Organic crystals with second-order optical nonlinearity feature very high and ultra-fast optical nonlinearities and are therefore attractive for various photonics applications. During the last decade, they have been found particularly attractive for terahertz (THz) photonics. This is mainly due to the very intense and ultra-broadband THz-wave generation possible with these crystals. We review recent progress and challenges in the development of organic crystalline materials for THz-wave generation and detection applications. We discuss their structure, intrinsic properties, and advantages compared to inorganic alternatives. The characteristic properties of the most widely employed organic crystals at present, such as DAST, DSTMS, OH1, HMQ-TMS, and BNA are analyzed and compared. We summarize the most important principles for THz-wave generation and detection, as well as organic THz-system configurations based on either difference-frequency generation or optical rectification. In addition, we give state-of-the-art examples of very intense and ultra-broadband THz systems that rely on organic crystals. Finally, we present some recent breakthrough demonstrations in nonlinear THz photonics enabled by very intense organic crystalline THz sources, as well as examples of THz spectroscopy and THz imaging using organic crystals as THz sources for various scientific and technological applications.

ordering in the crystalline state should be simultaneously considered when designing organic π-conjugated crystals to achieve the desired physical properties. However, the prediction of the molecular ordering of organic π-conjugated chromophores in the crystalline state is still significantly difficult. This is because most organic π-conjugated chromophores exhibit several complex intermolecular and intramolecular interactions (and interionic interactions) with multiple possible molecular conformations during the self-assembling process in the crystalline state. [17,18] For each specific target application, a different targeted control of the molecular ordering of chromophores in the crystalline state is required, which is still an important issue in the molecular (and crystal) engineering of various organic π-conjugated crystalline materials.This issue is more critical for organic nonlinear optical (NLO) crystals and will be the focus of this review. Organic NLO crystals can be used in diverse nonlinear photonic applications, such as frequency down-and up-conversion, terahertz (THz) wave generation and detection, phase and amplitude electro-optic modulation, and high-speed telecommunication integrated optics. [19][20][21][22][23] Organic crystals must possess a noncentrosymmetric molecular ordering of chromophores to achieve second-order optical nonlinearity. However, in addition to the aforementioned complicated molecular interactions, the introduction of strong polar substituents (electron-donating groups (EDGs) and electron-withdrawing groups (EWGs)) on widely used push-pull π-conjugated chromophores to increase their molecular nonlinearity also increases their dipole moment. In many cases, a high dipole moment leads to a centrosymmetric ordering of chromophores with antiparallel dipole-dipole aggregation in the crystalline state (i.e., there is no macroscopic second-order optical nonlinearity). This tendency further complicates the development of new organic NLO crystals with large second-order optical nonlinearity. This is one of the reasons for only a few classes of organic crystals with state-of-theart optical nonlinearity being reported in the last few decades. Moreover, in addition to large macroscopic second-order optical nonlinearity, different NLO applications require different targeted physical properties (e.g., refractive index, dispersion of the refractive index, dielectric constant, and absorption coefficient) and crystal characteristics (e.g., direction of the polar axis, morphology, aperture size, thickness, and facets). Therefore, it Organic π-conjugated crystals with second-order optical nonlinearity are considerably attractive materials for diverse terahertz (THz) wave photonics. An overview of the research of organic nonlinear optical (NLO) crystals for THz wave generation, detection, and applications is provided here. First, the status of organic NLO crystals compared to other alternative THz materials is described. Second, the basic theory and requirements for organic THz generators and d...

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.

Terahertz time-domain spectroscopy and imaging is used to study the effects of various hiding techniques of spectral features of drug and explosive simulants in combination with different paper and textile barriers. Results show that rapid detection and identification of concealed simulants is possible in the frequency range from 1.5 to 4.0 THz by using an organic-crystal-based terahertz time-domain system and the spectral peak analysis method.

Ultra‐broadband THz photonics covering the 0.3–20 THz range provides a very attractive foundation for a wide range of basic research and industrial applications. However, the lack of ultra‐broadband THz devices has yet to be overcome. In this work, high‐density organic electro‐optic crystals are newly developed for efficient THz wave generation in a very broad THz spectral range and are successfully used for a broadband THz time‐domain spectroscopy. The new organic THz generator crystals, namely the OHP‐TFS crystals, have very low void volume, high density, and are shown to cover the ultra‐broadband THz spectrum up to about 15 THz, which cannot be easily accessed with the more widely used inorganic‐based THz generators. In addition to the very favorable broadband properties, the generated THz electric‐field amplitude at the pump wavelength of 1560 nm is about 40 times higher than that generated by a commercial inorganic THz generator (ZnTe crystal). By using the newly developed OHP‐TFS as generation crystal in a compact table‐top all‐organic THz time‐domain spectrometer based on a low‐cost telecom fiber laser, the optical characteristics of a model material are successfully determined in the broad 1.5–12.5 THz range with high accuracy.