Sensitive Characterization of the Graphene Transferred onto Varied Si Wafer Surfaces via Terahertz Emission Spectroscopy and Microscopy (TES/LTEM).

Graphene shows great potential in developing the next generation of electronic devices. However, the real implementation of graphene-based electronic devices needs to be compatible with existing silicon-based nanofabrication processes. Characterizing the properties of the graphene/silicon interface rapidly and non-invasively is crucial for this endeavor. In this study, we employ terahertz emission spectroscopy and microscopy (TES/LTEM) to evaluate large-scale chemical vapor deposition (CVD) monolayer graphene transferred onto silicon wafers, aiming to assess the dynamic electronic properties of graphene and perform large-scale graphene mapping. By comparing THz emission properties from monolayer graphene on different types of silicon substrates, including those treated with buffered oxide etches, we discern the influence of native oxide layers and surface dipoles on graphene. Finally, the mechanism of THz emission from the graphene/silicon heterojunction is discussed, and the large-scale mapping of monolayer graphene on silicon is achieved successfully. These results demonstrate the efficacy of TES/LTEM for graphene characterization in the modern graphene-based semiconductor industry.

An innovative detection technique for capillary electrophoresis: Localized terahertz emission-time domain spectroscopy.

Terahertz (THz) time-domain spectroscopy (TDS) is a recently emerging analysis method which can provide unique information on molecular vibration and rotation induced by inter/intra-molecular interactions. Although the application of THz-TDS to high-performance microscale separation methods like capillary electrophoresis (CE) has been anticipated, it has been hindered due to the diffraction limit of THz wave (typically, hundreds µm). In order to realize CE-THz-TDS, in this study, we placed a narrow open-tubular capillary on the surface of a GaAs semiconductor substrate as a "localized" THz-emitter. By focusing femtosecond pulsed laser beams at the surface of a gallium arsenide (GaAs) substrate closest to the capillary, THz waves were locally generated to pass through the capillary, so that THz absorbance spectra were obtained from the capillary which has narrower inner diameter than the diffraction limit. As a typical result from acetic acid analysis in the CE-THz-TDS platform, information on the refractive index and extinction coefficient was obtained, which showed non-linear and linear concentration dependence, respectively, similar to conventional THz-TDS using large liquid cells. Finally, CE-THz-TDS analysis of several carboxylic acids was demonstrated. Two acids were successfully separated and detected with THz-TDS, where their electrophoretic mobility values were estimated as close to those obtained with conventional contactless conductivity detection. Our proposed CE-THz-TDS showed the potential for the systematic analysis of inter/intra-molecular weak interactions like hydrogen bonds, which are unable to obtain with conventional detectors.

Influence of dichroism on the optical properties of a twisted nematic liquid crystal cell in the terahertz region.

Polarization control is essential in terahertz (THz) imaging. Liquid crystals (LCs) have the potential to functionalize tunable polarization-control devices. Here, a twisted nematic (TN) cell using a hydrogen-bonded LC is fabricated, and the influence of dichroism in the THz region is discussed. Our results indicate that the polarization state in the Gooch-Tarry minimum condition is affected by the LC dichroism; a nondichroic LC is required for complete linearly polarized output. The output intensity of the dichroic LC-TN cell changed when electrically switched or when the incident THz wave polarization direction was rotated 90°. These intensity variations disappeared when using the nondichroic hydrogen-bonded LC.

Transition from Diffusive to Superdiffusive Transport in Carbon Nanotube Networks via Nematic Order Control.

The one-dimensional confinement of quasiparticles in individual carbon nanotubes (CNTs) leads to extremely anisotropic electronic and optical properties. In a macroscopic ensemble of randomly oriented CNTs, this anisotropy disappears together with other properties that make them attractive for certain device applications. The question however remains if not only anisotropy but also other types of behaviors are suppressed by disorder. Here, we compare the dynamics of quasiparticles under strong electric fields in aligned and random CNT networks using a combination of terahertz emission and photocurrent experiments and out-of-equilibrium numerical simulations. We find that the degree of alignment strongly influences the excited quasiparticles' dynamics, rerouting the thermalization pathways. This is, in particular, evidenced in the high-energy, high-momentum electronic population (probed through the formation of low energy excitons via exciton impact ionization) and the transport regime evolving from diffusive to superdiffusive.

Rapid, noncontact, sensitive, and semiquantitative characterization of buffered hydrogen-fluoride-treated silicon wafer surfaces by terahertz emission spectroscopy.

Advances in modern semiconductor integrated circuits have always demanded faster and more sensitive analytical methods on a large-scale wafer. The surface of wafers is fundamentally essential to start building circuits, and quantitative measures of the surface potential, defects, contamination, passivation quality, and uniformity are subject to inspection. The present study provides a new approach to access those by means of terahertz (THz) emission spectroscopy. Upon femtosecond laser illumination, THz radiation, which is sensitive to the surface electric fields of the wafer, is generated. Here, we systematically research the THz emission properties of silicon surfaces under different surface conditions, such as the initial surface with a native oxide layer, a fluorine-terminated surface, and a hydrogen-terminated surface. Meanwhile, a strong doping concentration dependence of the THz emission amplitude from the silicon surface has been revealed in different surface conditions, which implies a semiquantitative connection between the THz emission and the surface band bending with the surface dipoles. Laser-induced THz emission spectroscopy is a promising method for evaluating local surface properties on a wafer scale.

Intensity-dependent self-induced dual-color laser phase modulation and its effect on terahertz generation.

Powerful, broadband terahertz (THz) pulses and its application attract an exponential growth of interests. Dual-color laser filamentation in gases is one of the promising THz sources because of the scalability of the THz energy and wavelength with input parameters. But the additional phase induced by the nonlinearities associated with high intensities cannot be neglected because it may result in modulation of the THz waves. We investigate the influences of the infrared pump energy and air dispersion on the terahertz generation in dual-color laser filament. We observe that optimum dual-color laser relative phase of the THz generation undergoes a linear shift with increasing pump energy due to the intensity-induced refractive index change. This phase shift is verified by the spectral broadening of a two-color laser affected by the same mechanism. The result improves our understanding of the theoretical framework for a higher power THz source.

Terahertz Spectroscopy Tracks Proteolysis by a Joint Analysis of Absorptance and Debye Model.

Terahertz waves have attracted great attention in biomolecule research because of the fact that they cover the range of energy levels of weak interactions, skeleton vibrations, and dipole rotations during inter- and intramolecular interactions in biomacromolecules. In this study, we validated the feasibility of employing terahertz time-domain spectroscopy (THz-TDS) for the nondestructive and label-free monitoring of protein digestion. The acid protease, pepsin, was used at its optimal pH to hydrolyze bovine serum albumin. Correspondingly, the control group experiment was also conducted by adjusting the pH value to inactivate pepsin. The progress of these two experiments was tracked by a compact commercial THz-TDS for 1 h. On one hand, the reaction-time-dependent absorption coefficient was calculated, and a direct absorption coefficient analysis was completed. The results indicate that protein hydrolysis can be easily monitored over time by focusing on the variation tendency of the absorption coefficient from a macroscopic perspective. On the other hand, we explored the use of the Debye model to analyze the dielectric properties of the solution during protein hydrolysis. The results of the Debye analysis prove that it is possible to investigate in detail the microscopic dynamics of biomacromolecule solutions at the molecular level by THz-TDS. Our research examined the process of protein hydrolysis by a combination of absorption spectra and Debye analysis and demonstrated that terahertz spectroscopy is a powerful technology for the investigation of biomolecular reactions, with potential applications in variety of fields.

Ultrafast spatiotemporal photocarrier dynamics near GaN surfaces studied by terahertz emission spectroscopy.

Gallium nitride (GaN) is a promising wide-bandgap semiconductor, and new characterization tools are needed to study its local crystallinity, carrier dynamics, and doping effects. Terahertz (THz) emission spectroscopy (TES) is an emerging experimental technique that can probe the ultrafast carrier dynamics in optically excited semiconductors. In this work, the carrier dynamics and THz emission mechanisms of GaN were examined in unintentionally doped n-type, Si-doped n-type, and Mg-doped p-type GaN films. The photocarriers excited near the surface travel from the excited-area in an ultrafast manner and generate THz radiation in accordance with the time derivative of the surge drift current. The polarity of the THz amplitude can be used to determine the majority carrier type in GaN films through a non-contact and non-destructive method. Unique THz emission excited by photon energies less than the bandgap was also observed in the p-type GaN film.

Terahertz Excitonics in Carbon Nanotubes: Exciton Autoionization and Multiplication.

Excitons play major roles in optical processes in modern semiconductors, such as single-wall carbon nanotubes (CNTs), transition metal dichalcogenides, and 2D perovskite quantum wells. They possess extremely large binding energies (>100 meV), dominating absorption and emission spectra even at high temperatures. The large binding energies imply that they are stable, that is, hard to ionize, rendering them seemingly unsuited for optoelectronic devices that require mobile charge carriers, especially terahertz emitters and solar cells. Here, we have conducted terahertz emission and photocurrent studies on films of aligned single-chirality semiconducting CNTs and find that excitons autoionize, i.e., spontaneously dissociate into electrons and holes. This process naturally occurs ultrafast (<1 ps) while conserving energy and momentum. The created carriers can then be accelerated to emit a burst of terahertz radiation when a dc bias is applied, with promising efficiency in comparison to standard GaAs-based emitters. Furthermore, at high bias, the accelerated carriers acquire high enough kinetic energy to create secondary excitons through impact exciton generation, again in a fully energy and momentum conserving fashion. This exciton multiplication process leads to a nonlinear photocurrent increase as a function of bias. Our theoretical simulations based on nonequilibrium Boltzmann transport equations, taking into account all possible scattering pathways and a realistic band structure, reproduce all of our experimental data semiquantitatively. These results not only elucidate the momentum-dependent ultrafast dynamics of excitons and carriers in CNTs but also suggest promising routes toward terahertz excitonics despite the orders-of-magnitude mismatch between the exciton binding energies and the terahertz photon energies.

Measurable lower limit of thin film conductivity with parallel plate waveguide terahertz time domain spectroscopy.

Parallel plate waveguide (PPWG) terahertz (THz) time domain spectroscopy (TDS) is a powerful tool to investigate the properties of thin and low conductive materials. In this Letter, we determine the lower limit of detection of the PPWG-THz-TDS approach. We provide a closed-form expression of the minimal measurable conductivity by the system. The experimental results of amorphous YBa2Cu3O7-δ films indicate that the factor limiting the spectroscopic modality is the waveguide device misalignment. On the other hand, the expression of the minimal detectable conductivity provides a clear scheme of optimization by increasing the waveguide length and therefore enhancing the sensitivity of the system.

Adsorption energy of oxygen molecules on graphene and two-dimensional tungsten disulfide.

Adsorption of gas molecules on the surface of atomically layered two-dimensional (2D) materials, including graphene and transition metal dichalcogenides, can significantly affect their electrical and optical properties. Therefore, a microscopic and quantitative understanding of the mechanism and dynamics of molecular adsorption and desorption has to be achieved in order to advance device applications based on these materials. However, recent theoretical calculations have yielded contradictory results, particularly on the magnitude of the adsorption energy. Here, we have experimentally determined the adsorption energy of oxygen molecules on graphene and 2D tungsten disulfide using temperature-programmed terahertz (THz) emission microscopy (TPTEM). The temperature dependence of THz emission from InP surfaces covered with 2D materials reflects the change in oxygen concentration due to thermal desorption, which we used to estimate the adsorption energy of oxygen molecules on graphene (~0.15 eV) and tungsten disulphide (~0.24 eV). Furthermore, we used TPTEM to visualize relative changes in the spatial distribution of oxygen molecules on monolayer graphene during adsorption and desorption. Our results provide much insight into the mechanism of molecular adsorption on the surface of 2D materials, while introducing TPTEM as a novel and powerful tool for molecular surface science.

Probing low-density carriers in a single atomic layer using terahertz parallel-plate waveguides.

As novel classes of two-dimensional (2D) materials and heterostructures continue to emerge at an increasing pace, methods are being sought for elucidating their electronic properties rapidly, non-destructively, and sensitively. Terahertz (THz) time-domain spectroscopy is a well-established method for characterizing charge carriers in a contactless fashion, but its sensitivity is limited, making it a challenge to study atomically thin materials, which often have low conductivities. Here, we employ THz parallel-plate waveguides to study monolayer graphene with low carrier densities. We demonstrate that a carrier density of ~2 × 10(11) cm(-2), which induces less than 1% absorption in conventional THz transmission spectroscopy, exhibits ~30% absorption in our waveguide geometry. The amount of absorption exponentially increases with both the sheet conductivity and the waveguide length. Therefore, the minimum detectable conductivity of this method sensitively increases by simply increasing the length of the waveguide along which the THz wave propagates. In turn, enabling the detection of low-conductivity carriers in a straightforward, macroscopic configuration that is compatible with any standard time-domain THz spectroscopy setup. These results are promising for further studies of charge carriers in a diverse range of emerging 2D materials.

Visualization of GaN surface potential using terahertz emission enhanced by local defects.

Wide-gap semiconductors have received significant attention for their advantages over existing semiconductors in energy-efficient power devices. To realize stable and reliable wide-gap semiconductor devices, the basic physical properties, such as the electric properties on the surface and at the interface, should be revealed. Here, we report visualization of terahertz (THz) emission from the surface of GaN, which is excited by ultraviolet femtosecond laser pulses. We found that the THz emission is enhanced by defects related to yellow luminescence, and this phenomenon is explained through the modification of band structures in the surface depletion layer owing to trapped electrons at defect sites. Our results demonstrate that the surface potential in a GaN surface could be detected by laser-induced THz emission. Moreover, this method enables feasible evaluation of the distribution of non-radiative defects, which are undetectable with photoluminescence, and it contributes to the realization normally-off GaN devices.

Broadband plasmon induced transparency in terahertz metamaterials.

Plasmon induced transparency (PIT) could be realized in metamaterials via interference between different resonance modes. Within the sharp transparency window, the high dispersion of the medium may lead to remarkable slow light phenomena and an enhanced nonlinear effect. However, the transparency mode is normally localized in a narrow frequency band, which thus restricts many of its applications. Here we present the simulation, implementation, and measurement of a broadband PIT metamaterial functioning in the terahertz regime. By integrating four U-shape resonators around a central bar resonator, a broad transparency window across a frequency range greater than 0.40 THz is obtained, with a central resonance frequency located at 1.01 THz. Such PIT metamaterials are promising candidates for designing slow light devices, highly sensitive sensors, and nonlinear elements operating over a broad frequency range.

Tunable narrowband terahertz generation in lithium niobate crystals using a binary phase mask.

We present a simple scheme of narrowband terahertz (THz) generation by optical rectification in the lithium niobate crystal covered by a binary phase mask. It is shown that a single-domain crystal illumination by spatiotemporal shaped fs-laser pulses is equivalent to the formation of a transversally patterned, quasi-phase-matching structure. Decrease of the optical beam size on the mask leads to an increase of the THz-wave linewidth from 17 GHz to a few THz. The frequency of the generation was tuned in the range of 0.4-1.0 THz by building images of the mask in the crystal with various magnifications. Application results of the presented THz source for measuring transmittance of the superconducting NbN thin film in the 4.2-15 K temperature range are also presented.

Terahertz generation by optical rectification in lithium niobate crystal using a shadow mask.

A simple approach to generate high energy, frequency and bandwidth tunable multicycle THz pulses by optical rectification (OR) of spatially shaped femtosecond laser pulses in the lithium niobate (LN) crystal is proposed and demonstrated. A one dimensional binary shadow mask is used as a laser beam shaper. By building the mask's image in the bulk LN crystal with various demagnifications, the frequency of THz generation was tuned in the range of 0.3 - 1.2 THz. There exist also an opportunity to tune the bandwidth of THz generation from 20 GHz to approximately 1 THz by changing the optical beam size on the crystal. The energy spectral density of narrowband THz generation is almost independent of the bandwidth and is typically 0.18 µJ/THz for ~1 W pump power at 1 kHz repetition rate.

Terahertz generation in quasi-phase-matching structure formed by a phase mask.

It is theoretically shown that application of a phase mask in optical rectification scheme is equivalent to spatial modulation of the crystal's nonlinear coefficient in cross-section plane of the laser beam. It allows using the technique of quasi-phase-matching for efficient noncollinear terahertz (THz) generation by using high-power wide-aperture optical beam. According to calculations, the linewidth of THz generation can be varied from 10 GHz to a few THz by changing the optical beam size. It is shown that the frequency of THz generation can be also tuned by building the image of the phase mask in the crystal with variable magnification.

Distributed source model for the full-wave electromagnetic simulation of nonlinear terahertz generation.

The process of terahertz generation through optical rectification in a nonlinear crystal is modeled using discretized equivalent current sources. The equivalent terahertz sources are distributed in the active volume and computed based on a separately modeled near-infrared pump beam. This approach can be used to define an appropriate excitation for full-wave electromagnetic numerical simulations of the generated terahertz radiation. This enables predictive modeling of the near-field interactions of the terahertz beam with micro-structured samples, e.g. in a near-field time-resolved microscopy system. The distributed source model is described in detail, and an implementation in a particular full-wave simulation tool is presented. The numerical results are then validated through a series of measurements on square apertures. The general principle can be applied to other nonlinear processes with possible implementation in any full-wave numerical electromagnetic solver.

Terahertz and infrared spectroscopy of gated large-area graphene.

We have fabricated a centimeter-size single-layer graphene device with a gate electrode, which can modulate the transmission of terahertz and infrared waves. Using time-domain terahertz spectroscopy and Fourier-transform infrared spectroscopy in a wide frequency range (10-10 000 cm(-1)), we measured the dynamic conductivity change induced by electrical gating and thermal annealing. Both methods were able to effectively tune the Fermi energy, E(F), which in turn modified the Drude-like intraband absorption in the terahertz as well as the "2E(F) onset" for interband absorption in the mid-infrared. These results not only provide fundamental insight into the electromagnetic response of Dirac fermions in graphene but also demonstrate the key functionalities of large-area graphene devices that are desired for components in terahertz and infrared optoelectronics.