Macroscopic Optical Nonlinearity Research Articles

Symmetry Reduction of Molecular Shape of Cationic Chromophores for High‐Performance Terahertz Generators

AbstractThe symmetry reduction of molecular shape of cationic chromophores as a design strategy to develop organic terahertz (THz) generators is used. Electron donating group (EDG) with an asymmetric shape is introduced into two types of cationic styryl‐quinolinium chromophores, leading to the development of several novel non‐centrosymmetric crystals with high macroscopic optical nonlinearity. In contrast, when an EDG with a symmetric shape is introduced, centrosymmetric crystal structure is obtained in all investigated crystals. For THz wave generation, crystals based on asymmetrically shaped EDG exhibit several optimal crystal characteristics, including a plate‐shape morphology, a large size, and an in‐plane polar axis. Furthermore, over the entire range of molecular phonon vibrations, 0.5–4 THz, the steric hindrance group in the asymmetrically shaped EDG has a strong influence on the suppression of THz phonon vibrations, leading to a low THz absorption coefficient. The crystals based on asymmetrically shaped EDG generate an ≈40 times stronger THz electric field than the inorganic ZnTe crystal and very broad THz spectra, extending up to 16 THz. Thus, the symmetry reduction of the molecular shape of cationic chromophores through the introduction of an asymmetrically shaped EDG is an effective design approach for the development of novel organic THz crystals.

Design of High-Performance Organic Nonlinear Optical and Terahertz Crystals by Controlling the van der Waals Volume.

In the development of new organic crystals for nonlinear optical and terahertz (THz) applications, it is very challenging to achieve the essentially required non-centrosymmetric molecular arrangement. Moreover, the resulting crystal structure is mostly unpredictable due to highly dipolar molecular components with complex functional substituents. In this work, new organic salt crystals with top-level macroscopic optical nonlinearity by controlling the van der Waals volume (VvdW ), rather than by trial and error, are logically designed. When the VvdW of molecular ionic components varies, the corresponding crystal symmetry shows an observable trend: change from centrosymmetric to non-centrosymmetric and back to centrosymmetric. All non-centrosymmetric crystals exhibit an isomorphic P1 crystal structure with an excellent macroscopic second-order nonlinear optical response. Apart from the top-level macroscopic optical nonlinearity, new organic crystals introducing highly electronegative fluorinated substituents with strong secondary bonding ability show excellent performance in efficient and broadband THz wave generation, high crystal density, high thermal stability, and good bulk crystal growth ability.

Broadband THz wave generation in organic benzothiazolium crystals at MHz repetition rates [Invited

We present broadband terahertz wave generation based on benzothiazolium crystals at a 100 MHz repetition rate. Among various benzothiazolium crystals, we chose PMB-4TFS (2-(4-(4-(hydroxymethyl)piperidin-1-yl)styryl)-3-methylbenzothiazol-3-ium 4-(trifluorome-thyl)benzenesulfonate) due to its large macroscopic optical nonlinearity, good crystal characteristics, and suppressed molecular phonon vibrations. When pumped at the telecommunication wavelength of 1560 nm, the generated THz spectrum covers up to ∼15 THz and the corresponding THz amplitude for a 0.29 mm thick crystal at normal incidence is by more than one order of magnitude higher compared to the inorganic standard, 1.0 mm thick ZnTe generator crystal.

A New Class of Organic Crystals with Extremely Large Hyperpolarizability: Efficient THz Wave Generation with Wide Flat‐Spectral‐Band

AbstractIn organic π‐conjugated crystals, enhancing molecular optical nonlinearity of chromophores (e.g., first hyperpolarizability β ≥ 300 × 10−30 esu) in most cases unfortunately results in zero macroscopic optical nonlinearity, which is a bottleneck in organic nonlinear optics. In this study, a new class of nonlinear optical organic crystals introducing a chromophore possessing an extremely large first hyperpolarizability is reported. With newly designed 4‐(4‐(4‐(hydroxymethyl)piperidin‐1‐yl)styryl)‐1‐(pyrimidin‐2‐yl)pyridin‐1‐ium (PMPR) chromophore, incorporating a head‐to‐tail cation‐anion OH⋯O hydrogen‐bonding synthon and an optimal selection of molecular anion into crystals results in extremely large macroscopic optical nonlinearity with effective first hyperpolarizability of 335 × 10−30 esu. This is in sharp contrast to zero value for previously reported analogous crystals. An ultrathin PMPR crystal with a thickness of ≈10 µm exhibits excellent terahertz (THz) wave generation performance. Both i) broadband THz wave generation with a wide flat‐spectral‐band in the range of 0.7–3.4 THz defined at −3 dB and high upper cut‐off generation frequency of > 7 THz as well as ii) high‐generation efficiency (5 times higher THz amplitude than ZnTe crystal with a mm‐scale thickness) are simultaneously achieved. Therefore, new PMPR crystals are highly promising materials for diverse applications in nonlinear optics and THz photonics.

Orthogonal Molecular Assembly: Eliminating Intrinsic Phonon Modes in Organic THz Generators

AbstractThis work reports a series of new organic electro‐optic salt crystals possessing unusual orthogonal dipole‐coupling assembly that act as dimple‐free THz generators. In the new crystals, optically anisotropic aromatic anions introducing highly electronegative fluorinated substituents are orthogonally assembled with optically anisotropic nonlinear optical benzothiazolium cations. These orthogonal cation–anion assembled crystals exhibit strong suppression of intrinsic THz phonon modes along the polar axis, which results in a wide THz absorption‐free range from 1.5 to 4.0 THz without substantial absorption peaks. This is sharply in contrast to previous benchmark crystals with parallel cation–anion assembly; for example, in analogous crystals, several strong absorption peaks appear in this frequency range. This absence of strong absorption peaks is attributed to the orthogonal cation–anion dipole coupling assembly, the formation of fluorinate‐induced strong interionic interactions, and a high packing ability of uniaxial anions. With top‐level macroscopic optical nonlinearity, new orthogonal‐dipole assembled crystals make dimple‐free THz wave generation possible in the range of about 1.5–4.0 THz, which is very beneficial for characterizing signature peaks related to molecular phonon motions of analytes in THz spectroscopy. Therefore, orthogonal molecular assembly of optically highly anisotropic molecules provides an efficient way to substantially reduce and control intrinsic THz phonon modes.

New organic 4‐(4‐methoxystyryl)‐1‐methylpyridinium crystals for nonlinear optical applications

AbstractIn this study, an organic nonlinear optical salt crystal, 4‐(4‐methoxystyryl)‐1‐methylpyridinium 4‐bromobenzenesulfonate (MOS‐BBS), is newly reported. MOS‐BBS crystals exhibit perfectly parallel molecular ordering of 4‐(4‐methoxystyryl)‐1‐methylpyridinium (MOS) cationic chromophores with noncentrosymmetric P1 space group symmetry, which provides an optimal configuration for maximizing the macroscopic second‐order optical nonlinearity. The macroscopic optical nonlinearity of the MOS‐BBS crystals is very large, with the diagonal effective first hyperpolarizability of 160 × 10−30 esu. Furthermore, the MOS‐BBS crystals exhibit a high thermal crystal‐phase stability. The lowest phase transition temperature of the MOS‐BBS crystals is 265°C, which is ~90°C higher than that of previously reported MOS‐based crystals.

New N-pyrimidinyl stilbazolium crystals for second-order nonlinear optics

We report a new π-conjugated cationic chromophore based on phenolic N-pyrimidinyl stilbazolium and its corresponding non-centrosymmetric crystals. The new cationic chromophore, HPR (4-(4-hydroxy-3-methoxystyryl)-1-(pyrimidin-2-yl)pyridin-1-ium), consists of a strong electron donor, the 4-hydroxy-3-methoxyphenyl group based on two electron-donating groups, and a strong electron acceptor, the N-pyrimidinyl pyridinium group based on two electron-withdrawing groups. The HPR chromophore possesses large molecular optical nonlinearity with first hyperpolarizability of up to 264 × 10−30 esu, which is significantly larger than that of the benchmark stilbazolium chromophores. In solution, the HPR chromophore showed co-existence of phenol- and phenolate-like forms with two absorption bands (∼460 and ∼610 nm, respectively). In the crystalline state, all HPR-based derivatives with three different counter anions, N2S (naphthalene-2-sulfonate), VBS (4-vinylbenzenesulfonate), and NBS (3-nitrobenzenesulfonate), exhibit a macroscopic second-order nonlinear optical response. HPR-N2S crystals exhibit non-centrosymmetric monoclinic Pn space group symmetry and large off-diagonal effective macroscopic optical nonlinearity (94 × 10−30 esu), which is approximately four times higher than that of the benchmark stilbazolium crystals. Therefore, the newly developed HPR-based crystals are highly promising materials for second-order nonlinear optical applications.

Design Strategy of Highly Efficient Nonlinear Optical Orange‐Colored Crystals with Two Electron‐Withdrawing Groups

A new class of highly efficient nonlinear optical organic salt crystals is reported. In nonlinear optics based on organic materials, it is well known that using two electron‐withdrawing groups (EWGs) onto cationic electron acceptors instead of conventional one EWG remarkably enhances microscopic optical nonlinearity for chromophores. However, the corresponding organic crystals possessing enhanced large macroscopic optical nonlinearity have not been reported yet. Herein, a design strategy is proposed for obtaining highly efficient nonlinear optical crystals based on two EWGs in cationic electron acceptors. Introducing a phenolic electron donor, promoting a head‐to‐tail interionic assembly, along with a two‐EWG N‐pyrimidinyl pyridinium electron acceptor in cationic chromophores results in a preferred non‐centrosymmetric, perfectly parallel alignment of chromophores in crystal. Newly designed OPR (4‐(4‐hydroxystyryl)‐1‐(pyrimidin‐2‐yl)pyridinium) crystals exhibit approximately two times larger effective first hyperpolarizability than that of analogous N‐alkyl OHP (4‐(4‐hydroxystyryl)‐1‐methylpyridinium) crystals based on only one EWG. OPR crystals exhibit comparable second‐order optical nonlinearity to benchmark red‐colored DAST (4‐(4‐(dimethylamino)styryl)‐1‐methylpyridinium 4‐methylbenzenesulfonate) crystals, but a significant blue‐shifted absorption resulting in orange‐color crystals. Therefore, phenolic organic salt crystals using two EWGs are highly promising materials for various nonlinear optical applications.

Solid‐State Molecular Motions in Organic THz Generators

AbstractOrganic nonlinear optical salt crystals are widely used as efficient broadband THz generators. Although solid state molecular motions of organic crystals can greatly influence THz generation characteristics, their origin and effects on THz photonics are not clearly identified. In this work, the origin of solid‐state molecular motions of the state‐of‐the‐art nonlinear optical organic salt crystals and their effects on THz generation characteristics are theoretically investigated. A model crystal, HMQ‐TMS (2‐(4‐hydroxy‐3‐methoxystyryl)‐1‐methylquinolinium 2,4,6‐trimethylbenzenesulfonate) with large macroscopic optical nonlinearity, which is very attractive for intense broadband and narrowband THz wave generation, is chosen. The solid‐state molecular vibrations of HMQ‐TMS crystals can be classified in three frequency regions: phonon mode region, intramolecular motion region, and their mixing region. For the first time for ionic organic crystalline THz generators, the contributions of cationic chromophores and anionic matchmakers on each of vibrational modes are quantitatively separated. In addition, the influence of solid‐state molecular vibrations of HMQ‐TMS crystals on the generated THz spectra is investigated. These results provide an essential information for design of new organic nonlinear optical salt crystals for THz generators as well as detectors and for optimization of THz generation performance.

Wide‐Bandgap Organic Crystals: Enhanced Optical‐to‐Terahertz Nonlinear Frequency Conversion at Near‐Infrared Pumping

AbstractEnhanced 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.

Organic σ‐Hole Containing Crystals with Enhanced Nonlinear Optical Response and Efficient Optical‐to‐THz Frequency Conversion

AbstractA new approach for the molecular design of highly efficient nonlinear optical organic crystals is proposed by introducing substituents that form σ‐holes on both nonlinear optical cationic chromophores and aromatic anions. Introducing chlorinated substituents, in which a relatively positive σ‐hole and a negative belt coexist, provides selective reduction capability of specific π–π intermolecular interactions and simultaneous multiple secondary bonding capabilities. This leads to a crystalline state with enhanced first‐order hyperpolarizability βcrystal of chromophores that favors parallel chromophore alignment and suppression of molecular vibrations, which are optimal characteristics for electro‐optic and nonlinear optical applications, including efficient THz wave generation. Compared to benchmark nonhalogenated and fluorinated analogous crystals with state‐of‐the‐art macroscopic optical nonlinearity, σ‐hole containing chloro‐quinolinium crystals exhibit up to two times higher macroscopic nonlinear optical response and remarkably different crystal characteristics. As a result, a 0.16 mm thick chloro‐quinolinium crystal exhibits ≈22 times higher optical‐to‐THz conversion efficiency than the widely used 1.0 mm thick ZnTe inorganic crystal. Moreover, chloro‐quinolinium crystals exhibit very broad THz spectra, up to 8 THz with significantly different THz spectral shape compared to benchmark organic crystals, which is attributed to different phase matching between optical and THz frequencies and molecular vibration motions.

Efficient Gap‐Free Broadband Terahertz Generators Based on New Organic Quinolinium Single Crystals

AbstractNew organic electro‐optic crystals containing orthogonally oriented electron‐withdrawing groups are developed for efficient and gap‐free THz wave generation with a very flat broadband spectral shape. These crystals consist of 2‐(4‐hydroxystyryl)‐1‐methylquinolinium (OHQ) cationic chromophores and nonplanar 4‐(trifluoromethoxy)benzenesulfonate (TFO) anions with orthogonally oriented highly electronegative trifluoromethoxy groups capable of strong hydrogen bonds. OHQ‐TFO crystals exhibit enhanced macroscopic optical nonlinearity with a second harmonic generation efficiency 2.3 times greater than that of benchmark OHQ‐based crystals with conventional planar anions. This enhancement is attributed to reduced edge‐to‐face π–π interactions between cations and anions due to the orthogonal orientation and electron‐withdrawing characteristics of trifluoromethoxy groups. Moreover, OHQ‐TFO crystals exhibit excellent THz wave characteristics generated by optical rectification; 0.52 mm thick OHQ‐TFO crystal generate a peak‐to‐peak THz electric field 15 times higher than that of inorganic standard 1.0 mm thick ZnTe crystal and a broader spectrum with an upper cut‐off frequency near 8 THz at pump wavelengths of 1140–1500 nm. Unlike previously reported state‐of‐the‐art organic electro‐optic salt crystals with strong phonon absorption in the frequency range of 0.8–3 THz, OHQ‐TFO crystals facilitate gap‐free broadband THz wave generation without strong absorption modulations due to the strong hydrogen bond ability of trifluoromethoxy groups.

First-principle study on structural, linear and nonlinear optical properties of selenocyanate complex ZnCd(SeCN)4 crystal

Bimetallic selenocyanate complex ZnCd(SeCN)4 (ZCSC) crystals are a novel material with ultraviolet nonlinear optical (NLO) properties. To the best of our knowledge, theoretical studies on these complexes have mostly focused on the microcosmic NLO responses of single complex molecular system and ignored their macroscopic NLO effects. In this paper, the geometric structure of ZCSC crystal was optimized on the basis of first principle, and the electronic band structure and linear optical (LO) properties were investigated via pseudopotential plane wave method. The macroscopic NLO properties of ZCSC crystal were evaluated through the combination of density functional theory and a devised anionic group method for the first time, and good agreement with the experimental results was obtained. The absorption spectrum of ZCSC was located at 95–325 nm, and the NLO properties were mainly caused by the transitions of electronic states from N2p and Se3p valence bands to C2p, N2p, Se3p, and Cd4p conduction bands. Results showed that the second-order NLO coefficients were d14 = 2.304–3.55 pm/V and d15 = 8.07–9.91 pm/V, showing an evident increase compared with those of ZnCd(SCN)4 crystals.

Efficient terahertz generation in highly nonlinear organic crystal HMB-TMS.

We report on generation of strong and broadband terahertz (THz) pulses via collinearly phase-matched optical rectification of near-infrared femtosecond pulses in the organic nonlinear optical HMB-TMS (2-(4-hydroxy-3-methoxystyryl)-3-methylbenzo[d]thiazol-3-ium 2,4,6-trimethylbenzenesulfonate) single crystals which exhibit optimal molecular orientation and large macroscopic optical nonlinearity for efficient THz wave generation. Single-cycle THz pulses with a peak electric field strength of 0.66 MV/cm and a bandwidth from 0.1 to 5.4 THz are achieved from an HMB-TMS crystal with only a 2-mm clear aperture pumped by 1350 nm pulses at moderate fluences. The generated THz energy is about 1 µJ and the corresponding pump-to-THz energy conversion efficiency reaches 0.23%.

Organic Three‐Component Single Crystals with Pseudo‐Isomorphic Cocrystallization for Nonlinear Optics and THz Photonics

AbstractA new organic three‐component single crystals are developed using the so‐called “pseudo‐isomorphic cocrystallization” for nonlinear optical and terahertz (THz) photonic applications. The pseudo‐isomorphic cocrystallization is based on two homocrystals exhibiting similar molecular ordering feature in the crystalline state, but different crystallographic space groups. Such new organic cocrystals consist of three components, highly nonlinear optical 2‐(4‐hydroxystyryl)‐1‐methylquinolinium (OHQ) cation, and two different counter anions. Compared to homocrystals having two components (OHQ cation and a single anion type), OHQ‐based cocrystals by isomorphic cocrystallization from isomorphic homocrystals exhibit an isomorphic crystal structure with very similar physical properties. In contrast, OHQ‐based cocrystals by pseudo‐isomorphic cocrystallization provide a different molecular ordering with a different crystallographic space group, resulting in remarkably distinguishable crystal characteristics and physical properties, while maintaining large macroscopic optical nonlinearity with excellent optical quality and morphology suitable for diverse optical experiments. To show a potential for nonlinear optical applications, THz wave generation is demonstrated by optical rectification pumped at fundamental wavelength of 1300 nm. A 0.92 mm thick OHQ‐based cocrystal by pseudo‐isomorphic cocrystallization delivers efficient optical‐to‐THz conversion with one order of magnitude higher peak‐to‐peak THz electric field than the 1.0 mm thick inorganic standard ZnTe crystal and presents a broad spectral bandwidth of up to 8 THz.

Yellow‐Colored Electro‐Optic Crystals as Intense Terahertz Wave Sources

AbstractThis study presents newly developed yellow‐colored organic electro‐optic crystals to provide high terahertz (THz) wave generation efficiency. Compared with currently existing red‐ or orange‐colored electro‐optic crystals, which are used for most benchmark organic THz sources, yellow‐colored crystals have additional superior advantages for THz wave generation, e.g., higher transparency in the visible wavelength range with accompanying different phase‐matching possibilities. The new yellow‐colored crystals consist of a highly nonlinear optical 4‐(4‐hydroxystyryl)‐1‐methylpyridinium (OHP) cation, with a relatively short wavelength of maximal absorption at 390 nm in solution, and various halogen‐substituted benzenesulfonate anions, with strong secondary‐bonding ability. OHP 4‐chlorobenzenesulfonate (OHP‐CBS) crystals exhibit large off‐resonant macroscopic optical nonlinearity and high transparency, with a cut‐off wavelength for solid‐state absorption near 490 nm. OHP‐CBS crystals provide excellent THz wave generation characteristics based on optical rectification. A 0.53 mm thick OHP‐CBS crystal delivers ≈27 times higher optical‐to‐THz conversion efficiency and a much broader spectrum bandwidth compared with the standard 1.0 mm thick ZnTe at 1300 nm pumping. Particularly, compared with a benchmark organic quinolinium crystal with a similar thickness of 0.55 mm, OHP‐CBS crystals exhibit 1.7 times higher optical‐to‐THz conversion efficiency, and show a significantly different THz spectral shape.

Benzothiazolium Single Crystals: A New Class of Nonlinear Optical Crystals with Efficient THz Wave Generation.

Highly efficient nonlinear optical organic crystals are very attractive for various photonic applications including terahertz (THz) wave generation. Up to now, only two classes of ionic crystals based on either pyridinium or quinolinium with extremely large macroscopic optical nonlinearity have been developed. This study reports on a new class of organic nonlinear optical crystals introducing electron-accepting benzothiazolium, which exhibit higher electron-withdrawing strength than pyridinium and quinolinium in benchmark crystals. The benzothiazolium crystals consisting of new acentric core HMB (2-(4-hydroxy-3-methoxystyryl)-3-methylbenzo[d]thiazol-3-ium) exhibit extremely large macroscopic optical nonlinearity with optimal molecular ordering for maximizing the diagonal second-order nonlinearity. HMB-based single crystals prepared by simple cleaving method satisfy all required crystal characteristics for intense THz wave generation such as large crystal size with parallel surfaces, moderate thickness and high optical quality with large optical transparency range (580-1620 nm). Optical rectification of 35 fs pulses at the technologically very important wavelength of 800 nm in 0.26 mm thick HMB crystal leads to one order of magnitude higher THz wave generation efficiency with remarkably broader bandwidth compared to standard inorganic 0.5 mm thick ZnTe crystal. Therefore, newly developed HMB crystals introducing benzothiazolium with extremely large macroscopic optical nonlinearity are very promising materials for intense broadband THz wave generation and other nonlinear optical applications.

The design of second-order nonlinear optical dendrimers: From “branch only” to “root containing”

Dendrimers are considered as a promising family of organic second-order nonlinear optical (NLO) polymers because of their well-defined structures, easily modified peripheral functional groups, interior branches and central cores. In order to obtain NLO materials with high performance, dendrimer structures have been optimized in the past years, such as the “branch only” and the “root containing” type dendrimers. This feature article highlights the achievements in exploring the rational design of dendrimers, partially marked by their macroscopic NLO performance.

Terahertz Phonon Mode Engineering of Highly Efficient Organic Terahertz Generators

For terahertz (THz) wave generators based on organic electrooptic crystals, their intrinsic phonon modes are playing an essential role in THz generation characteristics. Here, this study proposes an effective design strategy for THz phonon mode engineering of organic electrooptic salt crystals for efficient optical‐to‐THz frequency conversion. To reduce phonon‐mode intensity, strongly electronegative trifluoromethyl group acting as strong hydrogen‐bond acceptor is incorporated into molecular anions. New 2‐(4‐hydroxy‐3‐methoxystyryl)‐1‐methylquinolinium 4‐(trifluoromethyl)benzenesulfonate (HMQ‐4TFS) crystals exhibit a relatively small absorption coefficient in the THz spectral range between 0.5 and 4 THz, which is attributed to suppressed molecular vibrations due to strong hydrogen bonds involving the 4TFS anion. In addition, HMQ‐4TFS crystals possess a very large macroscopic optical nonlinearity, comparable (or even higher) to benchmark stilbazolium crystals. Based on the low‐intensity THz phonon modes and the large optical nonlinearity, a 0.37 mm thick HMQ‐4TFS crystal pumped with 150 fs infrared laser pulses facilitates very efficient THz wave generation by optical rectification, delivering 23 times higher peak‐to‐peak THz electric field than the widely used standard inorganic ZnTe crystal (1.0 mm thick) and a broader spectral bandwidth. Therefore, strongly electronegative groups introduced into molecular salt electrooptic crystals provide a very promising design strategy of THz phonon mode engineering for developing intense broadband THz sources.

Quinolinium single crystals with a high optical nonlinearity and unusual out-of-plane polar axis

New phenolic quinolinium crystals with very large macroscopic optical nonlinearity and good crystal-growth ability exhibit an out-of-plane polar axis, which is very unusual considering other state-of-the-art organic nonlinear optical crystals exhibiting an in-plane polar axis.