Takeshi Matsukawa

Polymorphs of Rubrene Crystal Grown from Solution

Single crystals of rubrene were grown by slow cooling of solutions in various solvents. Hexagonal single crystals were obtained from p-xylene, whereas parallelogram-shaped crystals were grown from aniline. Both types of crystal were obtained from propan-1-ol. Single-crystal X-ray diffraction analyses showed that the hexagonal and parallelogram-shaped crystals belonged to the orthorhombic system and the triclinic system, respectively. The triclinic crystals showed much poorer carrier mobilities than did the orthorhombic crystals.

Solution Growth of Rubrene Single Crystals Using Various Organic Solvents

To fabricate organic field-effect transistors (OFETs) with high carrier mobility, we attempted to grow 5,6,11,12-tetraphenylnaphthacene (rubrene) single crystals from solution and to improve their quality. Investigations into solvents in which rubrene was highly soluble proved that its solubility depended on the presence or absence of aromatic rings and chloro groups rather than on the polarity of the solvents. Rubrene crystals were grown from aromatic solvents, specifically from toluene, p-xylene, and aniline solvents, as well as from 1,2-dichloroethane (DCE) solvent. As a result, rubrene single crystals larger than 1 mm were obtained. Powder X-ray diffraction (XRD) analysis showed that the crystals obtained from the p-xylene and toluene solvents were rubrene, and 1H-nuclear magnetic resonance (1H-NMR) measurement proved that the crystals had not incorporated the solvent at the detection level. In addition, atomic force microscopy (AFM) confirmed that the rubrene crystals grown from the p-xylene and aniline solvents had flat faces and that the crystal from the p-xylene solvent had monomolecular steps on parts of the surfaces. Rubrene single crystal OFETs with graphite electrodes and parylene as an insulator showed carrier mobilities of ~0.75 cm2 V-1 s-1.

Development of an ultra-widely tunable DFG-THz source with switching between organic nonlinear crystals pumped with a dual-wavelength BBO optical parametric oscillator.

We developed a difference frequency generation (DFG) source with an organic nonlinear optical crystal of DAST or BNA selectively excited by a dual-wavelength β-BaB(2)O(4) optical parametric oscillator (BBO-OPO). The dual-wavelength BBO-OPO can independently oscillate two lights with different wavelengths from 800 to 1800 nm in a cavity. THz-wave generation by using each organic crystal covers ultrawide range from 1 to 30 THz with inherent intensity dips by crystal absorption modes. The reduced outputs can be improved by switching over the crystals with adequately tuned pump wavelengths of the BBO-OPO.

Bulk Crystal Growth of Stilbazolium Derivatives for Terahertz Waves Generation

The two stilbazolium derivatives, 4-dimethylamino-N-methyl-4-stilbazolium tosylate (DAST) and 4-dimethylamino-N-methyl-4-stilbazolium p-chlorobenzenesulfonate (DASC), are organic ionic nonlinear optical materials that have a tendency to form bulk crystals when grown in a mixed solvent of methanol and acetonitrile. We observed the generation of broadband high-power terahertz (THz) waves from the bulk crystals of DASC. DASC crystals have superior transmission characteristics in the THz band than DAST crystals, and it is expected that the THz waves generated using DASC crystals will have higher power than those generated using DAST crystals.

Terahertz emission from coherent phonons in lithium ternary chalcopyrite crystals illuminated by 1560 nm femtosecond laser pulses

We have investigated terahertz (THz) emission from lithium ternary chalcopyrite crystals LiInSe2, LiGaSe2, LiInS2, and LiGaS2 that were illuminated by 1560 nm femtosecond pump laser pulses. Monocyclic THz emission caused by nonlinear optical effects was initially observed in all the illuminated crystals. Narrow-band THz emission from the coherent phonons were observed in LiInSe2 (2.87 THz) and LiGaSe2 (2.60 and 3.45 THz). These phonon modes were most likely caused by impulsive stimulated Raman scattering.

Single Crystal Preparation of DAST for Terahertz-Wave Generation

DAST (1-methyl-4-{2-[4-(dimethylamino)phenyl]ethenyl}pyridinium p-toluenesulfonate) is a promising crystalline material for electro-optic applications and THz-wave generation. DAST powder for crystal growth was prepared by two synthesis routes including the conventional one and we confirmed that purity of DAST powder became indistinguishable after proper recrystallization even using conventional synthesis process. The highest solubility of DAST was found for methanol-acetonitrile mixture, and DAST crystal growth in this mixture or methanol-ethanol mixture gave thicker crystals than those grown in methanol. Thus, morphological control of DAST single crystals was found to be possible by varying solvents.

Solution growth of high-quality organic N-benzyl-2-methyl-4-nitroaniline crystal for ultra-wideband tunable DFG-THz source

We firstly obtained organic N-benzyl-2-methyl-4-nitroaniline (BNA) single crystals using solution growth method. The crystal quality obtained by solution growth method was much better than that of crystals grown by the Bridgman method. Furthermore, using difference frequency generation (DFG) in solution-grown BNA, we generated ultra-wideband tunable THz radiation.

10 aJ-level sensing of nanosecond pulse below 10 THz by frequency upconversion detection via DAST crystal: more than a 4 K bolometer

By using frequency upconversion detection of terahertz (THz) waves via 4-dimethylamino-N-methyl-4-stilbazolium tosylate (DAST) crystal with an optimized frequency conversion process, ultrahigh sensitivity has been achieved. Direct comparisons with a 4 K bolometer were implemented. By using a simple positive intrinsic negative (PIN) diode without either electrical amplification or optical amplification, frequency upconversion detection can compete with the commercial 4 K bolometer, while by replacing the PIN diode with an avalanche photo diode (APD), it performs more than three orders better than the 4 K bolometer. Based on power calibration, the minimum detectable THz pulse energy is in the order of 10 aJ (9-25 aJ) at 4.3 THz, with a pulse duration of 6 ns. Thus, the minimum number of THz photons that can be detected is down to the order of 10(3) at room temperature. The current THz detection system gives a noise equivalent power (NEP) in the order of 100  fW/Hz(1/2) (50-128  fW/Hz(1/2)). Moreover, by switching current optical detectors, the dynamic range is over six orders.

An ultra-broadband frequency-domain terahertz measurement system based on frequency conversion via DAST crystal with an optimized phase-matching condition

By applying the frequency conversion technique to 4-dimethylamino-N-methyl-4-stilbazolium tosylate crystal, a monochromatic terahertz (THz) measurement system, including both generation and detection, has been developed over quite a broad frequency band, from 1.85 to 30 THz. In the case of frequency upconversion detection of THz waves, for the first time, we used gratings instead of filters to tackle the tough phase-matching conditions for broadband operations. By synchronizing the rotation of two gratings to extract the frequency upconverted signal, the infrared (IR) pumping beam can be tuned freely over 300 nm with decent diffraction efficiency and sufficient isolation between the weak frequency upconversion signal and the strong IR pumping beam to be realized. Such a large tuning range has overcome the limit of commercial filters with a fixed passband, while such a high optical density value has been beyond the limit of commercial tunable filters. Consequently, the proposed frequency domain system gives the largest THz frequency band. Unlike THz time-domain spectroscopy systems in which a fs laser is applied and broadband THz pulses are applied, our system works based on a ns laser and it can function at a single THz frequency with random frequency access ability from pulse to pulse.

Real-time terahertz wave imaging by nonlinear optical frequency up-conversion in a 4-dimethylamino-N′-methyl-4′-stilbazolium tosylate crystal

Real-time terahertz (THz) wave imaging has wide applications in areas such as security, industry, biology, medicine, pharmacy, and arts. In this letter, we report on real-time room-temperature THz imaging by nonlinear optical frequency up-conversion in organic 4-dimethylamino-N′-methyl-4′-stilbazolium tosylate crystal. The active projection-imaging system consisted of (1) THz wave generation, (2) THz-near-infrared hybrid optics, (3) THz wave up-conversion, and (4) an InGaAs camera working at 60 frames per second. The pumping laser system consisted of two optical parametric oscillators pumped by a nano-second frequency-doubled Nd:YAG laser. THz-wave images of handmade samples at 19.3 THz were taken, and videos of a sample moving and a ruler stuck with a black polyethylene film moving were supplied online to show real-time ability. Thanks to the high speed and high responsivity of this technology, real-time THz imaging with a higher signal-to-noise ratio than a commercially available THz micro-bolometer cam...