency upconversion and two-photon absorption of salicylaldehyde azine 1

Two-photon absorption and two-photon excitation fluorescence of salicylaldehyde azine 1 crystals were investigated. It was observed an intense visible fluorescence when this material was excited with a laser tuned at the near infrared region. Varying the laser intensity we characterized this phenomenon as a simultaneous two-photon laser absorption process. Using open aperture Z-scan measurements we characterized this two-photon absorption phenomenon and measured the value of the two-photon absorption cross-section of this molecule to be equal to 87 GM. Our results indicate that this is a promising organic material aiming nonlinear photonics applications.     

Nonlinear transmission and excited-state absorption in fluorene derivatives

The nonlinear transmission and the excited-state absorption spectra of three fluorene derivatives exhibiting large two-photon absorptivity were measured by the third harmonic of a picosecond Nd:YAG laser. We analyzed their capability for exhibiting stimulated emission in polar solvents and found that asymmetrical fluorene compounds with a diphenylamino substituent exhibited large Stokes shifts (approximately 8000 cm(-1)), high quantum yields (approximately 0.9-1.0), and no optical gain over their entire fluorescence spectral region. In contrast, a symmetrical fluorene derivative with vinylphenylbenzothiazole substituents in positions 2 and 7 underwent lasing under one-photon excitation by use of picosecond pulsed irradiation.     

Homogeneous immunoassay based on two-photon excitation fluorescence resonance energy transfer

A two-photon excitable small organic molecule (abbreviated as TP-NH 2) with large two-photon absorption cross section and competitive fluorescence quantum yield was prepared, which emitted fluorescence in the visible region upon excitation at 800 nm. Using the TP-NH 2 molecule as an energy donor, a two-photon excitation fluorescence resonance energy-transfer (TPE-FRET) based homogeneous immunoassay method was proposed. The donor and the acceptor (DABS-Cl, a dark quencher) were labeled to bovine serum albumin (BSA) separately, and anti-BSA protein was determined by employing an antibody bridging assay scheme. Rabbit anti-BSA serum containing other biomolecules was intentionally used as the sample to introduce interference. A parallel assay was performed using the traditional one-photon excitation FRET model, which failed to carry out quantitative determination due to the serious background luminescence arising from those biomolecules in the sample. The TPE-FRET model showed its strong ability to overcome the problem of autofluorescence and provided satisfying analytical performance. Quite good sensitivity and wide linear range (0.05-2.5 nM) for anti-BSA protein was obtained. The results of this work suggest that TPE-FRET could be a promising technique for homogeneous assays excluding separation steps, especially in complicated biological sample matrixes.     

Size-dependent electron transfer from PbSe quantum dots to SnO2 monitored by picosecond Terahertz spectroscopy

We report the direct and unambiguous determination of electron transfer rates and efficiencies from PbSe quantum dots (QDs) to mesoporous SnO2 films. We monitor the time-dependent electron density within the oxide with picosecond time resolution using Terahertz spectroscopy, following optical excitation of the QDs using a femtosecond laser pulse. QD-oxide electron transfer occurs with efficiencies of ～2% in our samples under 800 nm pumping with a marked dependence on QD size, ranging from ～100 ps injection times for the smallest, ～2 nm diameter QDs, to ～1 ns time scale for ～7 nm QDs. The size-dependent electron transfer rates are modeled within the framework of Marcus theory and the implications of the results for device design are discussed.     

High-density optical data storage with one-photon and two-photon near-field fluorescence microscopy

A spatially localized photochemical reaction induced by near-field femtosecond laser pulses is demonstrated on a nanometer scale and used for high-density optical data storage. Recorded domains down to 120 and 70 nm are obtained with one-photon and two-photon excitation, respectively. It is shown that the local-field confinement that is due to the quadratic dependence of two-photon excitation on light intensity has the potential to increase the near-field optical storage density.     

Two-photon excited coherence gratings in inhomogeneously broadened organic solid

For the first time a frequency-domain grating is observed in the visible region as a result of coherence excited by two-photon absorption of time-delayed near-IR femtosecond pulses in an inhomogeneously broadened organic solid-state system. The grating appears in chlorin (2,3-dihydroporphyrin)-doped polymer film at low temperature and is detected in two different ways. First, modulation is observed in the pure electronic fluorescence band upon 'resonant' two-photon excitation with laser carrier frequency equal to one-half of the fluorescence band maximum. Second, upon long exposure time at half of the transition frequency, a persistent spectral hole with periodic structure is observed. The two-photon absorption spectrum of the chlorin molecule in the spectral range 1130–1310nm is also presented for the first time.     

Polarized Fluorescence in NADH Two-Photon Excited by Femtosecond Laser Pulses in the Wavelength Range of 720–780 nm

Technical Physics Letters - The decay of polarized fluorescence in coenzyme NADH in aqueous-methanol solution under two-photon excitation by femtosecond laser pulses within the spectral range of...     

Two-photon fluorescence excitation spectroscopy by pulse shaping ultrabroad-bandwidth femtosecond laser pulses

A fast and automated approach to measuring two-photon fluorescence excitation (TPE) spectra of fluorophores with high resolution (~2 nm) by pulse shaping ultrabroad-bandwidth femtosecond laser pulses is demonstrated. Selective excitation in the range of 675-990 nm was achieved by imposing a series of specially designed phase and amplitude masks on the excitation pulses using a pulse shaper. The method eliminates the need for laser tuning and is, thus, suitable for non-laser-expert use. The TPE spectrum of Fluorescein was compared with independent measurements and the spectra of the pH-sensitive dye 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS) in acidic and basic environments were measured for the first time using this approach.