Optical-pump THz-probe Spectroscopy Research Articles

Optical-pump-terahertz-probe spectroscopy in high magnetic fields with kHz single-shot detection.

We demonstrate optical pump-THz probe (OPTP) spectroscopy with a variable external magnetic field (0-9T), in which the time-dependent THz signal is measured by echelon-based single-shot detection at a repetition rate of 1kHz. The method reduces data acquisition times by more than an order of magnitude compared to conventional electro-optic sampling using a scanning delay stage. The approach illustrates the wide applicability of the single-shot measurement approach to non-equilibrium systems that are studied through OPTP spectroscopy, especially in cases where parameters such as magnetic field strength (B) or other experimental parameters are varied. We demonstrate the capabilities of our measurement by performing cyclotron resonance experiments in bulk silicon, where we observe B-field-dependent carrier relaxation and distinct relaxation rates for different carrier types. We use a pair of economical linear array detectors to measure 500 time points on each shot, offering an equivalent performance to camera-based detection with possibilities for higher repetition rates.

Terahertz spectroscopy of MOFs reveals dynamic structure and contact free ultrafast photoconductivity

Metal-organic frameworks (MOFs) are porous crystalline materials. Their large pores make them particularly interesting for membranes, gas separation, and gas storage. Furthermore, MOFs are ultralight, making them suitable for a large realm of exciting applications ranging from wearable devices to space technology. Optimizing MOFs for these applications demands a detailed understanding of their low energy dynamics and photophysics, which can be provided by terahertz (THz) spectroscopy. MOFs exhibit structural modes, or phonons, with energies in the meV range, which corresponds to the THz spectral range (0.1–10 THz, 0.4–40 meV). Understanding these modes is crucial in determining how a MOF interacts with guest molecules in the process of gas capture and storage. In this perspective, we discuss how gas-MOF interactions alter the MOFs’ spectral fingerprints. We demonstrate that THz spectroscopy can be used for gas adsorption monitoring and explain how density functional theory, together with THz spectra, can illuminate the dynamic structure of MOFs, providing unique insight into their functionality. THz is also a contact free probe for conductivity and allows us to measure short range conductivity within an individual MOF crystal. We will discuss the advantages of THz as a conductivity probe for MOFs as compared to more established direct current techniques. We will then expand our view to incorporate ultrafast photoconductivity in MOFs measured via optical pump-THz probe spectroscopy, in comparison to more established ultrafast spectroscopic tools such as optical transient absorption and photoluminescence. We will supplement this section with a discussion of THz studies on perovskites, which unveiled electron–phonon interactions not yet explored in MOFs.

Charge Carriers Localization Effect Revealed through Terahertz Spectroscopy of MXene: Ti3C2Tx.

The transport properties of charge carriers in MXene, a promising material, have been studied using terahertz time-domain spectroscopy (THz-TDS) to examine its potential applications in optical and electronic devices. However, previous studies have been limited by narrow frequency ranges, which have hindered the understanding of the intrinsic mechanisms of carrier transport in MXenes. To address this issue, ultrabroadband THz-TDS with frequencies of up to 15 THz to investigate the complex photoconductances of MXene (Ti3C2Tx) films with different thicknesses are employed. The findings indicate that the electronic localization is substrate-dependent, and this effect decreases with an increase in the number of layers. This is attributed to the screening effect of the high carrier density in Ti3C2Tx. Additionally, the layer-independent photocarrier relaxations revealed by optical pump THz probe spectroscopy (OPTP) provide evidence of the carrier heating-induced screening effect. These results are significant for practical applications in both scientific research and various industries.

Optimum Optical Designs for Diffraction-Limited Terahertz Spectroscopy and Imaging Systems Using Off-Axis Parabolic Mirrors

Off-axis parabolic mirrors (OAPMs) are widely used in the THz and mm-wave communities for spectroscopy and imaging applications, as a result of their broadband, low-loss operation and high numerical apertures. However, the aspherical shape of an OAPM creates significant geometric aberrations: these make achieving diffraction-limited performance a challenge, and lower the peak electric field strength in the focal plane. Here, we quantify the impact of geometric aberrations on the performance of the most widely used spectrometer designs, by using ray tracing and physical optics calculations to investigate whether diffraction-limited performance can be achieved in both the sample and the detector plane. We identify simple rules, based on marginal ray propagation, that allow spectrometers to be designed that are more robust to misalignment errors, and which have minimal aberrations for THz beams. For a given source, this allows the design of optical paths that give the smallest THz beam focal spot, with the highest THz electric field strength possible. This is desirable for improved THz imaging, for better signal-to-noise ratios in linear THz spectroscopy and optical-pump THz-probe spectroscopy, and to achieve higher electric field strengths in non-linear THz spectroscopy.

Optical Pump Terahertz Probe (OPTP) and Time Resolved Terahertz Spectroscopy (TRTS) of emerging solar materials

Photoconductivity is the crucial benchmark to assess the potential of any emerging material for future solar applications. Many optical techniques, like transient absorption and photoluminescence, explore bound electron states and provide indirect access to photoconductivity. Direct current (DC) measurements under solar simulation determine the total performance of a novel solar device. While this technique has a clear appeal, it involves electrical contacts, causing contact resistance, which impacts the measured conductivity. Furthermore, DC measurements do not provide any insight into ultrafast effects and the photophysics defining a novel material. Terahertz (THz) spectroscopy presents a contact-free technique to measure photoconductivity on a sub-ps time scale. These measurements can be performed on as-synthesized sample materials, including powders. The ultrafast time resolution informs us of trapping dynamics and reveals what physical processes limit the carrier lifetime in a novel material. Additionally, complex conductivity can be measured at THz frequencies. THz-conductivity and photoconductivity shed light on scattering effects, providing a road map toward minimizing these effects. However, THz spectroscopy is less intuitive than widely used DC measurements, and the interpretation of THz-results is more challenging. This tutorial aims to familiarize the reader with the main THz techniques used to explore emerging materials. We will illustrate how carrier lifetimes can be extracted from optical pump THz probe measurements. We will guide the reader through the process of extracting accurate photoconductivities from time resolved THz spectroscopy measurements and present the most commonly used models to describe the underlying physics. We will then discuss the difference between sample and material parameters and highlight potential pitfalls. The tutorial concludes with a perspective view on the ever evolving field of optical pump-THz probe spectroscopy of emerging materials.

Ultrafast hot-carrier cooling in quasi freestanding bilayer graphene with hydrogen intercalated atoms.

Femtosecond-THz optical pump probe spectroscopy is employed to investigate the cooling dynamics of hot carriers in quasi-free standing bilayer epitaxial graphene with hydrogen interacalation. We observe longer decay time constants, in the range of 2.6 to 6.4 ps, compared to previous studies on monolayer graphene, which increase nonlinearly with excitation intensity. The increased relaxation times are due to the decoupling of the graphene layer from the SiC substrate after hydrogen intercalation which increases the distance between graphene and substrate. Furthermore, our measurements show that the supercollision mechanism is not related to the cooling process of the hot carriers, which is ultimately achieved by electron optical phonon scattering.

Unraveling the Photophysics of Liquid-Phase Exfoliated Two-Dimensional ReS2 Nanoflakes

Few-layered transition metal dichalcogenides (TMDs) are increasingly popular materials for optoelectronics and catalysis. Amongst the various types of TMDs available today, rhenium-chalcogenides (ReX2) stand out due to their remarkable electronic structure, such as the occurrence of anisotropic excitons and potential direct bandgap behavior throughout multi-layered stacks. In this letter, we have analyzed the nature and dynamics of charge carriers in highly crystalline liquid-phase exfoliated ReS2, using a unique combination of optical pump-THz probe and broadband transient absorption spectroscopy. Two distinct time regimes are identified, both of which are dominated by unbound charge carriers despite the high exciton binding energy. In the first time regime, the unbound charge carriers cause an increase and a broadening of the exciton absorption band. In the second time regime, a peculiar narrowing of the excitonic absorption profile is observed, which we assign to the presence of built-in fields and/or charged defects. Our results pave the way to analyze spectrally complex transient absorption measurements on layered TMD materials and indicate the potential for ReS2 to produce mobile free charge carriers, a feat relevant for photovoltaic applications.

Unraveling the degradation process of 2D passivated and Cs stabilized FAPbI3 by optical pump THz probe spectroscopy

The carrier dynamics and time-dependent photo-physical properties in the degradation period of hybrid organic-inorganic lead halide perovskites (HOIPs) are still unclear. Here a non-contact optical pump THz probe measurement was performed to observe the long-term degradation process of 2D passivated and cesium stabilized formamidinium lead iodide perovskite (FAPbI3) films. We find that photoconductivity and carrier mobility of the FA0.9Cs0.1PbI3 film decay steadily, while these of the 2D phenylethylammonium lead iodide (PEA2PbI4) passivated FAPbI3 film show an accelerated decay rate. Moreover, it’s also revealed that the localization of charge carriers increases with the transformation process from the fitted results by the Drude-Smith model. These results indicate that the stabilized effect of Cs incorporation is continuous, while the passivated effect of PEA2PbI4 can be weakened by the newly emerged phase boundaries. This report proposes a new perspective and sheds light on the degradation process of HOIPs.

Charge Transport in Networks of sp3-Functionalized Single-Walled Carbon Nanotubes

The controlled introduction of luminescent sp3 defects into semiconducting single-walled carbon nanotubes (SWCNTs) leads to narrowband, tunable emission in the near-infrared and increases their photoluminescence (PL) quantum yield for potential optoelectronic applications [ACS Nano 2019, 13, 9259]. While the spectroscopic properties of sp3-functionalized SWCNTs are already well-established, a detailed understanding of the impact of functionalization on their electrical performance especially in a network is still lacking. Here, we investigate charge transport in ambipolar, light-emitting field-effect transistors based on networks of pristine and sp3-functionalized (6,5) SWCNTs. While both hole and electron mobilities decrease with increasing degree of functionalization, the transistors remain fully operational, showing electroluminescence from the defect states. Charge-modulated PL spectroscopy, which exclusively probes the mobile charge carriers in SWCNT networks [ACS Nano 2020, 14, 2412], confirms that the defects are efficiently sampled by mobile carriers and consequently, sp3-functionalized SWCNTs actively participate in the charge transport within the network. Temperature-dependent transport measurements of transistors combined with ultrafast photoconductivity dynamics of individually dispersed SWCNTs measured by optical-pump THz-probe spectroscopy provide further insights into the impact of sp3-functionalization on charge transport within a single nanotube and within a network.

Decoupling the effects of defects on efficiency and stability through phosphonates in stable halide perovskite solar cells

Summary Understanding defects is of paramount importance for the development of stable halide perovskite solar cells (PSCs). However, isolating their distinctive effects on device efficiency and stability is currently a challenge. We report that adding the organic molecule 3-phosphonopropionic acid (H3pp) to the halide perovskite results in unchanged overall optoelectronic performance while having a tremendous effect on device stability. We obtained PSCs with ∼21% efficiency that retain ∼100% of the initial efficiency after 1,000 h at the maximum power point under simulated AM1.5G illumination. The strong interaction between the perovskite and the H3pp molecule through two types of hydrogen bonds (H…I and O…H) leads to shallow point defect passivation that has a significant effect on device stability but not on the non-radiative recombination and device efficiency. We expect that our work will have important implications for the current understanding and advancement of operational PSCs.

Refractive index and optical-pump THz-probe measurement of ReSe2

In this paper, refractive index and optical-pump THz-probe measurement of ReSe2 nanosheets by using THz time-domain spectroscopy and optical-pump THz-probe spectroscopy were reported. The refractive index range of ReSe2 nanosheets is from 3.62 to 3.81 with frequency from 0.2 THz to 1.0 THz. The fast and slow decay times of the carrier dynamics of ReSe2 nanosheets were 1.28 ps and 8.7 ps, respectively. Our work provides the ultrafast dynamics of THz photoconductivity in ReSe2 nanosheets and facilitates its application in THz wave.

Terahertz Emission and Ultrafast Carrier Dynamics of Ar-Ion Implanted Cu(In,Ga)Se2 Thin Films

We investigated THz emission from Ar-ion-implanted Cu(In,Ga)Se2 (CIGS) films. THz radiation from the CIGS films increases as the density of implanted Ar ions increases. This is because Ar ions contribute to an increase in the surface surge current density. The effect of Ar-ion implantation on the carrier dynamics of CIGS films was also investigated using optical pump THz probe spectroscopy. The fitted results imply that implanted Ar ions increase the charge transition of intra-and carrier–carrier scattering lifetimes and decrease the bandgap transition lifetime.

Terahertz probe of nonequilibrium carrier dynamics and ultrafast photocurrents in the topological insulator Sb2Te3

In this study, we report the ultrafast excitation and dynamics of the carrier and photocurrent in a 3D typical topological insulator Sb2Te3. We utilize time-resolved optical pump-THz probe spectroscopy to explore the nonequilibrium carrier dynamics of Sb2Te3. The electron system undergoes an ultrafast relaxation and releases through intra-band and inter-band scattering. Additionally, THz emission spectroscopy is employed to investigate the different ultrafast photocurrents in Sb2Te3 through tuning the polarization of excitation pulses and rotating the sample's azimuthal angle. We distinguish the different ultrafast photocurrents driven by the linear photogalvanic effect, circular photogalvanic effect, and thermoelectric effect. Our results potentially enable an all-optical modulation of THz emission without any external bias field, which could play an important role in the development of topological insulator-based high-speed THz optoelectronic and opto-spintronic devices.

Ultrafast control of slow light in THz electromagnetically induced transparency metasurfaces

In this paper, we experimentally demonstrate ultrafast optical control of slow light in the terahertz (THz) range by combining the electromagnetically induced transparency (EIT) metasurfaces with the cut wire made of P+-implanted silicon with short carrier lifetime. Employing the optical-pump THz-probe spectroscopy, we observed that the device transited from a state with a slow light effect to a state without a slow light effect in an ultrafast time of 5 ps and recovered within 200 ps. A coupled oscillator model is utilized to explain the origin of controllability. The experimental results agree very well with the simulated and theoretical results. These EIT metasurfaces have the potential to be used as an ultrafast THz optical delay device.

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.

Ultrafast Photoexcited-Carrier Behavior Induced by Hydrogen Ion Irradiation of a Cu(In,Ga)Se2 Thin Film in the Terahertz Region

We investigated the effects of H <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">+</sup> ion irradiation on a chalcogenide Cu(In,Ga)Se <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> (CIGS) thin film as a function of the dose concentration (10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">14</sup> ∼ 10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">16</sup> /cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sup> ) at 200 keV by using time-resolved THz spectroscopy. The optical conductivity of these films was derived from THz time-domain spectroscopy (THz-TDS) in the THz region. THz emission spectroscopy revealed the emission of a strong-intensity THz pulse from the H <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">+</sup> ion-irradiated CIGS thin film. This is explained by considering the ultrafast behavior of photocarriers, resulting in strong surface band bending induced by the built-in potential with a conversion of the CIGS thin film from <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">p</i> - to <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">n</i> -type. Finally, we used optical pump THz probe spectroscopy to examine the ultrafast photocarrier dynamics determined by the time of capture at the increased number of surface and bulk defect states. This clearly showed that irradiation with H <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">+</sup> ions could generate a number of defect states while simultaneously pacifying the Cu vacancy defects.

Ultrafast electron transport in metallic antiferromagnetic Mn2Au thin films probed by terahertz spectroscopy

The ultrafast electron transport is central to the requirement of all-electrically controlled spintronics in metallic collinear antiferromagnetic (AFM) ${\mathrm{Mn}}_{2}\mathrm{Au}$ thin films within the terahertz (THz) range. Here we use the THz time-domain spectroscopy to measure the conductivity spectra of ${\mathrm{Mn}}_{2}\mathrm{Au}$ thin films with different thicknesses and temperatures. We demonstrate an onset of carrier localization in ${\mathrm{Mn}}_{2}\mathrm{Au}$ with decreasing the film thickness from 15 to 5 nm. By using optical pump-THz probe spectroscopy, we found the surface trapping states in the thinnest ${\mathrm{Mn}}_{2}\mathrm{Au}$ film limit its photoconductivity significantly. The DC conductivity and scattering time become larger and longer with decreasing temperature for all samples, which suggests that ${\mathrm{Mn}}_{2}\mathrm{Au}$ behaves in a typical metallic fashion. The THz optical and conductivity properties of ${\mathrm{Mn}}_{2}\mathrm{Au}$ films will advance our understanding of ultrafast electronic transport processes in AFM ${\mathrm{Mn}}_{2}\mathrm{Au}$ thin films.

Ultrafast charge carrier dynamics in quantum confined 2D perovskite.

We studied the charge carrier dynamics in 2D perovskite NBT2PbI4 by ultrafast optical pump-THz probe spectroscopy. We observed a few ps long relaxation dynamics that can be ascribed to the band to band carrier recombination, in the absence of any contribution from many-body and trap assisted processes. The transient conductivity spectra show that the polaron dynamics is strongly modulated by the presence of a rich exciton population. The polarization field resulting from the exciton formation acts as the source of a restoring force that localizes polarons. This is revealed by the presence of a negative imaginary conductivity. Our results show that the dynamics of excitons in 2D perovskites at room temperature can be detected by monitoring their effect on the conductivity of the photoinduced polaronic carrier.

Ultrafast wavelength-dependent carrier dynamics related to metastable defects in Cu(In,Ga)Se2 solar cells with chemically deposited Zn(O,S) buffer layer

The Cu(In,Ga)Se2 (CIGS) solar cells were fabricated with a Zn(O,S) buffer layer via chemical bath deposition method (CBD) using different thiourea (TU) mole concentration. The solar cells showed a substantial increment in the performance after light soaking treatment for 1 h. The performance increment was found to be in proportion to the TU mole concentration used in Z(O,S) layer deposition. To understand the cause of increased efficiency, we examined the metastable defect states that were reversible and reproducible in the CIGS solar cell. Firstly, to understand the film quality and the interface between CBD-Zn(O,S) and the CIGS layer, chemical states and band alignment along the depth direction was studied from the results of X-ray photoemission spectroscopy (XPS). It was observed that as the TU mole concentration increased, the distribution of S atoms in the CBD-Zn(O,S) layer changed from Gaussian to almost straight line due to the existence of numerous Zn–S bonds at the interface. With the actively diffused S atoms toward CIGS, a hollow band region was formed at the interface of the CIGS/CBD-Zn(O,S) layers, suppressing the electron-hole recombination, and thus enhancing the cell efficiency. Further, to measure the metastable defect states, optical pump-THz probe (OPTP) spectroscopy was utilized with two pumps having beam energies of 400 nm and 800 nm, which were sensitive enough to detect the defect states at an ultrafast time scale. We observed a unique and unusual decay curve of a re-excitation process after the initial ultrafast decay. The decay was contributed by “(VSe–VCu) divacancy complex,” which is considered a metastable defect state predominantly found near the surface of CIGS layer. The (VSe–VCu) metastable defect states were filled by photocarriers and then the re-excited photocarriers contributed to the expeditious flow of the photocurrent, giving rise to the increment of the cell efficiency.

Ultrafast THz Probe of Photoinduced Polarons in Lead-Halide Perovskites.

We study the nature of photoexcited charge carriers in CsPbBr_{3} nanocrystal thin films by ultrafast optical pump-THz probe spectroscopy. We observe a deviation from a pure Drude dispersion of the THz dielectric response that is ascribed to the polaronic nature of carriers; a transient blueshift of observed phonon frequencies is indicative of the coupling between photogenerated charges and stretching-bending modes of the deformed inorganic sublattice, as confirmed by DFT calculations.