Time-resolved Terahertz Spectroscopy Research Articles

Highly Crystalline and Semiconducting Imine-Based Two-Dimensional Polymers Enabled by Interfacial Synthesis.

Single‐layer and multi‐layer 2D polyimine films have been achieved through interfacial synthesis methods. However, it remains a great challenge to achieve the maximum degree of crystallinity in the 2D polyimines, which largely limits the long‐range transport properties. Here we employ a surfactant‐monolayer‐assisted interfacial synthesis (SMAIS) method for the successful preparation of porphyrin and triazine containing polyimine‐based 2D polymer (PI‐2DP) films with square and hexagonal lattices, respectively. The synthetic PI‐2DP films are featured with polycrystalline multilayers with tunable thickness from 6 to 200 nm and large crystalline domains (100–150 nm in size). Intrigued by high crystallinity and the presence of electroactive porphyrin moieties, the optoelectronic properties of PI‐2DP are investigated by time‐resolved terahertz spectroscopy. Typically, the porphyrin‐based PI‐2DP 1 film exhibits a p‐type semiconductor behavior with a band gap of 1.38 eV and hole mobility as high as 0.01 cm2 V−1 s−1, superior to the previously reported polyimine based materials.

Influence of a substrate on ultrafast interfacial charge transfer and dynamical interlayer excitons in monolayer WSe2/graphene heterostructures.

Efficient interfacial light-electric interconversion in van der Waals heterostructures is critical for their optoelectronic applications. Using time-resolved terahertz spectroscopy and transient absorption spectroscopy, the charge transfer and the dynamical interlayer excitons were investigated in the heterostructures comprising monolayer WSe2 and monolayer graphene with varying stacking order on a sapphire substrate. Herein, a more comprehensive understanding of ultrafast charge transfer and exciton dynamics in two-dimensional heterostructures is shown. Owing to the effective electric field induced by the sapphire substrate, the WSe2/graphene heterostructure exhibits positive terahertz photoconductivity after photoexcitation, while negative terahertz photoconductivity is observed in the graphene/WSe2 heterostructure. The transient absorption spectra indicate that the exciton lifetimes also exhibit a considerable difference, where WSe2/graphene exhibits the longest exciton lifetime, followed by monolayer WSe2, while graphene/WSe2 exhibits the shortest lifetime. These observations provide a new idea for using van der Waals heterostructures in electronic and photonic devices.

Ultrafast Carrier Dynamics of Monolayer WS2 via Broad-Band Time-Resolved Terahertz Spectroscopy

We report on the ultrafast carrier dynamics of monolayer WS2 using broad-band time-resolved terahertz spectroscopy (TRTS). We find that upon photoexcitation, there is an increase in the conductivit...

Comparative Study of Photocarrier Dynamics in CVD-deposited CuWO4, CuO, and WO3 Thin Films for Photoelectrocatalysis

Abstract The temporal evolution of photogenerated carriers in CuWO4, CuO and WO3 thin films deposited via a direct chemical vapor deposition approach was studied using time-resolved microwave conductivity and terahertz spectroscopy to obtain the photocarrier lifetime, mobility and diffusion length. The carrier transport properties of the films prepared by varying the copper-to-tungsten stoichiometry were compared and the results related to the performance of the compositions built into respective photoelectrochemical cells. Superior carrier mobility was observed for CuWO4 under frontside illumination.

Effects of cation composition on carrier dynamics and photovoltaic performance in Cu2ZnSnSe4 monocrystal solar cells

Understanding the relationship of doping density, carrier lifetime, and interface recombination to device performance is critical to designing solar cells with high power conversion efficiency (PCE). In turn, it is necessary to understand how bulk material composition determines doping density and carrier lifetime. The most efficient kesterite Cu2ZnSn(S,Se)4 (CZTSSe) thin film solar cells have had Cu-poor, Zn-rich compositions, while more stoichiometric compositions have lower PCEs. However, thin films are grown under highly non-equilibrium conditions, complicating fundamental studies. Here we report on a set of CZTSe monocrystals with varied cation stoichiometry, enabling correlation of bulk composition to material and device properties without the complication of grain boundaries or secondary phases. Copper-poor, zinc-rich compositions (Cu/(Zn + Sn) = 0.77–0.90 and Zn/Sn = 1.17–1.25) yield bulk carrier lifetimes longer than 200 ps and PCE >5%. In contrast, near-stoichiometric compositions, with Cu/(Zn + Sn) > 0.90 and Zn/Sn < 1.15, have carrier lifetimes shorter than 20 ps and PCE <2%. CZTSe/CdS interface recombination velocity has a similar value to the CZTSe surface recombination velocity, with values of 104–105 cm/s determined by time-resolved terahertz spectroscopy and transport-recombination modeling. Device modeling reveals the dependence of open circuit voltage (VOC) on doping density, carrier lifetime and interface recombination. For a crystal with low doping density of 1015 cm−3, the maximum VOC is limited by the bulk lifetime. Higher VOC can be attained with higher doping density, but interface recombination becomes more significant with increased lifetime and doping density. These simulations indicate limitations and potential pathways to high performance.

Electronic transport and optoelectronic applications of a new layered semiconductor CuTaS3

Two-dimensional layered bi-transition metal chalcogenides with exotic physical and optoelectronic properties are becoming attractive and promising candidates for next-generation electronics and optoelectronics. Herein, we report a representative of bi-transition metal sulfide, the strip-shaped CuTaS3 crystal, analyzing its intrinsic electrical transport properties and potential optoelectronic applications by fabricating CuTaS3-based devices. The time-resolved Terahertz (THz) spectroscopy (TRTS) results indicate a rapid quenching of photoconductivity in CuTaS3 bulk within 4.1 ps photoexcitation. PL measurement and CuTaS3-based field effect transistors (FETs) show a typical n-type semiconducting behavior with a small, direct bandgap of 1.24 eV. Density functional theory (DFT) calculations reveal charge transfers between different atoms and phonon dispersion relations to help understand the structural and vibrational properties of CuTaS3. A CuTaS3-based-phototransistor was demonstrated with a responsivity of 7.6 mA W−1 and fast photoresponse time of 0.3–0.4 s, as well as excellent photoswitching stability. Our results may pave the way for developing other layered bi-transition metal chalcogenides and implementations in electronic and optoelectronic applications.

Time‐Resolved Terahertz Spectroscopy Studies on 2D Van der Waals Materials

AbstractOwing to the fascinating and technologically useful electronic and optical properties, 2D van der Waals (vdW) materials are viewed as the key component for the next‐generation optoelectronic, photovoltaic, and nanoelectronic devices. Fully understanding the ultrafast carrier dynamics in 2D vdW materials is essential to study the fundamental physics and realize potential applications. Time‐resolved terahertz (THz) spectroscopy is a powerful tool used to investigate the ultrafast carrier dynamics and transport properties in semiconducting materials. In recent years, the time‐domain THz spectroscopy measurements, with or without photoexcitation on samples, are widely used to investigate the carrier dynamics of 2D vdW materials. A brief summary on the recent progress of time‐domain THz spectroscopy studies on ultrafast dynamics processes is provided. These include exciton formation and relaxation processes in semiconducting 2D materials, the relaxation of hot electrons in graphene layers, the conductivity of 2D materials modulated by femtosecond laser pulses, and their related physical properties. Finally, the physical properties of 2D vdW materials observed using the time‐domain THz spectroscopy approach are highlighted and the future challenges for time‐resolved THz spectroscopy investigations on 2D vdW materials are presented.

Monitoring Electron-Phonon Interactions in Lead Halide Perovskites Using Time-Resolved THz Spectroscopy.

Lead halide perovskite semiconductors have low-frequency phonon modes within the lead halide sublattice and thus are considered to be soft. The soft lattice is considered to be important in defining their interesting optoelectronic properties. Electron-phonon coupling governs hot-carrier relaxation, carrier mobilities, carrier lifetimes, among other important electronic characteristics. Directly observing the interplay between free charge carriers and phonons can provide details on how phonons impact these properties (e.g., exciton populations and other collective modes). Here, we observe a delicate interplay among carriers, phonons, and excitons in mixed-cation and mixed-halide perovskite films by simultaneously resolving the contribution of charge carriers and phonons in time-resolved terahertz photoconductivity spectra. We are able to observe directly the increase in phonon population during carrier cooling and discuss how thermal equilibrium populations of carriers and phonons modulate the carrier transport properties, as well as reduce the population of carriers within band tails. We are also able to observe directly the formation of free charge carriers when excitons interact with phonons and dissociate and to describe how free carriers and exciton populations exchange through phonon interactions. Finally, we also time-resolve how the carriers are screened via the Coulomb interaction at low and room temperatures. Our studies shed light on how charge carriers interact with the low-energy phonons and discuss implications.

A semiconducting layered metal-organic framework magnet

The realization of ferromagnetism in semiconductors is an attractive avenue for the development of spintronic applications. Here, we report a semiconducting layered metal-organic framework (MOF), namely K3Fe2[(2,3,9,10,16,17,23,24-octahydroxy phthalocyaninato)Fe] (K3Fe2[PcFe-O8]) with spontaneous magnetization. This layered MOF features in-plane full π-d conjugation and exhibits semiconducting behavior with a room temperature carrier mobility of 15 ± 2 cm2 V−1 s−1 as determined by time-resolved Terahertz spectroscopy. Magnetization experiments and 57Fe Mössbauer spectroscopy demonstrate the presence of long-range magnetic correlations in K3Fe2[PcFe-O8] arising from the magnetic coupling between iron centers via delocalized π electrons. The sample exhibits superparamagnetic features due to a distribution of crystal size and possesses magnetic hysteresis up to 350 K. Our work sets the stage for the development of spintronic materials exploiting magnetic MOF semiconductors.

Sub-Picosecond Carrier Dynamics Induced by Efficient Charge Transfer in MoTe2/WTe2 van der Waals Heterostructures.

Demonstration of van der Waals (vdW) semiconductor/metal heterostructures (SMHs) based on transition metal dichalcogenides has been a central approach in high-speed electronics by introducing ultrafast carrier dynamics. In this regard, a Weyl semimetal WTe2 is of great interest due to its vdW layered nature, low work function, and superior electrical properties. However, little is still known about its heterostructures, and a few picoseconds photocarrier lifetimes hinder its applications in high-speed electronics. Here, we propose a SMH: semimetallic Td phase WTe2 with its sister compound of semiconducting 2H phase MoTe2. Time-resolved terahertz (THz) spectroscopy demonstrated that WTe2 exhibited the significantly shorter carrier lifetimes of sub-picosecond when forming a junction with MoTe2. We provided explicit characteristic signatures, revealing charge transfer across the interface and the subsequent interlayer exciton decay. This work not only offers the extension of the THz detection scope of ultrafast phenomena from atomically thin materials but also provides a building block of vertical SMHs for high-speed electronic devices with sub-picosecond photocarrier lifetimes.

Metal-Organic Framework Photoconductivity via Time-Resolved Terahertz Spectroscopy.

While metal-organic frameworks (MOFs) have been under thorough investigation over the pasttwo decades, photoconductive MOFs are an emerging class of materials with promising applications in light harvesting and photocatalysis. To date, there is not a general method to investigate the photoconductivity of polycrystalline MOF samples as-prepared. Herein, we utilize time-resolved terahertz spectroscopy along with a new sample preparation method to determine the photoconductivity of Zn2TTFTB, an archetypical conductive MOF, in a noncontact manner. Using this technique, we were able to gain insight into MOF photoconductivity dynamics with subpicosecond resolution, revealing two distinct carrier lifetimes of 0.6 and 31 ps and a long-lived component of several ns. Additionally, we determined the frequency dependent photoconductivity of Zn2TTFTB which was shown to follow Drude-Smith behavior. Such insights are crucially important with regard to developing the next generation of functional photoconductive MOF materials.

Transient photoconductivity and free carrier dynamics in a monolayer WS2 probed by time resolved Terahertz spectroscopy

The frequency and time resolved conductivity in a photoexcited large-area monolayer tungsten disulfide (WS2) have been simultaneously determined by using time-resolved terahertz spectroscopy. We use the Drude–Smith model to successfully reproduce the transient photoconductivity spectra, which demonstrate that localized free carriers, not bounded excitons, are responsible for the THz transport. Upon the optical excitation with 400 nm and 530 nm wavelength, the relaxation dynamics of the free carriers include fast and slow decay components with time constants approximately smaller than 1 ps and between 5–7 ps, respectively. The former sub-picosecond decay is attributed to the charge carrier loss induced by the exciton formation, while both the Auger recombination and the surface trapping can contribute to the slow relaxation.

Chemisorption of Atomically Precise 42-Carbon Graphene Quantum Dots on Metal Oxide Films Greatly Accelerates Interfacial Electron Transfer.

Graphene quantum dots (GQDs) are emerging as environmentally friendly, low-cost, and highly tunable building blocks in solar energy conversion architectures, such as solar (fuel) cells. Specifically, GQDs constitute a promising alternative for organometallic dyes in sensitized oxide systems. Current sensitized solar cells employing atomically precise GQDs are based on physisorbed sensitizers, with typically limited efficiencies. Chemisorption has been pointed out as a solution to boost photoconversion efficiencies, by allowing improved control over sensitizer surface coverage and sensitizer-oxide coupling strength. Here, employing time-resolved THz spectroscopy, we demonstrate that chemisorption of atomically precise C42-GQDs (hexa-peri-hexabenzocoronene derivatives consisting of 42 sp2 carbon atoms) onto mesoporous metal oxides, enabled by their functionalization with a carboxylate group, enhances electron transfer (ET) rates by almost 2 orders of magnitude when compared with physisorbed sensitizers. Density functional theory (DFT) calculations, absorption spectroscopy and valence band X-ray photoelectron spectroscopy reveal that the enhanced ET rates can be traced to stronger donor–acceptor coupling strength enabled by chemisorption.

Fermi Volume Evolution and Crystal-Field Excitations in Heavy-Fermion Compounds Probed by Time-Domain Terahertz Spectroscopy.

We measure the quasiparticle weight in the heavy-fermion compound CeCu_{6-x}Au_{x} (x=0, 0.1) by time-resolved terahertz spectroscopy for temperatures from 2 up to 300K. This method distinguishes contributions from the heavy Kondo band and from the crystal-electric-field satellite bands by different terahertz response delay times. We find that the formation of heavy bands is controlled by an exponentially enhanced, high-energy Kondo scale once the crystal-electric-field states become thermally occupied. We corroborate these observations by temperature-dependent dynamical mean-field calculations for the multiorbital Anderson lattice model and discuss consequences for quantum-critical scenarios.

On The Generation of Terahertz Pulses Using Thermoelastic Effect

Time-resolved terahertz spectroscopy can be proposed as a method of non-destructive testing of various parts, for example, aircraft composite materials. The theoretical background and the possibility of exciting pulses of electromagnetic waves in the range of terahertz oscillations using picosecond acoustic pulses excited by laser pulses based on the thermoelastic effect are studied.

Ultrafast THz modulators with WSe2 thin films [Invited

Tungsten diselenide (WSe2) thin films exhibit ultrafast carrier recombination lifetimes, which makes them promising candidates for high speed modulators. With pulsed optical excitation, they could be used to realize all-optical, frequency agile, terahertz devices. Looking into the potential of this material for such applications, time-resolved terahertz spectroscopy can provide significant insight into its free carrier and exciton dynamics such as recombination lifetimes, photo-induced conductivity and decay pathways. In this study, we measure transient terahertz conductivity and photo-generated carrier lifetimes in custom-grown large-area WSe2 thin-films. We discuss its dependence on grain size and number of layers. By analyzing the tradeoffs between carrier-lifetimes, photo-generated conductivity, grain size, and the number of layers, we show that the response of these films can be tailored by controlling the growth parameters. Customizing the film terahertz response can enable large modulation without the need for integration with bulk semiconductors, as widely reported in the literature, thereby achieve high terahertz photoconductivity and high-speed operation. Across samples, our measurements show carrier decay timescale on the order ~10 to 100 ps and a transient conductivity that shows non-Drude behavior. This deviation from a Drude response is dominant within the first few picoseconds (<10 ps) before changing into a Drude like free-carrier response at longer delays. Based on our grown films, we experimentally demonstrate a metamaterial terahertz modulator with WSe2 as the only active element, attaining ~40% modulation depth.

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.

Pump fluence dependence of ultrafast carrier dynamics in InSb measured by optical pump-terahertz probe spectroscopy.

Ultrafast carrier dynamics in intrinsic and n-doped InSb crystals were studied by time-resolved terahertz spectroscopy using an optical pump-terahertz probe setup with pump fluence from 32 μJ/cm2 to 1910 μJ/cm2. With photoexcitation at 800nm, the ultrafast photoinduced absorption and carrier recovery process of intrinsic and n-doped InSb showed strong pump fluence dependence. It was found that the magnitude of photoinduced absorption first increased and then decreased with pump fluence. The carrier recovery process could be well fitted with a single exponential curve at low pump fluence, but could be well fitted with a biexponential curve at high pump fluence when a fast photocarrier relaxation appeared. The magnitude of photoinduced absorption increased gradually at low pump fluence due to the increase of the carrier at the bottom of the conduction band by impact ionization. The magnitude of photoinduced absorption decreased gradually at high pump fluence, possibly due to the efficiency of transient Auger recombination greater than the rate of carriers generated in the impact ionization process. The fast decay process appearing at high pump fluence was thought to be dominated by transient Auger recombination.

Ultrafast photoinduced insulator-metal transition in epitaxial samarium nickelate thin films investigated by time-resolved terahertz spectroscopy

We investigate the ultrafast dynamic behavior of photoinduced insulator-metal phase transition in an epitaxially grown $\mathrm{SmNi}{\mathrm{O}}_{3}$ thin film by using time-resolved terahertz (THz) spectroscopy at different excitation fluences. It is found that the relaxation of the photoexcited carriers is characterized by two components with different time scales: (i) an ultrafast one with time constant varying between 0.3 ps (at 4.4 $\mathrm{mJ}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}2}$) and 0.35 ps (at 0.88 $\mathrm{mJ}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}2}$) and (ii) a slow one with a time constant varying between 1.7 ps (at 2 $\mathrm{mJ}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}2}$) and 4.7 ps (at 0.88 $\mathrm{mJ}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}2}$). These relaxation times could be primarily attributed to the coexistence of conducting and insulating charge-ordering domains. The observed behavior of the transient THz conductivity of $\mathrm{SmNi}{\mathrm{O}}_{3}$ thin film is well fitted by the Drude-Smith model, revealing that insulating domains emerge between the metallic domains, which in turn increase the carrier confinement during the relaxation process. Furthermore, the ultrafast dynamic behavior at different temperatures suggests that the insulating gap shrinks gradually between the Ni $3d$ and O $2p$ states as the temperature applied to the film increases. Our experimental findings pave the way to scientific opportunities and to technological applications of epitaxially grown $\mathrm{SmNi}{\mathrm{O}}_{3}$ thin film such as ultrafast optical switching and modulation devices.

Role of geminate electron-hole pairs in the time-resolved terahertz spectroscopy of organic semiconductors

Losses of the terahertz (THz) radiation energy transmitted through an organic semiconductor are examined for the time-resolved pump-probe experiments, in which electrons and holes are produced by the pump femtosecond laser pulse followed by the action of the THz probe pulse with duration of the order of 1 ps. Non-stationary electric polarization of electron-hole pairs by the electric field of THz probe pulse is considered to be responsible for the THz energy losses. The relative decrease of the THz energy density is found as a function of the sum of the electron – hole mobilities and delay time of the probe pulse with respect to the pump one.