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For nonlinear optical materials to be applicable as efficient broadband terahertz (THz) wave generators, low absorption with wide transparency in the THz frequency range is highly important. In this study, we report efficient organic THz wave generators, 2-(4-hydroxystyryl)-1-methylquinolinium 4-bromobenzenesulfonate (OHQ-BBS) single crystals. Interestingly, the OHQ-BBS crystals exhibit a wide molecular vibrational mode-free range in the THz frequency region from 1.7 to 5.1 THz with an absorption coefficient of <20 mm−1. By optical rectification employing 130 fs pump pulses at 1300 nm wavelength, the OHQ-BBS crystals generate extremely broad, dimple-free THz waves in the range of 1.2–5.5 THz. Additionally, a THz electric field that is 20 times higher than the field generated from the widely used ZnTe inorganic crystal is achieved. Therefore, the OHQ-BBS single crystals are highly promising materials for diverse THz photonic applications.

Although in terahertz (THz) source materials molecular anions significantly influence the performance of THz generation, only limited classes of molecular counter anions have been reported. Here, utilizing dichlorinated molecular anions in THz generators is reported for the first time, to the best of our knowledge. In these new crystals, two dichlorinated molecular anions with different molecular symmetries, asymmetric 3,4-dichlorobenzenesulfonate (34DCS) and symmetric 3,5-dichlorobenzenesulfonate (35DCS), are incorporated with a 2-(4-hydroxystyryl)-1-methylquinolinium (OHQ) cation possessing top-level molecular optical nonlinearity. OHQ-34DCS exhibits a strong nonlinear optical response, in contrast to OHQ-35DCS. In OHQ-34DCS crystals, the dichlorinated groups form strong halogen bonds (XBs) and hydrogen bonds (HBs), which are beneficial for suppressing molecular (phonon) vibrations. The optical-to-THz conversion efficiency of the OHQ-34DCS crystals is extremely high, comparable to that of the benchmark organic THz generators. Moreover, the THz emission spectra from the OHQ-34DCS crystals, compared to those of previously reported benchmark analogous crystals, are stronger modulated toward a flatter shape, but possess substantially reduced spectral dimples. Therefore, the introduction of dichlorinated molecular anions is an efficient approach for the design of highly efficient electro-optic salt crystals as efficient broadband THz wave sources.

In the last decade, terahertz (THz) technologies have been introduced to the detection, identification, and quantification of biomolecules in various biological samples. This review focuses on substances that represent important biomarkers in the urine associated with various cancers and their treatments. From a diagnostic point of view, urine liquid biopsy is particularly important because it allows the non-invasive and rapid collection of large volumes of samples. In this review, the THz spectral responses of substances considered metabolic biomarkers in urine and obtained in previous studies are collected. In addition, the findings from the relatively small number of prior studies that have already been carried out on urine samples are summarised. In this context, we also present the different THz methods used for urine analysis. Finally, a brief discussion is given, presenting perspectives for future research in this field, interpreted based on the results of previous studies. This work provides important information on the further application of THz techniques in biomedicine for detecting and monitoring urinary biomarkers for various diseases, including cancer.

Terahertz (THz) waves interact with molecular phonon vibrations of organic matter. When designing organic THz-device materials, conformational flexible groups (CFGs) are in most cases avoided. CFGs create many low-energy conformers with high conformational entropy, which results in large and many phonon vibration modes that lead to undesired self-absorption of THz waves. Here, nonpolar CFGs only having weak intermolecular interaction capability are unusually introduced into organic THz-device materials, utilized for efficient THz wave generation. Newly designed THz-source crystals possess nonpolar methylene (CH2)n units having high conformational flexibility. Compared to previously reported benchmark crystals without methylene CFGs, introducing methylene CFGs significantly reduces void volume in newly designed crystals. This leads to the suppression of molecular phonon vibrations below 2.0 THz (i.e., introducing flexibility results in local rigidity). At infrared pump wavelengths, new CFG-contained crystals generate a strong THz electric field that is one order of magnitude stronger than that generated in inorganic ZnTe crystals. CFG-contained crystals exhibit a flatter spectral shape of the generated THz wave than benchmark crystals without methylene CFGs. Therefore, the introduction of CFGs is a very intriguing design strategy for organic THz-device materials to reduce the limitations caused by phonon vibrations.

Development of new organic crystals possessing large second-order optical nonlinearity is very challenging because of strong tendency of centrosymmetric dipole–dipole molecular assembly in crystals. This tendency makes it difficult to develop various analogous crystals that allow fine tuning of optical and physical properties to enhance the device performance. A design approach of an isomorphic crystal library consisting of 11 highly efficient nonlinear optical salt crystals is reported. Analyzing the so-called isomorphic tolerance space in previously reported mother crystals (PMnXQ chromophores, where PM denotes piperidin-4-ylmethanol electron donor, n corresponds to the substi-tuted position of halogen (X) group on the quinolinium (Q) electron acceptor), various substituents are introduced into the PMnXQ crystals at different posi-tions, considering their space-filling characteristics and interionic interaction ability. All 11 PMnXQ crystals exhibit an isomorphic (or pseudo-isomorphic) crystal structure, in which the cationic chromophores form a perfectly parallel assembly for maximizing the second-order nonlinear optical susceptibility. The optical, physical, and crystal characteristics of newly designed, synthesized, and grown isomorphic PMnXQ crystals show both similarities and differences. Excellent THz wave-generation performance is demonstrated in both kHz- and MHz-repetition optical pump systems with new PMnXQ crystals. Therefore, the design approach using isomorphic tolerance space is very attractive for developing diverse isomorphic analogous organic crystals.

Newly designed halogenated organic quinolinium crystals proposed in this work provide fully optimized molecular ordering for maximizing the optical nonlinearity and high-performance broadband terahertz (THz) wave generation. The ultralarge diagonal optical nonlinearity (almost 300 × 10−30 esu) of the new halogenated crystals is approximately two times larger than that of state-of-the-art pyridinium-based crystals. In contrast, nonhalogenated analogous crystals exhibit very low (or vanishing) diagonal optical nonlinearity. This is attributed to halogen-induced unique interionic interactions and fine-tuning of the space-filling characteristics. In addition, the halogenated crystals show a good ability for bulk crystal growth of few millimetres lateral size with plate-like morphology and high thermal stability that are finally required for real-world applications. The new halogenated quinolinium crystals exhibit excellent THz wave generation characteristics, significantly surpassing the limit of conversion efficiency and spectral bandwidth of inorganic benchmark crystals. A 0.16 mm thick chlorinated crystal generates a 29-times larger THz field than 1.0 mm thick inorganic ZnTe crystals at 1500 nm pump wavelength with a flat and broadband spectrum extending up to ≈8 THz. Therefore, introducing halogen substituents is a potential design strategy for designing new organic crystals showing ultralarge macroscopic hyperpolarizability and high-performance THz wave generation.

In this study, we develop new organic benzothiazolium crystals possessing very large off-diagonal optical nonlinearity. In these crystals, benzothiazolium-based 2-(4-(4-(hydroxymethyl)piperidin-1-yl)styryl)-3-methyl-benzothiazol-3-ium (PMB) cations with large molecular optical nonlinearity are incorporated with two anions: 4 (trifluoromethoxy)benzenesulfonate (TFO) with an orthogonal non-planar shape and 5-bromothiophene-2-sulfonate (BTS) with a planar shape. Both PMB-TFO and PMB-BTS crystals exhibit state-of-the-art off-diagonal effective hyperpolarizability that results from the V-shape and X-shape alignments of PMB chromophores, respectively. Newly developed PMB crystals indicate excellent characteristics for second-order nonlinear optical applications such as difference-frequency generation (e.g. optical rectification) and sum-frequency generation (e.g. second-harmonic generation), which are comparable to current benchmark organic crystals.

We experimentally demonstrated a series of photonics-wireless transmissions in the 300–500 GHz band at the Technical University of Denmark (DTU) and the Zhejiang University (ZJU), with special efforts to drive the data rates beyond 100 Gbps and to extend the THz wireless reach by combining the techniques of state-of-the-art optoelectronic THz devices, spectrally efficient modulation formats and advanced digital signal processing., Part of book: ISBN 978-3-030-73738-2QC 20220610

Metamaterials are extremely important in advanced technologies, but usually,they rely on the resonant behavior of their constituent blocks. This strongly limitsthe application of metamaterials to particular frequency band ranges. However,metamaterials with broadband behaviors are highly desirable and are essentialfor many applications. Herein, recently discovered metamaterials that arecomposed of densely packed metallic nanoparticles but behave as effectivedielectrics are explored. Such metamaterials are extremely transparent for allwavelengths within or exceeding the near infrared and their performance isconstant across an ultra-broadband range of frequencies, which is vital to manydevices that operate across the same frequency range. The ability to tune therefractive index of these metamaterials to unnaturally high values while main-taining transparency opens new avenues, such as creatingflat, thin metalensesin the terahertz region where only bulk lenses are currently available. To highlightthose features, several new possible infrared and terahertz applications of thesemetamaterials which push the boundary of existing technology in THz photonicsare shown.

Metamaterials are extremely important in advanced technologies, but usually, they rely on the resonant behavior of their constituent blocks. This strongly limits the application of metamaterials to particular frequency band ranges. However, metamaterials with broadband behaviors are highly desirable and are essential for many applications. Herein, recently discovered metamaterials that are composed of densely packed metallic nanoparticles but behave as effective dielectrics are explored. Such metamaterials are extremely transparent for all wavelengths within or exceeding the near infrared and their performance is constant across an ultra-broadband range of frequencies, which is vital to many devices that operate across the same frequency range. The ability to tune the refractive index of these metamaterials to unnaturally high values while maintaining transparency opens new avenues, such as creating flat, thin metalenses in the terahertz region where only bulk lenses are currently available. To highlight those features, several new possible infrared and terahertz applications of these metamaterials which push the boundary of existing technology in THz photonics are shown.

The ideal laser source for nonlinear terahertz spectroscopy offers large versatility delivering both ultra-intense broadband single-cycle pulses and user-selectable multi-cycle pulses at narrow linewidths. Here we show a highly versatile terahertz laser platform providing single-cycle transients with tens of MV/cm peak field as well as spectrally narrow pulses, tunable in bandwidth and central frequency across 5 octaves at several MV/cm field strengths. The compact scheme is based on optical rectification in organic crystals of a temporally modulated laser beam. It allows up to 50 cycles and central frequency tunable from 0.5 to 7 terahertz, with a minimum width of 30 GHz, corresponding to the photon-energy width of ΔE=0.13 meV and the spectroscopic-wavenumber width of Δ(λ-1)=1.1 cm-1. The experimental results are excellently predicted by theoretical modelling. Our table-top source shows similar performances to that of large-scale terahertz facilities but offering in addition more versatility, multi-colour femtosecond pump-probe opportunities and ultralow timing jitter.

The terahertz range of the electromagnetic spectrum reveals important insights when studying material properties. An ultra-broadband terahertz time-domain spectroscopy system based on state-of-the-art, high-stability organic nonlinear optical crystals used as both THz wave generator and detector is presented. In transmission geometry, a broad spectrum exceeding 20 THz and a high dynamic range of more than 80 dB is achieved using a compact 100 MHz femtosecond laser working at telecom wavelength 1560 nm. In the normal-incidence reflection geometry, a similar bandwidth with a dynamic range surpassing 60 dB is reported. The experimental results are supported by a complete theoretical model, which includes the pump pulse duration, THz phonon/vibrational modes of the organic crystals and optical/THz beam path optimizations. The effectiveness of the newly developed system is demonstrated by measuring pharmaceutical samples with distinct THz features in the ultra-broadband THz range and by measuring narrow water vapor lines at a spectral resolution of 2.7 GHz (0.090 cm−1), resulting in an excellent accuracy with a frequency deviation of less than 0.05% from the reference values.

We demonstrate the first megahertz (MHz) repetition-rate, broadband terahertz (THz) source based on optical rectification in the organic crystal HMQ-TMS driven by a femtosecond Yb:fibre laser. Pumping at 1035 nm with 30 fs pulses, we achieve few-cycle THz emission with a smooth multi-octave spectrum that extends up to 6 THz at -30 dB, with conversion efficiencies reaching 10-4 and an average output power of up to 0.38 mW. We assess the thermal damage limit of the crystal and conclude a maximum fluence of ∼1.8 mJ·cm-2 at 10 MHz with a 1/e2 pump beam diameter of 0.10 mm. We compare the performance of HMQ-TMS with the prototypical inorganic crystal gallium phosphide (GaP), yielding a tenfold electric field increase with a peak on-axis field strength of 7 kV·cm-1 and almost double the THz bandwidth. Our results further demonstrate the suitability of organic crystals in combination with fibre lasers for repetition-rate scaling of broadband, high-power THz sources for time-domain spectroscopic applications.

Efficient broadband organic terahertz (THz) generators using X‐shaped alignment of the nonlinear optical chromophores, as an alternative to the parallel alignment of chromophores in benchmark organic crystals, are reported. All the developed six organic benzothiazolium crystals exhibit an isomorphic X‐shaped alignment of chromophores, resulting in an unprecedentedly large off‐diagonal optical nonlinearity (>100 × 10−30 esu), which presents one of the largest off‐diagonal optical nonlinearity of organic crystals. The benzothiazolium crystals exhibit efficient broadband THz wave generation employing the off‐diagonal optical nonlinearity, in contrast to the present state‐of‐the‐art organic THz generators that mostly utilize diagonal optical nonlinearity. For using off‐diagonal and diagonal optical nonlinearities, the polarization of the optical pump is perpendicular and parallel, respectively, to the polar axis of crystals. In addition to a large THz wave generation efficiency with one order of magnitude higher peak‐to‐peak THz electric field than that generated in a 1.0‐mm‐thick inorganic benchmark ZnTe crystal, the benzothiazolium crystals generate broadband THz spectra with an upper cut‐off frequency of near 8 THz, and the absence of strong absorption dimples in the range of 0.5−4 THz. Therefore, the X‐shaped alignment of chromophores presents an interesting potential alternative for efficient broadband organic THz generators.

Enhanced terahertz (THz) wave generation is demonstrated in nonlinear organic crystals through refractive index engineering, which improves phase matching characteristics substantially. Unlike conventional low‐bandgap nonlinear organic crystals, the newly designed benzimidazolium‐based HMI (2‐(4‐hydroxy‐3‐methoxystyryl)‐1,3‐dimethyl‐1H‐benzoimidazol‐3‐ium) chromophore possesses a relatively wide bandgap. This reduces the optical group index in the near‐infrared, allowing better phase matching with the generated THz waves, and leads to high optical‐to‐THz conversion. A unique feature of the HMI‐based crystals, compared to conventional wide‐bandgap aniline‐based crystals, is their remarkably larger macroscopic optical nonlinearity, a one order of magnitude higher diagonal component in macroscopic nonlinear susceptibility than NPP ((1‐(4‐nitrophenyl)pyrrolidin‐2‐yl)methanol) crystals. The HMI‐based crystals also exhibit much higher thermal stability, with a melting temperature Tm above 250 °C, versus aniline‐based crystals (116 °C for NPP). With pumping at the technologically important wavelength of 800 nm, the proposed HMI‐based crystals boost high optical‐to‐THz conversion efficiency, comparable to benchmark low‐bandgap quinolinium crystals with state‐of‐the‐art macroscopic nonlinearity. This performance is due to the excellent phase matching enabled by decreasing optical group indices in the near‐infrared through wide‐bandgap chromophores. The proposed wide‐bandgap design is a promising way to control the refractive index of various nonlinear organic materials for enhanced frequency conversion processes.

We report new organic nonlinear optical salt crystals comprising bis(head-to-tail) complementary cation–anion assembly that results in extremely efficient THz wave generation. In the new salt crystals, each of the ends of the molecular anion, 4-(trifluoromethyl)benzenesulfonate, possesses bis(hydrogen-bond acceptors), while each of the ends of the nonlinear optical molecular cationic chromophore, 2-(4-(4-(hydroxymethyl)piperidin-1-yl)styryl)-3-methylbenzothiazol-3-ium, possesses bis(hydrogen-bond donors). The resulting assembly fulfills the requirements for efficient broadband THz wave generation, namely, perfectly parallel alignment of the nonlinear optical cationic chromophores for maximizing the optical nonlinearity as well as strong interionic binding interactions for reducing self-absorption of the generated THz waves. The new benzothiazolium crystals provide extremely high optical-to-THz conversion efficiency with a broad THz spectral bandwidth of 8 THz, where the peak-to-peak THz electric field amplitude is 36 times higher than that of the benchmark inorganic 1.0 mm-thick ZnTe crystal when pumped at 1300 nm and also notably higher than those of benchmark organic analogous crystals.

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.

New organic THz generators are designed herein by molecular engineering of the refractive index, phonon mode, and spatial asymmetry. These benzothiazolium crystals simultaneously satisfy the crucial requirements for efficient THz wave generation, including having nonlinear optical chromophores with parallel alignment that provide large optical nonlinearity; good phase matching for enhancing the THz generation efficiency in the near-infrared region; strong intermolecular interactions that provide restraining THz self-absorption; high solubility that promotes good crystal growth ability; and a plate-like crystal morphology with excellent optical quality. Consequently, the as-grown benzothiazolium crystals exhibit excellent characteristics for THz wave generation, particularly at near-infrared pump wavelengths around 1100 nm, which is very promising given the availability of femtosecond laser sources at this wavelength, where current conventional THz generators deliver relatively low optical-to-THz conversion efficiencies. Compared to a 1.0-mm-thick ZnTe crystal as an inorganic benchmark, the 0.28-mm-thick benzothiazolium crystal yields a 19 times higher peak-to-peak THz electric field with a broader spectral bandwidth (>6.5 THz) when pumped at 1140 nm. The present work provides a valuable approach toward realizing organic crystals that can be pumped by near-infrared sources for efficient THz wave generation.

We experimentally demonstrate a terahertz (THz) photonic wireless transmission system in the 310 GHz band with four-level pulse amplitude modulation (PAM-4) signals. A zero-bias diode is used as a simple direct detection receiver, which is cost-effective compared to a conventional coherent receiver. Moreover, we comprehensively investigate the system performance by applying linear and nonlinear equalization schemes. The experimental results show that Volterra nonlinear filtering can significantly improve the system capacity by around 90%, and transmissions of up to 60 Gbit/s PAM-4 signals over a 3 m wireless link are successfully achieved. The advantageous features of this make it promising for high-speed THz wireless communications., QC 20210528

We report on a multi-dimensional multiplexed THz photonic wireless communication system. A record aggregated net rate of 1.059 Tbit/s over a wireless distance of 10 m in the 350 GHz band is experimentally demonstrated., SyskonpostNot duplicate with DiVA 1752579QC 20220609