Real-time high-spectral-resolution mid-infrared spectroscopy with a signal-to-noise ratio of ten thousand.

We developed a mid-infrared spectroscopy system with high spectral resolution and a high signal-to-noise ratio using an extremely high-order germanium immersion grating. The spectroscopic system covers wavelengths from 3 to 5 µm and has a spectral resolution of 1 GHz with a single-shot bandwidth of 2 THz. We proposed a method of improving the signal-to-noise ratio and achieved a ratio of over 3000 with a data acquisition rate of 125 Hz in the presence of fluctuations in the light source and environment. A signal-to-noise ratio of 10,000 was achieved with 0.1-s integration for 100-µW mid-infrared light.

Machined immersion grating with theoretically predicted diffraction efficiency.

An immersion grating composed of a transmissive material with a high refractive index (n>2) is a powerful device for high-resolution spectroscopy in the infrared region. Although the original idea is attributed to Fraunhofer about 200 years ago, an immersion grating with high diffraction efficiency has never been realized due to the difficulty in processing infrared crystals that are mostly brittle. While anisotropic etching is one successful method for fabricating a fine groove pattern on Si crystal, machining is necessary for realizing the ideal groove shape on any kind of infrared crystal. In this paper, we report the realization of the first, to the best of our knowledge, machined immersion grating made of single-crystal CdZnTe with a high diffraction efficiency that is almost identical to that theoretically predicted by rigorous coupled-wave analysis.

Wavefront analysis of high-efficiency, large-scale, thin transmission gratings.

Large-scale (180 × 60 × 1 mm(3)) transmission gratings with groove densities of 1250 and 1740 lines/mm have been developed, resulting in diffraction efficiencies above 95%. The throughput of a folded pulse compressor with two large-scale transmission gratings was approximately 80% in a 20-fs Ti:sapphire chirped-pulse amplification (CPA) laser. The parabolic bending of the transmission grating due to anti-reflection (AR) coating was minimized to 2.9 λ at 633 nm by improving the evaporation process. By a simple analysis, we explain why this level of bending does not induce a wavefront distortion through the transmission grating near the Littrow condition while the wavefront from a reflection grating is distorted to nearly twice the bending of the grating. The calculation based on the measured bending shows that both the group delay difference relative to the ideally flat grating from 750 to 850 nm and the spatial pulse front distortion over a 60-mm-diameter input beam are negligible, even when the dispersive beam covers ~140 mm on the grating. The spatial pulse front distortion measured after the compressor was less than the measurement limit (1.5 fs) for a 20-mm-diameter beam, where the beam size in the dispersive direction on the grating was 85 mm.

10-MHz, Yb-fiber chirped-pulse amplifier system with large-scale transmission gratings.

Large-scale transmission gratings were produced for a stretcher and a compressor in the Yb-fiber chirped-pulse amplification system. A 23-W, 200-fs laser system with a 10-MHz repetition rate was demonstrated. Focused intensity as high as 10(14) W/cm(2) was achieved, which is high enough for multi-photon processes such as high-order harmonics generation and multi-photon ionization of neutral atoms. High-order harmonics up to 7th order were observed using Xe gas as a nonlinear medium.

TEMPO/viologen electrochemical heterojunction for diffusion-controlled redox mediation: a highly rectifying bilayer-sandwiched device based on cross-reaction at the interface between dissimilar redox polymers.

A couple of totally reversible redox-active molecules, which are different in redox potentials, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and viologen (V(2+)), were employed to give rise to a rectified redox conduction effect. Single-layer and bilayer devices were fabricated using polymers containing these sites as pendant groups per repeating unit. The devices were obtained by sandwiching the redox polymer layer(s) with indium tin oxide (ITO)/glass and Pt foil electrodes. Electrochemical measurements of the single-layer device composed of polynorbornene-bearing TEMPO (PTNB) exhibited a diffusion-limited current-voltage response based on the TEMPO(+)/TEMPO exchange reaction, which was almost equivalent to a redox gradient through the PTNB layer depending upon the thickness. The bilayer device gave rise to the current rectification because of the thermodynamically favored cross-reaction between TEMPO(+) and V(+) at the polymer/polymer interface. A current-voltage response obtained for the bilayer device demonstrated a two-step diffusion-limited current behavior as a result of the concurrent V(2+)/V(+) and V(+)/V(0) exchange reactions according to the voltage and suggested that the charge transport process through the device was most likely to be rate-determined by a redox gradient in the polymer layer. Current collection experiments revealed a charge transport balance throughout the device, as a result of the electrochemical stability and robustness of the polymers in both redox states.

Anionic Polymerization of 4-Methacryloyloxy-TEMPO Using an MMA-Capped Initiator.

Anionic polymerization of 4-methacryloyloxy-TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidin-1-oxyl) was successfully carried out using methyl methacrylate-capped 1,1-diphenylhexyllithium (DPHLi/MMA), of which nucleophilicity is moderate enough to suppress the side reaction between the nitroxide radical of TEMPO moiety and the carbanion of DPHLi, to yield the radical polymer with well-controlled molecular weight, narrow polydispersity index (PDI < 1.10), high yield (>95%), and almost 1.0 radicals per monomer unit.