Development of a cryogenic passive-scattering-type near-field optical microscopy system.

Passive scattering-type, scanning near-field optical microscopy (s-SNOM) has been employed to study localized, long-wavelength infrared (LWIR) surface waves without external illumination. Here, we develop a cryogenic passive s-SNOM instrument in a vacuum chamber with 4 K liquid-helium cooling. Notably, the extremely low-temperature environment inside the chamber enables the realization of passive near-field detection with low background thermal noise. The technique mainly utilizes a highly sensitive LWIR confocal optical system and a tuning fork-based atomic force microscope, and the near-field detection was performed at a wavelength of 10.2 ± 0.9 µm. In this paper, we discuss the cryogenic s-SNOM implementation in detail and report the investigation of thermally excited surface electromagnetic fields on a self-heated NiCr wire deposited on SiO2 at a temperature of 5 K. The origin of the surface electromagnetic fields was established to be the thermally excited fluctuating charges of the conduction electrons. The cryogenic s-SNOM method presented herein shows significant promise for application in a variety of spheres, including hot-carrier dissipation in ballistic conductors.

Quasiadiabatic electron transport in room temperature nanoelectronic devices induced by hot-phonon bottleneck.

Since the invention of transistors, the flow of electrons has become controllable in solid-state electronics. The flow of energy, however, remains elusive, and energy is readily dissipated to lattice via electron-phonon interactions. Hence, minimizing the energy dissipation has long been sought by eliminating phonon-emission process. Here, we report a different scenario for facilitating energy transmission at room temperature that electrons exert diffusive but quasiadiabatic transport, free from substantial energy loss. Direct nanothermometric mapping of electrons and lattice in current-carrying GaAs/AlGaAs devices exhibit remarkable discrepancies, indicating unexpected thermal isolation between the two subsystems. This surprising effect arises from the overpopulated hot longitudinal-optical (LO) phonons generated through frequent emission by hot electrons, which induce equally frequent LO-phonon reabsorption ("hot-phonon bottleneck") cancelling the net energy loss. Our work sheds light on energy manipulation in nanoelectronics and power-electronics and provides important hints to energy-harvesting in optoelectronics (such as hot-carrier solar-cells).

Near-Field Radiative Nanothermal Imaging of Nonuniform Joule Heating in Narrow Metal Wires.

Probing spatial variation of temperature at the nanoscale provides key information for exploring diverse areas of modern science and technology. Despite significant progress in the development of contact thermometers with high spatial resolution, one inherent disadvantage is that the quantitative analysis of temperature can be complicated by the direct thermal contact. On the other hand, noncontact infrared radiation thermometer is free from such contact-induced disturbance, but suffers from insufficient spatial resolution stemming from diffraction-limit in the micrometer range. Combining a home-built sensitive infrared microscope with a noncontact scattering probe, we detected fluctuating electromagnetic evanescent fields on locally heated material surface, and thereby mapped temperature distribution in subwavelength scales. We visualize nanoscale Joule heating on current-carrying metal wires and find localized "hot-spots" developing along sharp corners of bended wires in the temperature mapping. Simulation calculations give quantitative account of the nanoscale temperature distribution, definitely indicating that the observed effect is caused by the nonuniform energy dissipation due to the current-crowding effect. The equipment in this work is a near-field version of infrared radiation thermometer with a spatial resolution far below the detection wavelength (<100 nm, or λ/140) in which local temperature distribution of operating nanoscale devices can be noninvasively mapped with a temperature resolution ∼2 K at room-temperature.

Imaging of nonlocal hot-electron energy dissipation via shot noise.

In modern microelectronic devices, hot electrons accelerate, scatter, and dissipate energy in nanoscale dimensions. Despite recent progress in nanothermometry, direct real-space mapping of hot-electron energy dissipation is challenging because existing techniques are restricted to probing the lattice rather than the electrons. We realize electronic nanothermometry by measuring local current fluctuations, or shot noise, associated with ultrafast hot-electron kinetic processes (~21 terahertz). Exploiting a scanning and contact-free tungsten tip as a local noise probe, we directly visualize hot-electron distributions before their thermal equilibration with the host gallium arsenide/aluminium gallium arsenide crystal lattice. With nanoconstriction devices, we reveal unexpected nonlocal energy dissipation at room temperature, which is reminiscent of ballistic transport of low-temperature quantum conductors.

A high signal-to-noise ratio passive near-field microscope equipped with a helium-free cryostat.

We have developed a passive long-wavelength infrared (LWIR) scattering-type scanning near-field optical microscope (s-SNOM) installed in a helium-free mechanically cooled cryostat, which facilitates cooling of an LWIR detector and optical elements to 4.5 K. To reduce mechanical vibration propagation from a compressor unit, we have introduced a metal bellows damper and a helium gas damper. These dampers ensure the performance of the s-SNOM to be free from mechanical vibration. Furthermore, we have introduced a solid immersion lens to improve the confocal microscope performance. To demonstrate the passive s-SNOM capability, we measured thermally excited surface evanescent waves on Au/SiO2 gratings. A near-field signal-to-noise ratio is 4.5 times the improvement with an acquisition time of 1 s/pixel. These improvements have made the passive s-SNOM a more convenient and higher-performance experimental tool with a higher signal-to-noise ratio for a shorter acquisition time of 0.1 s.

Tip size dependence of passive near-field microscopy.

We improve the spatial resolution and investigate the tip-sample coupling in a passive scattering-type scanning near-field optical microscope (s-SNOM), which probes thermally excited surface waves without any external light source. We study the spatial resolution, the intensity, and the decay behavior of the thermally excited near-field signals with different radii of curvatures of tungsten-tip apexes. We also study the tip size dependence of the interference pattern in the far-field region. The spatial resolution is closely related to the tip size, but the decay behavior of the near field is unrelated. These results suggest that the strength of the tip-sample coupling is unrelated to the tip size in the passive s-SNOM. We propose a theoretical model able to interpret the experimental data for the passive s-SNOM.

Design and synthesis of 2-amino-6-(1H,3H-benzo[de]isochromen-6-yl)-1,3,5-triazines as novel Hsp90 inhibitors.

A novel series of 2-amino-1,3,5-triazines bearing a tricyclic moiety as heat shock protein 90 (Hsp90) inhibitors is described. Molecular design was performed using X-ray cocrystal structures of the lead compound CH5015765 and natural Hsp90 inhibitor geldanamycin with Hsp90. We optimized affinity to Hsp90, in vitro cell growth inhibitory activity, water solubility, and liver microsomal stability of inhibitors and identified CH5138303. This compound showed high binding affinity for N-terminal Hsp90α (Kd=0.52nM) and strong in vitro cell growth inhibition against human cancer cell lines (HCT116 IC50=0.098µM, NCI-N87 IC50=0.066µM) and also displayed high oral bioavailability in mice (F=44.0%) and potent antitumor efficacy in a human NCI-N87 gastric cancer xenograft model (tumor growth inhibition=136%).

Plasmonic light harvesting for multicolor infrared thermal detection.

Here we combined experiments and theory to study the optical properties of a plasmonic cavity consisting of a perforated metal film and a flat metal sheet separated by a semiconductor spacer. Three different types of optical modes are clearly identified-the propagating and localized surface plasmons on the perforated metal film and the Fabry-Perot modes inside the cavity. Interactions among them lead to a series of hybridized eigenmodes exhibiting excellent spectral tunability and spatially distinct field distributions, making the system particularly suitable for multicolor infrared light detections. As an example, we design a two-color detector protocol with calculated photon absorption efficiencies enhanced by more than 20 times at both colors, reaching ~42.8% at f1 = 20.0THz (15µm in wavelength) and ~46.2% at f2 = 29.5THz (~10.2µm) for a 1µm total thickness of sandwiched quantum wells.

Enantioselective synthesis of derivatives and structure-activity relationship study in the development of NA255 as a novel host-targeting anti-HCV agent.

Hepatitis C virus (HCV) infection represents a serious health-care problem. Previously we reported the identification of NA255 from our natural products library using a HCV sub-genomic replicon cell culture system. Herein, we report how the absolute stereochemistry of NA255 was determined and an enantioselective synthetic method for NA255 derivatives was developed. The structure-activity relationship of the NA255 derivatives and rat pharmacokinetic profiles of the representative compounds are disclosed.

A new scheme for sensitive detection of terahertz photons.

Charge sensitive infrared photo transistors (CSIPs) made in GaAs/AlGaAs bilayer two-dimensional electron systems (2DESs) serve as sensitive photodetectors in the mid- and long-wavelength infrared regions. A new design of CSIP is proposed to expand the wavelength range to longer wavelengths (λ > 36 µm). Remarkably improved detector performance is demonstrated for λ ≈ 39 µm. In CSIPs electrons are photo-excited in a floating gate (FG) served by an isolated region of upper layer 2DESs. In the new design (i) a bow-tie antenna couples incident radiation to an FG far smaller in size (2-3 µm) than the wavelength and (ii) excited electrons 'laterally' escape from the FG via tunneling through a barrier formed by biased metal cross gates. The charge state of the FG is sensed by a source-drain channel in the lower layer of the 2DES. The sensitivity and the quantum efficiency have been greatly improved, indicating that CSIPs are promising detectors in an expanded wavelength range exceeding 36 µm.

Design and synthesis of novel macrocyclic 2-amino-6-arylpyrimidine Hsp90 inhibitors.

Macrocyclic compounds bearing a 2-amino-6-arylpyrimidine moiety were identified as potent heat shock protein 90 (Hsp90) inhibitors by modification of 2-amino-6-aryltriazine derivative (CH5015765). We employed a macrocyclic structure as a skeleton of new inhibitors to mimic the geldanamycin-Hsp90 interactions. Among the identified inhibitors, CH5164840 showed high binding affinity for N-terminal Hsp90α (K(d)=0.52nM) and strong anti-proliferative activity against human cancer cell lines (HCT116 IC(50)=0.15µM, NCI-N87 IC(50)=0.066µM). CH5164840 displayed high oral bioavailability in mice (F=70.8%) and potent antitumor efficacy in a HCT116 human colorectal cancer xenograft model (tumor growth inhibition=83%).

Thermally excited near-field radiation and far-field interference.

Thermal radiation from samples of Au layers patterned on GaAs, SiO(2), and SiC at 300 K are studied with a scattering-type scanning near-field optical microscope (wavelength: ~14.5 µm), without applying external illumination. Clear near-field images are obtained with a spatial resolution of ~60 nm. All the near field signals derived from different demodulation procedures decrease rapidly with increasing probe height h with characteristic decay lengths of 40 ~60 nm. Near-field images are free from any signature of in-plane spatial interference. The findings are accounted for by theoretically expected surface evanescent waves, which are thermally excited in the close vicinity of material surfaces. Outside the near-field zone (1 µm < h), signals reappear and vary as a sinusoidal function of h, exhibiting a standing wave-like interference pattern. These far-field signals are ascribed to the effect of weak ambient radiation.

A sensitive near-field microscope for thermal radiation.

A scattering-type scanning near-field optical microscope in long-wavelength infrared (LWIR) region is developed by using an extremely sensitive detector, called the charge-sensitive infrared phototransistor. A tungsten probe attached to a quartz tuning fork is controlled in shear-force mode. Evanescent wave at a sample surface is periodically scattered by slowly (2 Hz) modulating the probe in the direction normal to the sample surface. Near-field microscopy of thermal LWIR radiation from room-temperature Au/GaAs gratings is demonstrated without using any external illumination or excitation. Achieved spatial resolution is better than 300 nm.

Sensing individual terahertz photons.

One of the promising ways to perform single-photon counting of terahertz radiation consists in sensitive probing of plasma excitation in the electron gas upon photon absorption. We demonstrate the ultimate sensor operating on this principle. It is assembled from a GaAs/AlGaAs quantum dot, electron reservoir and superconducting single-electron transistor. The quantum dot is isolated from the surrounding electron reservoir in such a way that when the excited plasma wave decays, an electron could tunnel off the dot to the reservoir. The resulting charge polarization of the dot is detected with the single-electron transistor. Such a system forms an easy-to-use sensor enabling single-photon counting in a very obscure wavelength region.

Novel ultra-sensitive detectors in the 10-50 µm wavelength range.

We have developed novel single-photon detectors in the 10-50 µm wavelength region. The detectors are charge-sensitive infrared phototransistors (CSIPs) fabricated in GaAs/AlGaAs double quantum well (QW) structures, in which a photo-generated hole (+e) in the floating gate (upper QW) modulates the conductance of a capacitively-coupled channel located underneath (lower QW). The excellent noise equivalent power (NEP = 8.3 × 10(-19) W/Hz(1/2)) and specific detectivity (D(*) = 8 × 10(14) cm Hz(1/2)/W) are demonstrated for 15 micron detection up to 23 K, which are by a few orders of magnitude better than those of other state-of-the-art high-sensitivity detectors. The dynamic range exceeds 10(6) (~aW to pW) by repeatedly resetting the accumulated holes in the upper QW. Simple device structure makes the detectors feasible for array fabrication: Furthermore, monolithic integration with reading circuits will be possible.

A passive long-wavelength infrared microscope with a highly sensitive phototransistor.

A passive scanning confocal microscope in the long-wavelength infrared (LWIR) region has been developed for sensitive imaging of spontaneous LWIR radiation by utilizing an ultrahighly sensitive detector, called the charge-sensitive infrared phototransistor (CSIP). The microscope consisted of room-temperature components including a Ge objective lens and liquid helium temperature components including a confocal pinhole, Ge relay lenses, and CSIP detector. With the microscope, thermal radiation (wavelength of 14.7 microm) spontaneously emitted by the object was studied with a spatial resolution of 25 microm. Clear passive LWIR imaging pictures were obtained by scanning a sample consisting of glass, Al foil, Ag paste, and Au. Clear passive LWIR image was also obtained even when the sample surface was covered by a GaAs or Si plate. This work suggests usefulness of CSIP detectors for application of passive LWIR microscopy.

An efficient protocol of iridium-catalyzed allylic substitution reaction and its application to polymer synthesis: complementary regio- and stereoselective allylation polycondensation via Ir and Pd catalyses.

An efficient protocol of the Ir-catalyzed allylic substitution reaction is reported using N,O-bis(trimethylsilyl)acetamide as a base in the presence of nBu4NF as a cocatalyst. The reaction completely proceeded under very mild conditions, and a branched allylated compound that is not easy to access via the Tsuji-Trost reaction can be synthesized. The reaction system is practical enough to be applicable for polymer syntheses. The Ir- and Pd-catalyzed allylation polycondensations generally show complementary regio- and stereoselectivities. The Ir-catalyzed reaction is versatile, and a mixed dual regioselectivity such as a branched-linear selectivity on each electrophile can also be achieved.

Catalytic, Enantioselective Synthesis of α-Aminonitriles with a Novel Zirconium Catalyst.

Strecker reactions of aldimines with Bu3 SnCN in the presence of the novel chiral zirconium binuclear catalyst 1 provide α-aminonitriles in good yields and with high enantioselectivities. The reaction can be applied to a wide range of substrates. Since both enantiomers of the chiral sources are readily avaibable, both enantiomers of the α-aminonitriles are easily prepared according to this method. L=N-methylimidazole.

The First Enantioselective Aza-Diels-Alder Reactions of Imino Dienophiles on Use of a Chiral Zirconium Catalyst.

Chiral dihydropyridone derivatives 3 are obtained in high yields and with good enantioselectivities by the title reaction of aldimines such as 1 with Danishefsky's diene 2. 6,6'-Dibromo-1,1'-binaphthol complexes with Group 4 metals serve as catalysts; zirconium proved to be especially effective.