Transient Grating Signal Research Articles

Automated transient grating spectroscopy mapping and signal control for large samples.

We present developments for the mapping of large areas using transient grating spectroscopy (TGS) that allow for smoother, larger, autonomous measurements of material samples. The addition of a precise linear stage in the direction parallel to laser sampling coupled with signal optimizing control allows for hands free, self-correcting measurements. In addition, the simplification of the sample holding design to a form that is small enough to mount directly to the linear stage exhibits a straightforward, low-cost solution for automated TGS applications. This capability is demonstrated by taking large uninterrupted maps of gradient wafers, and the results are validated on calibrated tungsten samples and control TGS samples from gradient wafers.

Photodecarboxylation of ketoprofen studied by transient absorption spectroscopy and transient grating method: Estimation of the partial molar volume of carbon dioxide

The photoreaction of ketoprofen, a widely used nonsteroidal anti-inflammatory drug (NSAID), was intensively investigated in methanol by transient absorption spectroscopy and transient grating (TG) method. From quantitative analyses of the transient absorption and of the TG signal due to CO2, we successfully determined the partial molar volume of CO2 to be 46 ± 2 cm3 mol−1. With the partial molar volume of CO2 obtained in this work, the reaction quantum yield of photodecarboxylation of other NSAIDs can be estimated from only the TG signal. The approach with the TG method would be a new tool for evaluating photoreactivity of NSAIDs.

Investigation of capillary waves and thermal diffusion at the air–liquid interface of imidazolium-cation-based ionic liquids using transient grating spectroscopy

The capillary wave and thermal diffusion at the gas–liquid interface of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide [Cnmim][NTf2] (n = 4, 8, 12; where n indicates the number of carbons in the alkyl chain) were investigated using interface-selective transient grating (TG) spectroscopy. At the interface, the TG signal exhibited capillary wave damping (with no capillary wave oscillation). Moreover, the capillary wave damping constant was greater than that predicted by the hydrodynamic theory; the deviation increased with the cation alkyl-chain length. The thermal diffusivities at the gas–liquid interface of [C8mim][NTf2] and [C12mim][NTf2] were lower than those in the bulk, whereas both the values at the interface and in the bulk were similar for [C4mim][NTf2]. The difference is possibly owing to the formation of a layered structure at the interface.

Molecular diffusion and aggregate formation of photoproducts from ketoprofen in aqueous solutions

We investigated photochemical reaction of deprotonated ketoprofen (KP−) in aqueous solutions at neutral pH by transient grating (TG) method. At low excitation fluences or KP− concentrations, the TG signal showed molecular diffusion of KP− and its photoproducts such as hydrogen carbonate and 3-ethylbenzophenone (3-EBP). On the other hand, at high fluences or high KP− concentrations, the aggregation dynamics of 3-EBP was observed. The hydrodynamic radii of the formed aggregates reached beyond 5 nm, and their formation was driven in water-rich solutions.

All-reflective self-referenced spectral interferometry for single-shot measurement of few-cycle femtosecond pulses in a broadband spectral range

An all-reflective self-referenced spectral interferometry based on the transient grating (TG) effect is proposed for single-shot measuring of the amplitude and phase of ultrashort pulses in a broadband spectral range. Except for a thin third-order nonlinear medium, which was used to generate the TG signal, no transmitted optics were used in the proposed device, and few-cycle pulses in a broad spectral range from deep UV to mid-IR can be characterized. With a homemade compact and alignment-free device, a 5.0 fs pulse at 800 nm corresponding to about two cycles and a 14.3 fs pulse at 1800 nm corresponding to less than three cycles were successfully characterized.

Thermoelasticity of Nanoscale Silicon Carbide Membranes Excited by Extreme Ultraviolet Transient Gratings: Implications for Mechanical and Thermal Management

Understanding and controlling the thermal transport at nanoscale is a key ingredient for the development of future nanoelectronical devices. In this study of thin silicon carbide (SiC) membrane we demonstrate the potential of free electron laser extreme ultraviolet (EUV) transient grating (TG) technique as contactless probe for thermoelastic response at length scales of 84 nm, where the Fourier heat diffusion law is no longer valid. The results have revealed that the mechanical behavior of the system can be fully described in the framework of Lamb waves. Moreover, by use of a bidimensional spatial detector to measure the TG signal, a new feature is the observed, time dependence in the emission angle of the transient diffraction, correlated to the transient grating signal intensity.

Transient grating spectroscopy of β-carotene pumped with spectrally chirped pulses

Nonlinear optical responses of β-carotene were investigated upon excitation using chirped pulses. We especially focus on spectrally resolved transient grating (TG) signals to discuss the influence of the spectral chirp over a wide spectral range. A significant change in the TG signal was observed when negatively chirped pulses were used. The experimental results were qualitatively reproduced by employing the Brownian oscillator model. The relationship between the wave packet motion in the excited state and spectral chirp is discussed. It is concluded that the third order nonlinear optical response reflects the competition between the spectral chirp and the energy separation of the potential curves.

Synergetic Enhancement of Light-Matter Interaction by Nonlocality and Band Degeneracy in ZnO Thin Films.

This study aims to reveal the full potential of ZnO as an ultrafast photofunctional material. Based on nonlocal response theory to incorporate the spatially inhomogeneous quality of the samples coupled with experimental observations of linear and nonlinear optical responses, we establish the ultrafast radiative decay of excitons in ZnO thin films that reaches the speed of excitonic dephasing at room temperature in typical semiconductors at a couple tens of femtoseconds. The consistency between the observed delay-time dependence of the transient-grating signals and the theoretical prediction reveals that the ultrafast radiative decay is due to the synergetic effects of the giant light-exciton interaction volume and the radiative coupling between multicomponent excitons.

Probing Globular Protein Self-Assembling Dynamics by Heterodyne Transient Grating Experiments

In this work, we studied the propagation of ultrasonic waves of lysozyme solutions characterized by different degrees of aggregation and networking. The experimental investigation was performed by means of the transient grating (TG) spectroscopy as a function of temperature, which enabled measurement of the ultrasonic acoustic proprieties over a wide time window, ranging from nanoseconds to milliseconds. The fitting of the measured TG signal allowed the extraction of several dynamic properties, here we focused on the speed and the damping rate of sound. The temperature variation induced a series of processes in the lysozyme solutions: Protein folding-unfolding, aggregation and sol–gel transition. Our TG investigation showed how these self-assembling phenomena modulate the sound propagation, affecting both the velocity and the damping rate of the ultrasonic waves. In particular, the damping of ultrasonic acoustic waves proved to be a dynamic property very sensitive to the protein conformational rearrangements and aggregation processes.

Tracking intra-molecular electron and vibrational energy redistribution by time and frequency resolved transient grating spectroscopy

Theoretical calculation results show that electron flow occurs from xanthene to phenyl ring within the Rh101+ after its electronic transition from ground state (S0) to first excited state (S1). Time and frequency resolved transient grating (TG) spectroscopy is then conducted to seek the experimental evidence. Through Fourier analysis at different wavelengths of TG signal and their specific value spectra, vibrational enhancement corresponding to electron acceptor chromophore (phenyl ring) is observed. So the ultrafast vibrational energy redistribution process is detected experimentally and the direction of electron flow is confirmed.

Local vibrational coherences drive the primary photochemistry of vision.

The role of vibrational coherence-concerted vibrational motion on the excited-state potential energy surface-in the isomerization of retinal in the protein rhodopsin remains elusive, despite considerable experimental and theoretical efforts. We revisited this problem with resonant ultrafast heterodyne-detected transient-grating spectroscopy. The enhanced sensitivity that this technique provides allows us to probe directly the primary photochemical reaction of vision with sufficient temporal and spectral resolution to resolve all the relevant nuclear dynamics of the retinal chromophore during isomerization. We observed coherent photoproduct formation on a sub-50 fs timescale, and recovered a host of vibrational modes of the retinal chromophore that modulate the transient-grating signal during the isomerization reaction. Through Fourier filtering and subsequent time-domain analysis of the transient vibrational dynamics, the excited-state nuclear motions that drive the isomerization reaction were identified, and comprise stretching, torsional and out-of-plane wagging motions about the local C11=C12 isomerization coordinate.

Femtosecond Heterodyne Transient-Grating Studies of Nonradiative Decay of the S2 (1(1)Bu(+)) State of β-Carotene: Contributions from Dark Intermediates and Double-Quantum Coherences.

Femtosecond transient-grating spectroscopy with heterodyne detection was employed to characterize the nonradiative decay pathway in β-carotene from the S2 (1(1)Bu(+)) state to the S1 (2(1)Ag(-)) state in benzonitrile solution. The results indicate definitively that the S2 state populates an intermediate state, Sx, on an ultrafast time scale prior to nonradiative decay to the S1 state. Numerical simulations using the response function formalism and the multimode Brownian oscillator model were used to fit the absorption and dispersion components of the transient-grating signal with a common set of parameters for all of the relevant Feynman pathways, including double-quantum coherences. The requirement for inclusion of the Sx state in the nonradiative decay pathway is the observed fast rise time of the dispersion component, which is predominantly controlled by the decay of the stimulated emission signal from the optically prepared S2 state. The finding that the excited-state absorption spectrum from the Sx state is significantly red-shifted from that of S2 and S1 leads to a new assignment for the spectroscopic origin of the Sx state. Rather than assigning Sx to a discrete electronic state, such as the (1)Bu(-) state suggested in previous work, it is proposed that the Sx state corresponds to a transition-state-like structure on the S2 potential surface. In this hypothesis, the 12 fs time constant for the decay of the S2 state corresponds to a vibrational displacement of the C-C and C═C bond-length alternation coordinates of the conjugated polyene backbone from the optically prepared Franck-Condon structure to a potential energy barrier on the S2 surface that divides planar and torsionally displaced structures. The lifetime of the Sx state would be associated with a subsequent relaxation along torsional coordinates over a steep potential energy gradient toward a conical intersection with the S1 state. This hypothesis leads to the idea that twisted structures with intramolecular charge-transfer character along the S2 torsional gradient are active in excitation energy-transfer mechanisms to (bacterio)chlorophyll acceptors.

Characterization of hot carrier cooling and multiple exciton generation dynamics in PbS QDs using an improved transient grating technique

Multiple exciton generation (MEG) dynamics in colloidal PbS quantum dots (QDs) characterized with an improved transient grating (TG) technique will be reported. Only one peak soon after optical absorption and a fast decay within 1 ps can be observed in the TG kinetics when the photon energy of the pump light hν is smaller than 2.7Eg (Eg: band gap between LUMO and HOMO in the QDs), which corresponds to hot carrier cooling. When hν is greater than 2.7Eg, however, after the initial peak, the TG signal decreases first and soon increases, and then a new peak appears at about 2 to 3 ps. The initial peak and the new peak correspond to hot carriers at the higher excited state and MEG at the lowest excited state, respectively. By proposing a theoretical model, we can calculate the hot carrier cooling time constant and MEG occurrence time constant quantitatively. When MEG does not happen for hν smaller than 2.7Eg, hot carrier cools with a time constant of 400 fs. When MEG occurs for hν larger than 2.7Eg, hot carrier cools with a time constant as small as 200 fs, while MEG occurs with a time constant of 600 fs. The detailed hot carrier cooling and MEG occurrence dynamics characterized in this work would shed light on the further understanding of MEG mechanism of various type of semiconductor QDs.

Determination of elastic and thermal properties of a thin nanocrystalline diamond coating using all-optical methods

Results are presented on the thermal and elastic properties of a thin, 1.5μm, nanocrystalline diamond coating (NCD), deposited on a silicon substrate by microwave plasma enhanced chemical vapor deposition. A combination of two all-optical measurement techniques, impulsive stimulated thermal scattering and grating induced laser beam deflection, was employed to launch and detect surface acoustic waves (SAWs). The relation between the dispersive propagation velocity of SAWs to the coating-substrate geometry is exploited to determine the elastic properties of the NCD coating. The elastic properties are found to be consistent with literature values. The thermal properties of the coating were determined by monitoring the thermal diffusion induced washing away of the laser induced transient surface temperature grating. The transient thermal grating signals were fitted by the low-frequency limit of a thermoelastic model for a multilayer configuration. Similar to the dispersion of the surface acoustic wave velocity, the characteristic time of the thermal diffusion driven grating decay evolves from a coating-dominated value at short grating spacings towards a substrate-dominated value at grating spacings well exceeding the coating thickness. The grating spacing dependence of the corresponding effective thermal diffusivity was experimentally determined and fitted, leading to a value for the thermal diffusivity of the NCD coating αNCD=8.4−0.1+2.7mm2·s−1, which is an order of magnitude lower than that of the silicon substrate. The low value of the thermal diffusivity is interpreted with a simple touching model.

Pressure-sensitive reaction yield of the TePixD blue-light sensor protein.

The effect of pressure on the dissociation reaction of the TePixD decamer was investigated by high-pressure transient grating (TG). The TG signal intensity representing the dissociation reaction of the TePixD decamer significantly decreased by applying a relatively small pressure. On the other hand, the reaction rate increased with increasing pressure. The equilibrium between the pentamer and the decamer was investigated by high-pressure dynamic light scattering. The results indicated that the fraction of the decamer slightly increased in the high-pressure region. From these measurements, it was concluded that the pressure-dependent signal intensity originated from the decrease of the quantum yield of the dissociation reaction of the decamer, indicating that this reaction efficiency is very sensitive to pressure. Using densimetry at high pressures, the compressibility was found to be pressure dependent even in a relatively low pressure range. We attributed the origin of the pressure-sensitive reaction yield to the decrease of compressibility at high pressure. Because the compressibility is related to the volume fluctuation, this observation suggests that the driving force for this reaction is fluctuation of the protein. The relationship between the cavities at the interfaces of the monomer units and the reactivity is also discussed.

Photoinduced oligomerization of Arabidopsis thaliana phototropin 2 LOV1.

Phototropins are blue-light-sensitive photoreceptor proteins in plants. Phototropins consist of two LOV (light, oxygen, and voltage sensor) domains (LOV1 and LOV2) that undergo photochemical reactions. Although the photochemical reaction of the LOV2 domain has been investigated extensively, the reaction of the LOV1 domain remains unresolved. In this study, the reactions of the Arabidopsis phototropin 2 LOV1 (phot2LOV1) domain were revealed by the transient grating (TG) method. The TG signal showed a significant diffusion coefficient (D) change upon photoexcitation. This change was sensitive to the protein concentration and the observation time range. These observations were explained by assuming that there are reactive and nonreactive forms, and the fraction of these species is concentration dependent. From the concentration dependence of the dynamics, the monomer was found to form a dimer; however, the dimer does not exhibit an observable reaction. In the dark state, both species were in equilibrium and were not distinguishable spectroscopically. For the LOV1 domain with the hinge domain, the reaction scheme was the same as the LOV1 domain sample, but the D change was affected by the presence of the hinge region. This observation suggested that the hinge region undergoes a conformational change during the photoreaction.

Ultraviolet transient absorption, transient grating and photon echo studies of aqueous tryptophan

We compare UV transient grating (TG) experiments of aqueous tryptophan with transient absorption (TA) and fluorescence up-conversion measurements. The TG and TA signals show a bi-exponential rise with sub-ps and ps time constants, which are consistent with the fluorescence studies. Using experimental data, we provide an equation for the homodyne-detected TG signal, taking into account the sub-100fs internal conversion of tryptophan after excitation. In addition, we measure a sub-100fs homogeneous electronic dephasing time for tryptophan in water by the photon echo (PE) technique. These measurements provide a consistent picture of excited state dynamics of aqueous tryptophan that may serve as a basis for coherent 2D-UV spectroscopy of biosystems.

Diffusion of degenerate minority carriers in a p-type semiconductor

We report ultrafast transient-grating experiments on heavily p-type InP at 15 K. Our measurement reveals the dynamics and diffusion of photoexcited electrons and holes as a function of their density n in the range 2 × 1016 to 6 × 1017 cm−3. After the first few picoseconds, the grating decays primarily due to ambipolar diffusion. While, at low density, we observe a regime in which the ambipolar diffusion is electron-dominated and increases rapidly with n, it appears to saturate at 34 cm2/s at high n. We present a simple calculation that reproduces the main results of our measurements as well as of previously published measurements that had shown diffusion to be a flat or decreasing function of n. By accounting for effect of density on charge susceptibility, we show that, in p-type semiconductors, the regime we observe of increasing ambipolar diffusion is unique to heavy doping and low temperature, where both the holes and electrons are degenerate; in this regime, the electronic and ambipolar diffusion are nearly equal. The saturation is identified as a crossover to ambipolar diffusion dominated by the majority carriers, the holes. At short times, the transient-grating signal rises gradually. This rise reveals cooling of hot electrons and, at high photocarrier density, allows us to measure ambipolar diffusion of 110 cm2/s in the hot-carrier regime.

Investigation of Relaxation Processes in Nanocomposites by Transient Grating Experiments

We report a comparative study on the photo-elastic and photo-thermal features of two nanocomposites based on MoS2 nanotubes dispersed into two different polyurea elastomeric matrices, which have different crosslinking properties. The time-resolved laser spectroscopic investigation on these nanocomposites by transient grating (TG) experiments has been performed. The relaxation kinetics on a very wide time scale has been measured from nanosecond to hundred of microseconds. The TG data on both pure polymers shows fast acoustic oscillations and a slow thermal decay. No structural relaxation is appearing in the experimental time window. Surprisingly, the presence of nanotubes in both the polymeric matrixes induces intermediate dynamics clearly detected by the TG signal. The features of this unexpected dynamic features recall the structural relaxation typical of glass-formers but its origin is still unclear.

Phase-controlled, heterodyne laser-induced transient grating measurements of thermal transport properties in opaque material

The methodology for a heterodyned laser-induced transient thermal grating technique for non-contact, non-destructive measurements of thermal transport in opaque material is presented. Phase-controlled heterodyne detection allows us to isolate pure phase or amplitude transient grating signal contributions by varying the relative phase between reference and probe beams. The phase grating signal includes components associated with both transient reflectivity and surface displacement whereas the amplitude grating contribution is governed by transient reflectivity alone. By analyzing the latter with the two-dimensional thermal diffusion model, we extract the in-plane thermal diffusivity of the sample. Measurements on a 5 μm thick single crystal PbTe film yielded excellent agreement with the model over a range of grating periods from 1.6 to 2.8 μm. The measured thermal diffusivity of 1.3 × 10−6 m2/s was found to be slightly lower than the bulk value.