Time-resolved Second Harmonic Generation Research Articles

Time-Resolved Second-Harmonic Generation in Topological Insulator Bi2Te3: Competing Contributions from Dirac Surface States, Surface Photovoltage, and Band Bending

Time-Resolved Second-Harmonic Generation in Topological Insulator Bi₂Te₃: Competing Contributions from Dirac Surface States, Surface Photovoltage, and Band Bending

Femtosecond time-resolved nonlinear optical spectroscopy of charge transfer at the buried GaP/Si(001) interface

The ultrafast charge-carrier dynamics at the buried heterointerface of gallium phosphide on silicon(001) are investigated by means of time-resolved optical second-harmonic generation. Photon energy dependent measurements reveal the existence of electronic interface states in the bandgap of both materials. Charge carriers excited via these interface states are efficiently injected within a few hundred femtoseconds from the GaP/Si interface into the Si substrate, resulting in the build-up of an electric field perpendicular to the interface on a picosecond time scale.

Photo-induced meta-stable polar conformations in polystyrene microspheres revealed by time-resolved SHG microscopy

Photo-induced second harmonic generation (SHG) was observed in centrosymmetric polystyrene (PS) microspheres using 1064 nm, sub-nanosecond laser-pulse irradiation. The SHG signal gradually increased upon stationary laser-pulse irradiation. After stopping the irradiation, the increased SHG signal disappeared in approximately 30 min. When the PS bead was irradiated by laser pulses again, the SHG signal reappeared with similar temporal behavior, which was attributed to the probable growth and contraction of meta-stable polar conformations of PS chain segments under periodic photo-thermal stimuli.

Directional ultrafast charge transfer in a WSe2/MoSe2 heterostructure selectively probed by time-resolved SHG imaging microscopy.

Heterostructures of two-dimensional transition metal dichalcogenides (TMD) have shown promise for various optoelectronic and novel valleytronic applications. Due to their type-II band alignment, photoexcited electrons and holes can separate into different layers through ultrafast charge transfer. While this charge-transfer process is critical for potential applications, the underlying mechanisms still remain elusive. Here, we demonstrate for a rotationally mismatched WSe2/MoSe2 heterostructure that directional ultrafast charge transfer between the layers becomes accessible by time-resolved optical second-harmonic generation. By tuning the photon energy of the pump pulse, one of the two materials is resonantly excited, whereas the polarization of the probe pulse can be optimized to selectively detect the charge transfer into the other material. This allows us to explore the interlayer hole transfer from the WSe2 into the MoSe2 layer and vice versa, which appears within a few hundred femtoseconds via hybridized intermediate states at the Γ-point. Our approach enables systematic investigations of the charge transfer in dependence of the rotational layer mismatch in TMD heterostructures.

Study of the Photoswitching of a Fe(II) Chiral Complex through Linear and Nonlinear Ultrafast Spectroscopy.

Photoswitching the physical properties of molecular systems opens large possibilities for driving materials far from equilibrium toward new states. Moreover, ultrashort pulses of light make it possible to induce and to record photoswitching on a very short time scale, opening the way to fascinating new functionalities. Among molecular materials, Fe(II) complexes exhibit an ultrafast spin-state transition during which the spin state of the complex switches from a low spin state (LS, S = 0) to a high spin state (HS, S = 2). The latter process is remarkable: It takes place within ∼100 fs with a quantum efficiency of ∼100%. Moreover, the spin-state switching induces an important shift of the broad metal-to-ligand absorption band of the complex, and it results in large modifications of the physical and chemical properties of the compounds. But because most of the Fe(II) complexes crystallize in centrosymmetric space groups, this prevents them from exhibiting piezoelectric, ferroelectric, as well as second-order nonlinear optical properties such as second-harmonic generation (SHG). This considerably limits their potential applications. We have recently synthesized [Fe(phen)3] [Δ-As2(tartrate)2] chiral complexes that crystallize in a noncentrosymmetric 32 space group. Hereafter, upon the excitation of a thin film of these complexes by a femtosecond laser pulse and performing simultaneously transient absorption (TRA) and time-resolved SHG (TRSH) measurements, we have recorded the ultrafast LS to HS switching. Whereas a single TRA measurement gives only partial information, we demonstrate that TRSH readily reveals the different mechanisms in play during the HS-to-LS state relaxation. Moreover, a simple model makes it possible to evaluate the relaxation times as well as the hyperpolarizabilities of the different excited states through which the system travels during the spin-state transition.

Tracking the ultrafast motion of an antiferromagnetic order parameter

The unique functionalities of antiferromagnets offer promising routes to advance information technology. Their compensated magnetic order leads to spin resonances in the THz-regime, which suggest the possibility to coherently control antiferromagnetic (AFM) devices orders of magnitude faster than traditional electronics. However, the required time resolution, complex sublattice interactions and the relative inaccessibility of the AFM order parameter pose serious challenges to studying AFM spin dynamics. Here, we reveal the temporal evolution of an AFM order parameter directly in the time domain. We modulate the AFM order in hexagonal YMnO3 by coherent magnon excitation and track the ensuing motion of the AFM order parameter using time-resolved optical second-harmonic generation. The dynamic symmetry reduction by the moving order parameter allows us to separate electron dynamics from spin dynamics. As transient symmetry reductions are common to coherent excitations, we have a general tool for tracking the ultrafast motion of an AFM order parameter.

Transient carrier visualization of organic-inorganic hybrid perovskite thin films by using time-resolved microscopic second-harmonic generation (TRM-SHG)

Abstract Based on the transient electric field migration directly probed by the time-resolved microscopic optical second-harmonic generation (TRM-SHG) technique, we successfully detected the transient hole transport in the perovskite for the first time. From the spectroscopic point of view, SHG signal resonantly enhanced at the fundamental wavelength of around 1560 nm through the band-transition under the voltage application. Square dependence of the SH intensity on the applied voltage at the wavelength of 1560 nm clearly indicated the electric field induced process of the SHG. We could visualize the carrier motion in the channel of perovskite field effect transistor (FET) with this wavelength. Carrier mobility was estimated as 0.02 cm2/V by analyzing the transient carrier motion. TRM-SHG technique was also employed to investigate the effect of traps on the transient carrier motion. Based on the peak of the transient electric field distribution, trap density, and dynamic carrier mobility were separately estimated.

Molecular Adsorption and Transport at Liposome Surfaces Studied by Molecular Dynamics Simulations and Second Harmonic Generation Spectroscopy.

A fundamental understanding of the factors that determine the interactions with and transport of small molecules through phospholipid membranes is crucial in developing liposome-based drug delivery systems. Here we combine time-dependent second harmonic generation (SHG) measurements with molecular dynamics simulations to elucidate the events associated with adsorption and transport of the small molecular cation, malachite green isothiocyanate (MGITC), in colloidal liposomes of different compositions. The molecular transport of MGITC through the liposome bilayer is found to be more rapid in 1,2-dioleoyl-sn-glycero-3-phospho-(1'-rac-glycerol) and 1,2-dioleoyl-sn-glycero-3-phospho-l-serine (DOPG and DOPS, respectively) liposomes, while the molecular transport is slower in 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) liposomes. Interestingly, MGITC is observed to neither adsorb nor transport in trimethyl quinone-1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (QPADOPE) liposomes due to shielding by the quinone group. The modified Langmuir adsorption isotherm model is used to determine the free energy of adsorption for MGITC, which is found to be less negative in DOPC than in DOPG and DOPS, caused by lower electrostatic interactions between the positively charged dye and the zwitterionic DOPC liposome surface. The results are compared to our previous investigations, which showed that malachite green (MG) adsorbs and transports in DOPG and DOPS liposomes but not in DOPC and QPADOPE liposomes. Molecular dynamics simulations are used to investigate the adsorption and transport properties of MG and MGITC in DOPC and DOPG liposomes using umbrella sampling to determine the free energy profiles and interfacial molecular orientations. Together, these time-resolved SHG studies and corresponding molecular dynamics simulations characterize the complicated chemical interactions at different lipid membranes to provide key molecular-level insights for potential drug delivery applications. The results also point toward understanding the role of chemical functional groups, in this case isothiocyanate, in controlling molecular adsorption at and transport through lipid bilayers.

Enhanced photocatalytic hydrogen evolution of CdWO4 through polar organic molecule modification

In this work, a polar molecule 4-mercaptobenzoic acid (4-MBA) is anchored on the surface of CdWO4 by forming CdS and WS bond. Photocatalytic hydrogen evolution is significantly enhanced (about 3.41 times) after the modification. The reason is due to the modification of 4-MBA, which results in a polar surface and built-in electric field. The polar surface is confirmed by the steady state and time-resolved PL spectra, Voc and SHG results.

Probing the upper band gap of atomic rhenium disulfide layers

Here, we investigate the ultrafast carrier dynamics and electronic states of exfoliated ReS2 films using time-resolved second harmonic generation (TSHG) microscopy and density functional theory (DFT) calculations. The second harmonic generation (SHG) of layers with various thicknesses is probed using a 1.19-eV beam. Up to ~13 nm, a gradual increment is observed, followed by a decrease caused by bulk interferometric light absorption. The addition of a pump pulse tuned to the exciton band gap (1.57 eV) creates a decay-to-rise TSHG profile as a function of the probe delay. The power and thickness dependencies indicate that the electron–hole recombination is mediated by defects and surfaces. The two photon absorptions of 2.38 eV in the excited state that are induced by pumping from 1.57 to 1.72 eV are restricted because these transitions highly correlate with the forbidden d–d intrasubshell orbital transitions. However, the combined usage of a frequency-doubled pump (2.38 eV) with wavelength-variant SHG probes (2.60–2.82 eV) allows us to vividly monitor the variations in TSHG profiles from decay-to-rise to rise-to-decay, which imply the existence of an additional electron absorption state (s-orbital) at an approximate distance of 5.05 eV from the highest occupied molecular orbital states. This observation was critically examined by considering the allowance of each electronic transition and a small upper band gap (~0.5 eV) using modified DFT calculations.

Selective probe of coherent polar phonon and quasiferromagnetic resonance modes in multiferroic GdFeO3

Using time-resolved second harmonic generation (TRSHG) and optical transmission, we demonstrate simultaneous optical access to both magnetic and ferroelectric order parameters in a magnetoelectric multiferroic ${\mathrm{GdFeO}}_{3}$ below the transition temperature 2.2 K. In magnetoelectric phase, the pump pulses impulsively generate polar phonon modes of ${B}_{2}$ and ${A}_{1}$ symmetry and a quasiferromagnetic resonance mode, creating coherent lattice and spin motions. While collective motions associated with the ferroelectric and antiferromagnetic ordering are simultaneously excited, only the polar motion is detected in TRSHG, resulting in a direct subpicosecond excitation of the improper ferroelectric order. Our result also experimentally indicates that the soft mode in improper ferroelectrics is IR inactive above the phase transition, unlike proper ferroelectrics. Furthermore, we investigate the crystal polar symmetry and potential coupling between the polar phonons and the quasiantiferromagnetic resonance mode, which can shed light on the studies of subpicosecond magnetoelectric coupling based on collective quasiparticle excitations.

Ultrafast Charge Transfer at a Quantum Dot/2D Materials Interface Probed by Second Harmonic Generation.

Hybrid quantum dot (QD)/transition metal dichalcogenide (TMD) heterostructures are attractive components of next generation optoelectronic devices, which take advantage of the spectral tunability of QDs and the charge and exciton transport properties of TMDs. Here, we demonstrate tunable electronic coupling between CdSe QDs and monolayer WS2 using variable length alkanethiol ligands on the QD surface. Using femtosecond time-resolved second harmonic generation (SHG) microscopy, we show that electron transfer from photoexcited CdSe QDs to single-layer WS2 occurs on ultrafast (50 fs to 1 ps) time scales. Moreover, in the samples exhibiting the fastest charge transfer rates (≤50 fs) we observed oscillations in the time-domain signal corresponding to an acoustic phonon mode of the donor QD, which coherently modulates the SHG response of the underlying WS2 layer. These results reveal surprisingly strong electronic coupling at the QD/TMD interface and demonstrate the usefulness of time-resolved SHG for exploring ultrafast electronic-vibrational dynamics in TMD heterostructures.

Ultrafast Excited State Dynamics in Diindenoperylene Films

Diindenoperylene (DIP) is an interesting organic molecular semiconductor as a component in organic solar cells. Here, we studied the ultrafast excited state dynamics of DIP after optical excitation in thin films on sapphire and SiO2 substrates, respectively, using femtosecond (fs) time-resolved second harmonic generation (TR-SHG). Sapphire, an inert and noninteracting substrate, is known to deliver no noteworthily contribution to the SHG-signal; thus, the pure response of DIP to the electronic excitation can be resolved in contrast to the measurements on SiO2. For DIP/sapphire, the initial optical excitation leads to the generation of delocalized excitons, which localize within approximately 100 fs in order to generate singlet molecular excitons (Frenkel excitons) or excitons localized on dimers. These excitons have a lifetime of 470 ± 100 fs. In a subsequent step, they form excimer states, which decay on a time scale of 680 ± 110 ps. For DIP/SiO2, the molecular excitons decay on a faster time scale of 210 ± 95 fs and populate either substrate-mediated trap states or excimer states. The present study provides important insights in the excited states dynamics of DIP on the so far unresolved ultrashort time scale, essential for understanding the photophysics of DIP.

Time-resolved correlative optical microscopy of charge-carrier transport, recombination, and space-charge fields in CdTe heterostructures

From time- and spatially resolved optical measurements, we show that extended defects can have a large effect on the charge-carrier recombination in II–VI semiconductors. In CdTe double heterostructures grown by molecular beam epitaxy on the InSb (100)-orientation substrates, we characterized the extended defects and found that near stacking faults the space-charge field extends by 2–5 μm. Charge carriers drift (with the space-charge field strength of 730–1,360 V cm−1) and diffuse (with the mobility of 260 ± 30 cm2 V−1 s−1) toward the extended defects, where the minority-carrier lifetime is reduced from 560 ns to 0.25 ns. Therefore, the extended defects are nonradiative recombination sinks that affect areas significantly larger than the typical crystalline grains in II–VI solar cells. From the correlative time-resolved photoluminescence and second-harmonic generation microscopy data, we developed a band-diagram model that can be used to analyze the impact of extended defects on solar cells and other electronic devices.

Direct evaluation of anisotropic carrier mobility in uniaxially aligned polymer semiconductor film by time-resolved microscopic optical second-harmonic generation measurement

Mobility anisotropy in uniaxially-aligned fluorene co-polymer thin film was directly observed by using time-resolved microscopic optical second-harmonic generation (TRM-SHG) imaging. Main-chain orientation of fluorene co-polymer was determined by polarized absorption measurement, and the mobilities in the direction parallel and perpendicular to the main-chain were respectively estimated as cm2 Vs−1 and cm2 Vs−1 from the visualized carrier motion starting from a round-shape electrode. These results indicate that the mobility anisotropy of this sample was 4.0. Activation energy for each direction was also evaluated by the temperature dependence measurement as 117 and 94 meV, respectively. The TRM-SHG method enables us to estimate mobility and activation energy of the oriented polymer film in all directions at once.

Determine electric field directions at semiconductor surfaces by femtosecond frequency domain interferometric second harmonic (FDISH) generation

Optical excitations at semiconductor surfaces or interfaces are accompanied by transient interfacial electric fields due to charge redistribution or transfer. While such transient fields may be probed by time-resolved second harmonic generation (TR-SHG), it is difficult to determine the field direction, which is invaluable to unveiling the underlying physics. Here we apply a time-resolved frequency domain interferometric second harmonic (TR-FDISH) generation technique to determine the phase relationship between the SH field emitted from bulk GaAs(100) and the transient SH field from the space charge region. The interference between these two SH fields allow us to unambiguously determine the directions of transient electric fields. Since SH fields from a static bulk contribution and a changing electric field contribution are present at most semiconductor surfaces or interfaces under optical excitation, the TR-FDISH technique is of general significance to probing the dynamics of interfacial charge transfer/redistribution.

Band-like transport observed in TIPS-pentacene thin film by time-resolved microscopic optical second-harmonic generation imaging

Carrier transport in single-crystalline grains of 6,13-bis(triisopropylsilylethynyl) (TIPS) pentacene was studied using time-resolved microscopic optical second-harmonic generation (TRM-SHG). TRM-SHG is used to directly visualize carrier injection and transport behavior in TIPS pentacene. A strong SHG signal observed at the edge of a FET source electrode at low temperature suggests the presence of a potential drop associated with the carrier injection process. An accurate carrier mobility calculation, taking into account the potential drop, shows a negative slope with temperature that indicates band-like transport.

Excited-state dynamics of an environment-sensitive push-pull diketopyrrolopyrrole: major differences between the bulk solution phase and the dodecane/water interface.

The excited-state dynamics of a diketopyrrolopyrrole (DPP) derivative with push-pull substituents has been investigated in a variety of solvents and at the dodecane/water and dodecane/heavy-water interfaces using a combination of ultrafast spectroscopic techniques, including transient electronic absorption and time-resolved surface second-harmonic generation. Whereas the photophysics of a nonpolar DPP analogue is mostly independent of the solvent, the fluorescence decay of the push-pull DPP accelerates strongly by going from aprotic to protic solvents. As this effect increases with the polarity and the hydrogen-bond-donating ability of the solvent, it is attributed to the occurrence of H-bond-assisted nonradiative deactivation induced by the charge-transfer character of the excited state that favors the coupling of the molecule to the H-bond network of the solvent. At the dodecane/water interface, the excited-state lifetime is longer by a factor of ca. 20 than that estimated in pure water and increases further by a factor of about 3 when going to the dodecane/heavy-water interface. This isotope effect, that is more than twice as strong as that measured in bulk solutions, and molecular dynamic simulations indicate that the slowing down of the dynamics at the interface cannot be solely ascribed to a reduced accessibility of the DPP molecule to the aqueous phase. The slower excited-state decay is rather assigned to the conjunction of several effects, such as the strengthening of the H-bond network formed by the interfacial water molecules and the lower local polarity of the interfacial region.

Heterodyne-detected and ultrafast time-resolved second-harmonic generation for sensitive measurements of charge transfer.

In organic photovoltaics many key ultrafast processes occur at the interface between electron donor and acceptor molecules. Traditional ultrafast spectroscopies, such as pump-probe or time-resolved fluorescence, are not ideal for studying the interface because most of their signal is from the bulk material. Time-resolved second-harmonic generation (TRSHG) spectroscopy solves this problem by only generating signal from the interface. We demonstrate an optically heterodyned TRSHG to reduce the impact of stray light, enhance sensitivity, and detect the full complex signal field.

Probing Transient Electric Fields in Photoexcited Organic Semiconductor Thin Films and Interfaces by Time-Resolved Second Harmonic Generation

We have probed photoinduced charge separation dynamics in organic semiconductor thin films and at their interfaces by femtosecond time-resolved second harmonic generation (TR-SHG), using the model systems of fullerene (C70) thin films and copper phthalocyanine (CuPc)/C70 interfaces. In neat C70 thin films, the formation of an internal electric field on a ∼10-ps time scale following photoexcitation is attributed to the photo-Dember effect, namely, charge separation resulting from a gradient in excitation density and the differential electron/hole mobility. When an ultrathin film of the electron donor CuPc was deposited on top of the C70 film, an additional interfacial charge separation channel occurring on the ultrafast time scale of ∼0.1 ps was observed. We discuss how SHG fields from different origins can interfere to give the overall transient response.