Ultrafast Terahertz Spectroscopy Research Articles

Spontaneous exciton dissociation in transition metal dichalcogenide monolayers.

Since the seminal work on MoS2, photoexcitation in atomically thin transition metal dichalcogenides (TMDCs) has been assumed to result in excitons, with binding energies order of magnitude larger than thermal energy at room temperature. Here, we reexamine this foundational assumption and show that photoexcitation of TMDC monolayers can result in a substantial population of free charges. Performing ultrafast terahertz spectroscopy on large-area, single-crystal TMDC monolayers, we find that up to ~10% of excitons spontaneously dissociate into charge carriers with lifetimes exceeding 0.2 ns. Scanning tunneling microscopy reveals that photocarrier generation is intimately related to mid-gap defects, likely via trap-mediated Auger scattering. Only in state-of-the-art quality monolayers, with mid-gap trap densities as low as 109 cm-2, does intrinsic exciton physics start to dominate the terahertz response. Our findings reveal the necessity of knowing the defect density in understanding photophysics of TMDCs.

Evidence for d-wave superconductivity of infinite-layer nickelates from low-energy electrodynamics.

The discovery of superconductivity in infinite-layer nickelates established another category of unconventional superconductors that shares structural and electronic similarities with cuprates. However, key issues of the superconducting pairing symmetry, gap amplitude and superconducting fluctuations are yet to be addressed. Here we utilize static and ultrafast terahertz spectroscopy to address these. We demonstrate that the equilibrium terahertz conductivity and non-equilibrium terahertz responses of an optimally Sr-doped nickelate film (superconducting transition temperature of Tc = 17 K) are in line with the electrodynamics of d-wave superconductivity in the dirty limit. The gap-to-Tc ratio (2Δ/kBTc) is found to be 3.4, indicating that the superconductivity falls in the weak coupling regime. In addition, we observed substantial superconducting fluctuations near Tc that do not extend into the deep normal state as the optimally hole-doped cuprates do. Our results support a d-wave system that closely resembles the electron-doped cuprates.

Tuning the Inter-Nanoplatelet Distance and Coupling Strength by Thermally Induced Ligand Decomposition.

CdSe nanoplatelets (NPLs) are promising 2D semiconductors for optoelectronic applications, in which efficient charge transport properties are desirable. It is reported that thermal annealing constitutes an effective strategy to control the optical absorption and electrical properties of CdSe NPLs by tuning the inter-NPL distance. Combining optical absorption, transmission electron microscopy, and thermogravimetric analysis, it is revealed that the thermal decomposition of ligands (e.g., cadmium myristate) governs the inter-NPL distance and thus the inter-NPL electronic coupling strength. Employing ultrafast terahertz spectroscopy, it is shown that this enhanced electronic coupling increases both the free carrier generation efficiency and the short-range mobility in NPL solids. The results show a straightforward method of controlling the interfacial electronic coupling strength for developing functional optoelectronic devices through thermal treatments.

Generation of a Chirp-Controlled Terahertz Pulse by a Tapered Corrugated Wakefield Structure

Terahertz pulses with controlled spectral-temporal waveform have great potential in expanding the scope of state-of-the-art terahertz researches, such as terahertz-driven resonant and nonresonant control over matter and light, ultrafast terahertz spectroscopy, and terahertz-driven acceleration. Here, we propose and demonstrate a method to generate a prescribed terahertz chirped waveform with a well-designed tapered corrugated wakefield structure. We develop a deterministic procedure to derive the parameters of the corrugated structure that generates the desired spectral-temporal waveform with certain shape of chirp, central frequency, bandwidth, and pulse duration. The experimental results from ultrashort electron bunches passing through a well-designed tapered corrugated structure are demonstrated. Time-frequency analysis of the terahertz electric field measured by electro-optical sampling shows clear chirp from 0.38 to 0.6 THz. Calibrated measurements of the radiated energy indicate 10 \textmu{}J per pulse for an incident beam charge of 300 pC.

Spectroscopic Investigation of Structural Perturbations in CsPbCl3 Perovskite Nanocrystals: Temperature- and Excitation-Energy-Dependent Study

Inorganic lead halide perovskites are at the frontier of photovoltaic research due to their groundbreaking performance as an absorbing layer in solar cells. Cesium lead chloride (CsPbCl3), known to be a competent material for its blue emission, undergoes subsequent temperature-dependent phase transitions. The photophysical aspects reliant on temperature as well as the phase exhibited by the material are still unknown. Herein, we have studied the temperature- and excitation-energy-dependent underlying photophysics in CsPbCl3 nanocrystals (NCs) employing ultrafast transient absorption (TA) and terahertz (THz) spectroscopy. The direct dependence of carrier relaxation, carrier temperature, and energy loss on the phase transition has been established. Also, to comprehend the outcome of excitation energy, photoconductivity and mobility were determined with the help of optical pump THz probe spectroscopy, and it is established that as the excitation energy is reduced, mobility decay is found to be slow due to diminishing Auger recombination and augmented penetration depth.

Exciton Formation Dynamics and Band‐Like Free Charge‐Carrier Transport in 2D Metal Halide Perovskite Semiconductors

AbstractMetal halide perovskite (MHP) semiconductors have driven a revolution in optoelectronic technologies over the last decade, in particular for high‐efficiency photovoltaic applications. Low‐dimensional MHPs presenting electronic confinement have promising additional prospects in light emission and quantum technologies. However, the optimisation of such applications requires a comprehensive understanding of the nature of charge carriers and their transport mechanisms. This study employs a combination of ultrafast optical and terahertz spectroscopy to investigate phonon energies, charge‐carrier mobilities, and exciton formation in 2D (PEA)2PbI4 and (BA)2PbI4 (where PEA is phenylethylammonium and BA is butylammonium). Temperature‐dependent measurements of free charge‐carrier mobilities reveal band transport in these strongly confined semiconductors, with surprisingly high in‐plane mobilities. Enhanced charge‐phonon coupling is shown to reduce charge‐carrier mobilities in (BA)2PbI4 with respect to (PEA)2PbI4. Exciton and free charge‐carrier dynamics are disentangled by simultaneous monitoring of transient absorption and THz photoconductivity. A sustained free charge‐carrier population is observed, surpassing the Saha equation predictions even at low temperature. These findings provide new insights into the temperature‐dependent interplay of exciton and free‐carrier populations in 2D MHPs. Furthermore, such sustained free charge‐carrier population and high mobilities demonstrate the potential of these semiconductors for applications such as solar cells, transistors, and electrically driven light sources.

Ultrafast time-resolved carrier dynamics in tellurium nanowires using optical pump terahertz probe spectroscopy.

We report carrier relaxation dynamics in semiconducting tellurium nanowires (average diameter ∼ 10 nm) using ultrafast time-resolved terahertz spectroscopy. After photoexcitation using an 800 nm pump pulse, we observed an initial increase in the THz conductivity due to the absorption of THz radiation by photoexcited carriers. The time evolution of the differential conductivity (Δσ(τpp) = σpump on(τpp) - σpump off) shows a bi-exponential relaxation with the initial fast decay time scale of τ1 ∼ 25 ps followed by a longer relaxation time constant of τ2 ∼ 100 ps. Interestingly, the two time scales depend on the amount of the capping agent present on the surface of TeNWs, showing a faster relaxation of the photoexcited carriers as the percentage of capping decreases. This is physically interpreted as the surface state mediated relaxation mechanism of the photo-pumped carriers depending on the density of available surface states. A quantitative understanding is obtained using a coupled rate equation model taking into account the decay mechanisms determined from the surface mediated relaxation rate (DS) and direct recombination rate (DR) of the electron-hole pairs. Furthermore, the measured lattice temperature (TL) dependent dynamics, showing a faster relaxation at lower temperature, is understood using the same rate equation model, giving a power law dependence of the electron-hole recombination rate (DR) on TL as DR ∝ TL-1/2. This is explained by estimating DR using the van Roosbroeck-Shockley theory taking into account the density of states () of one-dimensional nanowires. Furthermore, to understand the measured frequency-dependent THz photoconductivity, we model Δσ(ω) using the Boltzmann transport equation taking into account the energy-dependent scattering rates showing the dominant role of short range (Γsr) and Coulomb scattering (ΓC) rates in the relaxation process, which further provides a measure of the charged and neutral impurity concentrations.

Stable Mott Polaron State Limits the Charge Density in Lead Halide Perovskites.

Large polarons are known to form in lead halide perovskites (LHPs). Photoinduced isolated polarons at low densities have been well-researched, but many-body interactions at elevated polaron densities, exceeding the Mott criterion (i.e., Mott polaron density), have remained elusive. Here, employing ultrafast terahertz spectroscopy, we identify a stable Mott polaron state in LHPs at which the polaron wavefunctions start to overlap. The Mott polaron density is determined to be ∼1018 cm-3, in good agreement with theoretical calculations based on the Feynman polaron model. The electronic phase transition across the Mott density is found to be universal in LHPs and independent of the constituent ions. Exceeding the Mott polaron density, excess photoinjected charge carriers annihilate quickly within tens to hundreds of picoseconds, before reaching the stable and long-lived Mott state. These results have considerable implications for LHP-based devices and for understanding exotic phenomena reported in LHPs.

Ultrafast probes of photovoltage and two-dimensional electron gas in the topological insulator Bi2Te3 by angle-resolved photoemission and terahertz spectroscopy

Photoexcited carriers in three-dimensional topological insulators (3D TIs) decay rapidly through the electron-electron and electron-phonon scattering. While most studies focus on such fast dynamics, recent experiments find the slow photovoltage (PV) dynamics arising from the band-bending potentials, in which the optical transitions in two-dimensional electron gas (2DEG) are effective. Although early investigations speculated the existence of multiple band-bending structures from the TI surface to the TI bulk, how PV and 2DEG are correlated in the presence of such multiple band bendings has been less explored. Here, we employ the combination of time- and angle-resolved photoemission spectroscopy (tr-ARPES) and ultrafast time-resolved terahertz (tr-THz) spectroscopy to investigate the PV and 2DEG dynamics in the prototypical topological insulator ${\mathrm{Bi}}_{2}{\mathrm{Te}}_{3}$. Our tr-ARPES analysis identifies two spatially separated PV dynamics associated with two types of band bending: one is the well-known surface PV, and another PV is formed deep within the bulk, which we call ``internal bulk PV.'' For the surface PV, our tr-THz spectra substantiate that the $\ensuremath{\mu}\mathrm{s}$-long transient signal arises from the surface-PV-induced increase of the TSS and 2DEG carrier density, which appears as a transient blueshift of a Fermi cutoff and an increased ARPES intensity in the tr-ARPES measurements. In contrast, the effect of the internal bulk PV shows only marginal changes in the 2DEG and TSS carrier densities but shifts the entire binding energy of the near-surface bands.

Revealing charge carrier dynamics and transport in Te-doped GaAsSb and GaAsSbN nanowires by correlating ultrafast terahertz spectroscopy and optoelectronic characterization

Recent advances in the growth of III-V semiconductor nanowires (NWs) hold great promise for nanoscale optoelectronic device applications. It is established that a small amount of nitrogen (N) incorporation in III-V semiconductor NWs can effectively red-shift their wavelength of operation and tailor their electronic properties for specific applications. However, understanding the impact of N incorporation on non-equilibrium charge carrier dynamics and transport in semiconducting NWs is critical in achieving efficient semiconducting NW devices. In this work, ultrafast optical pump-terahertz probe spectroscopy has been used to study non-equilibrium carrier dynamics and transport in Te-doped GaAsSb and dilute nitride GaAsSbN NWs, with the goal of correlating these results with electrical characterization of their equilibrium photo-response under bias and low-frequency noise characteristics. Nitrogen incorporation in GaAsSb NWs led to a significant increase in the carrier scattering rate, resulting in a severe reduction in carrier mobility. Carrier recombination lifetimes of 33 ± 1 picoseconds (ps) and 147 ± 3 ps in GaAsSbN and GaAsSb NWs, respectively, were measured. The reduction in the carrier lifetime and photoinduced optical conductivities are due to the presence of N-induced defects, leading to deterioration in the electrical and optical characteristics of dilute nitride NWs relative to the non-nitride NWs. Finally, we observed a very fast rise time of ∼2 ps for both NW materials, directly impacting their potential use as high-speed photodetectors.

Switching to Hidden Metallic Crystal Phase in Phase-Change Materials by Photoenhanced Metavalent Bonding.

Metavalent bonding is crucial for the determination of phase transition and improvement of device performance in phase-change materials, which are attracting interest for use in memory devices. Although monitoring dielectric and phononic parameters provides a direct measure of the metavalent bonding, the control of phase-change phenomena and metavalent bonding in the dynamical regime has yet to be demonstrated. This study reports the photoenhanced metavalent bonding and resulting hidden metallic crystalline state of Ti-doped Sb2Te3, a representative phase-change material with ultralong sustainability. Using ultrafast terahertz spectroscopy, Ti0.4Sb2Te3 was discovered to possess ultralong pump-probe dynamics, which is retained over hundreds of picoseconds, unlike the short-lived state of undoped Sb2Te3. Moreover, for Ti0.4Sb2Te3 during the long-lived transmission change, the infrared-active phonon is highly softened, even more than the amount of a thermal phonon shift, indicating the photoenhancement of lattice anharmonicity. Such a long-lived relaxation implies photoinduced transition into a crystalline state of ultrastrong metavalent bonding in Ti0.4Sb2Te3, on the basis of comparisons of the dynamical dielectric constant and temporal phonon shift. Our results show the realization of photoengineering of phase-change materials by tuning electron sharing or transferring.

Solution-Processed Graphene-Nanographene van der Waals Heterostructures for Photodetectors with Efficient and Ultralong Charge Separation.

Sensitization of graphene with inorganic semiconducting nanostructures has been demonstrated as a powerful strategy to boost its optoelectronic performance. However, the limited tunability of optical properties and toxicity of metal cations in the inorganic sensitizers prohibits their widespread applications, and the in-depth understanding of the essential interfacial charge-transfer process within such hybrid systems remains elusive. Here, we design and develop high-quality nanographene (NG) dispersions with a large-scale production using high-shear mixing exfoliation. The physisorption of these NG molecules onto graphene gives rise to the formation of graphene-NG van der Waals heterostructures (VDWHs), characterized by strong interlayer coupling through π-π interactions. As a proof of concept, photodetectors fabricated on the basis of such VDWHs show ultrahigh responsivity up to 4.5 × 107 A/W and a specific detectivity reaching 4.6 × 1013 Jones, being competitive with the highest values obtained for graphene-based photodetectors. The outstanding device characteristics are attributed to the efficient transfer of photogenerated holes from NGs to graphene and the long-lived charge separation at graphene-NG interfaces (beyond 1 ns), as elucidated by ultrafast terahertz (THz) spectroscopy. These results demonstrate the great potential of such graphene-NG VDWHs as prototypical building blocks for high-performance, low-toxicity optoelectronics.

Correlating Charge Transport Properties of Conjugated Polymers in Solution Aggregates and Thin-Film Aggregates.

The role of solution aggregates on the charge transport process of conjugated polymers in electronic devices has gained increasing attention; however, the correlation of the charge carrier mobilities between the solution aggregates and the solid-state films remains elusive. Herein, three polymers, FBDOPV-2T, FBDOPV-2F2T, and FBDOPV-4F2T, are designed and synthesized with distinct aggregation behavior in solution. By combining contact-free ultrafast terahertz (THz) spectroscopy and field-effect transistor measurements, we track the charge carrier mobility of the aggregates of these polymers from the solution to the thin-film state. Remarkably, the mobility of these three polymers is found to follow nearly the same trend (FBDOPV-2T>FBDOPV-2F2T≫FBDOPV-4F2T) in both solutions and thin-film states. The quantitative mobility correlation indicates that the charge transport properties of solution aggregates play a critical role in determining the thin-film charge transport properties and final device performance. Our results highlight the importance of investigating and controlling solution aggregation structures towards efficient organic electronic devices.

Correlating Charge Transport Properties of Conjugated Polymers in Solution Aggregates and Thin‐Film Aggregates

AbstractThe role of solution aggregates on the charge transport process of conjugated polymers in electronic devices has gained increasing attention; however, the correlation of the charge carrier mobilities between the solution aggregates and the solid‐state films remains elusive. Herein, three polymers, FBDOPV‐2T, FBDOPV‐2F2T, and FBDOPV‐4F2T, are designed and synthesized with distinct aggregation behavior in solution. By combining contact‐free ultrafast terahertz (THz) spectroscopy and field‐effect transistor measurements, we track the charge carrier mobility of the aggregates of these polymers from the solution to the thin‐film state. Remarkably, the mobility of these three polymers is found to follow nearly the same trend (FBDOPV‐2T>FBDOPV‐2F2T≫FBDOPV‐4F2T) in both solutions and thin‐film states. The quantitative mobility correlation indicates that the charge transport properties of solution aggregates play a critical role in determining the thin‐film charge transport properties and final device performance. Our results highlight the importance of investigating and controlling solution aggregation structures towards efficient organic electronic devices.

Accelerating Ultrafast Spectroscopy with Compressive Sensing

Ultrafast spectroscopy is an important tool for studying photoinduced dynamical processes in atoms, molecules, and nanostructures. Typically, the time to perform these experiments ranges from several minutes to hours depending on the choice of spectroscopic method. It is desirable to reduce this time overhead to not only to shorten time and laboratory resources, but also to make it possible to examine fragile specimens which quickly degrade during long experiments. In this article, we motivate using compressive sensing to significantly shorten data acquisition time by reducing the total number of measurements in ultrafast spectroscopy. We apply this technique to experimental data from ultrafast transient absorption spectroscopy and ultrafast terahertz spectroscopy and show that good estimates can be obtained with as low as 15% of the total measurements, implying a 6-fold reduction in data acquisition time.

Ultrafast terahertz spectroscopy provides insight into charge transfer efficiency and dynamics in artificial photosynthesis.

Terahertz (THz) spectroscopy provides a noncontact method to measure the ultrafast dynamics and photoconductivity of mobile carriers in semiconducting materials. This has proven useful in studying artificial photosynthesis devices which use semiconductor photoelectrodes. We present a brief introduction to optical-pump THz-probe (OPTP) spectroscopy, a technique that provides unique and useful insight into interfacial electron transfer (from the surface-attached dye to the conduction band of the semiconductor) in dye-sensitized photoelectrochemical cells. Compared with more familiar methods like visible transient absorption spectroscopy, OPTP spectroscopy stands out in offering both sub-picosecond time resolution as well as sensitivity to mobile carriers (electrons and holes) in the semiconductor portion of artificial photosynthesis devices. The mobile carriers are crucial to device performance as only they pass to the other half cell to complete the reaction. In order to highlight these advantages and illustrate the types of questions OPTP spectroscopy can address, we discuss three case studies. In the first, OPTP spectroscopy is used to measure the injection rates from a set of six different dyes, revealing the effect of the energetics and lifetimes of the dye excited states on interfacial electron transfer. The subsequent case studies investigate the influence of varying the moieties which bind to the surface (anchors), as well as the moieties that connect the chromophore with these anchors (linkers). OPTP spectroscopy was used to measure the interfacial electron transfer rate as these moieties were varied.

High-power few-cycle THz generation at MHz repetition rates in an organic crystal

Ultrafast terahertz (THz) spectroscopy is a potent tool for studying the fundamental properties of matter. Limitations of current THz sources, however, preclude the technique being applied in certain advanced configurations or in the measurement of, e.g., strongly absorbing samples. In response to this problem, here we demonstrate the generation of 1.38 mW broadband THz radiation at 10 MHz repetition rate by combining the highly efficient nonlinear organic crystal HMQ-TMS with ultrafast pump pulses generated using a simple and stable external pulse compression of a high power, near-infrared (NIR) femtosecond ytterbium-doped fiber (Yb:fiber) laser. Utilizing spectral broadening in a large core, polarization maintaining photonic crystal fiber and a pair of SF11 prisms, we achieve a tenfold pulse compression of the Yb:fiber laser, yielding compressed 0.35 µJ pulses with a full-width at half maximum pulse duration of 22 fs, exerting a peak power of 13.8 MW at a repetition rate of 10 MHz. THz generation through optical rectification of the NIR pulses is explored in two distinct thicknesses of the organic crystal, leading to a maximum conversion efficiency of ∼5.5 · 10−4, an order of magnitude higher than that achieved with inorganic nonlinear crystals, e.g., gallium phosphide, for similar pump parameters. The focused THz beam has a peak on-axis field strength greater than 6.4 kV cm−1 in unpurged atmosphere. We believe that our moderately strong-field THz source is well suited to a variety of applications in ultrafast THz spectroscopy, in particular THz-enabled scattering-type near-field, and scanning tunneling spectroscopy, where multi-MHz repetition rate sources are required.

Free Carrier, Exciton, and Phonon Dynamics in Lead‐Halide Perovskites Studied with Ultrafast Terahertz Spectroscopy

AbstractTerahertz time‐domain spectroscopy is a noncontact, coherent technique that can probe dynamics of carriers, phonons and excitons, and the interplay among these degrees of freedom, which determines the functionalities of the system. In the past few years, lead‐halide perovskites have shown to be a promising class of materials in the areas of solar cells, light emitting diodes, lasers, photodetectors, and field‐effect transistors. In these electronic and photonic devices, the knowledge of the dynamics of charge carriers and other low‐energy excitations is crucial to understand the underlying physics that ultimately determines the device performances. Here, some of the most representative works in the area of halide perovskite research using terahertz time‐domain spectroscopy and time‐resolved terahertz spectroscopy are reviewed, highlighting the power of ultrafast terahertz techniques on this class of material system.

Anomalous variations of spectral linewidth in internal excitonic quantum transitions of ultrafast resonantly excited single-walled carbon nanotubes

How the exciton fine structure and spectral linewidth in single-walled carbon nanotubes (SWNTs) evolve after ultrafast photoexcitation is critical for both understanding the fundamental optoelectronic properties and the development of nanophotonic functional devices. Yet, studies so far have mostly detected a subset of excitons near the Brillouin-zone center due to symmetry and momentum restrictions of the interband optical probes used, such as photoluminescence and absorption. Here we use ultrafast terahertz spectroscopy to probe the excitonic spectral linewidth associated with internal quantum transition across the entire momentum $K$ space in resonantly excited semiconducting SWNTs. The lowest-lying intraexcitonic transition surprisingly sharpens at both high pump fluence and initial times immediately following the photoexcitation. We attribute these anomalous variations in the spectral linewidth to the role of the dark state $1s(g)$ that influences the lifetime broadening of the bright state $1s(u)$, consistent with the temperature-dependent dephasing time with a crossover temperature set by the internal quantum level spacing of excitons.

How optical excitation controls the structure and properties of vanadium dioxide

We combine ultrafast electron diffraction and time-resolved terahertz spectroscopy measurements to link structure and electronic transport properties during the photoinduced insulator-metal transitions in vanadium dioxide. We determine the structure of the metastable monoclinic metal phase, which exhibits antiferroelectric charge order arising from a thermally activated, orbital-selective phase transition in the electron system. The relative contribution of the photoinduced monoclinic and rutile metals to the time-dependent and pump-fluence-dependent multiphase character of the film is established, as is the respective impact of these two distinct phase transitions on the observed changes in terahertz conductivity. Our results represent an important example of how light can control the properties of strongly correlated materials and demonstrate that multimodal experiments are essential when seeking a detailed connection between ultrafast changes in optical-electronic properties and lattice structure.