Influence of Vibrational Strong Coupling on an Ordered Liquid Crystal.

Vibrational strong coupling and the formation of vibrational polaritons are a result of strong light-matter interaction between a cavity photon and a molecular vibrational mode. The Rabi splitting parameter, which reflects the microscopic light-matter interaction strength, reveals information about the molecular alignment and concerted vibrational motion inside the cavity. We have investigated vibrational strong coupling of 4-cyano-4'-octylbiphenyl liquid crystal molecules in isotropic and smectic A phases. We observed a ∼30% change in the Rabi splitting with the phase transition from isotropic to smectic A by controlling the temperature, together with the onset of polarization-dependent anisotropy of the Rabi splitting in the smectic A phase. Based on the estimated orientational distribution function, we show that the observed Rabi splitting difference in the isotropic and smectic A phases can only be explained by taking into account the influence of collective vibrational motion in the cavity, which affects the molecular properties under the vibrational strong coupling regime.

Development of a Spacerless Flow-Cell Cavity for Vibrational Polaritons.

We developed a spacerless flow-cell cavity for the observation of vibrational strong coupling and demonstrate its availability in two samples with a C≡N bond: a metal complex (aq) and an ionic liquid. It is shown that the cavity length can be tuned over a wide range to investigate coupling with different order Fabry-Pérot cavity modes without reassembling the cavity. In the ionic liquid, analyses based on the coupled harmonic oscillator model with multiple vibrational modes show that the Rabi splitting parameters and the square root of the integrated absorption intensity are proportional among the three neighboring vibrational modes. Our spacerless cell structure simplifies the comparison of the different vibrational strong coupling measurements, such as the mode order dependence and the coupling to different molecular vibrations.

Anisotropic light-matter coupling and below-threshold excitation dynamics in an organic crystal microcavity.

Organic semiconductors are promising candidates as platforms for room temperature polaritonic devices. An issue for practical implementation of organic polariton devices is the lowering of condensation threshold. Here we investigate anisotropic light-matter coupling characteristics in an organic crystal microcavity showing strong molecular orientation. Furthermore, the below-threshold excitation dynamics are investigated to clarify the spontaneous transition pathways from reservoir to polariton states. Time-resolved photoluminescence measurements reveal that photonic/excitonic hybrid transition processes coexist in the microcavity system. This finding provides valuable insights into a detailed understanding of polariton dynamics and help in the design of polaritonic devices showing a low-threshold condensed phase.

Photon Energy-Dependent Ultrafast Photoinduced Terahertz Response in a Microcrystalline Film of CH3NH3PbBr3.

Time-resolved terahertz (THz) spectroscopy is applied for a microcrystalline film of methylammonium lead bromide perovskite, CH3NH3PbBr3, to observe the carrier dynamics around the band edge. The ultrafast response of the transmitted THz electric field amplitude after carrier generation is modeled with a biexponential curve with ∼5 and 180 ps time constants, which are ascribed to Auger and electron-hole recombination processes, respectively. From the pump photon energy dependence of the time evolution of the THz electric field amplitude, it is shown that the bound exciton states and free interband excited carrier states show a clearly different temporal response. These measurements support the idea that the bound excitons generated in CH3NH3PbBr3 remain as stable excitons even at room temperature (RT). This is in clear contrast to the cases in CH3NH3PbI3 in which the excitons and band-edge free carriers are interchangeable at RT.

Numerical simulations on strong coupling of Bloch surface waves and excitons in dielectric-semiconductor multilayers.

Simulations on Bloch surface waves and Bloch surface wave-exciton-polaritons based on the transfer matrix method were performed using only the layer thicknesses and refractive indices of the materials. We demonstrate that the incorporation of the influence of active layer is necessary to accurately determine the Bloch surface wave dispersion. Furthermore, the mode splitting that gives rise to the lower and upper polariton branches can be simulated by including the full dispersive refractive index of the active layer in the transfer matrix calculation. We show the dependence of coupling strength on active layer and truncation layer thicknesses, which implies that the Bloch surface wave-exciton interaction strength can be tuned just by changing these structural parameters. Furthermore, we calculate the area inside the dips corresponding to the lower and upper polariton modes, which can serve as an indicator of mode visibility. We find that in the Kretschmann-Raether configuration, a tradeoff between high Rabi splitting and good mode visibility must be taken into account in designing multilayer structures for Bloch surface wave-exciton-polaritons. Angle-resolved reflectivity maps were also calculated to illustrate how these results can be observed in an experimental set-up. This work serves as a guide map in the design and potential optimization of multilayer structures for the study of two-dimensional polaritonic systems.

Synthesis and characterization of methoxy- or cyano-substituted thiophene/phenylene co-oligomers for lasing application.

As new candidates of thiophene/phenylene co-oligomer (TPCO) species, 5,5''-bis(4'-methoxy-[1,1'-biphenyl]-4-yl)-2,2':5',2''-terthiophene (BP3T-OMe) and 4',4'''-([2,2':5',2''-terthiophene]-5,5''-diyl)bis(([1,1'-biphenyl]-4-carbonitrile)) (BP3T-CN) were synthesized for lasing applications. Although most unsubstituted TPCO species crystallize in monoclinic form, BP3T-OMe and BP3T-CN crystallized in orthorhombic and triclinic forms, respectively. Since the unsubstituted species, 5,5''-bis(4-biphenylyl)-2,2':5',2''-terthiophene (BP3T), shows unique and superior lasing performance in single crystals, the newly synthesized BP3T-OMe and BP3T-CN have possibilities to show different or improved optoelectronic characteristics. Amplified spontaneous emission (ASE) and optically pumped lasing were observed from both of the single crystals based on their well-shaped crystalline cavity and high group refractive index values of 3.7-5.3 for excellent light confinement. The lasing threshold for the BP3T-OMe crystal was lower than that for the BP3T-CN crystal, which was attributed to their different molecular orientation, standing in the former and inclining in the latter.

Mode selective excitation of terahertz vibrations in single crystalline rubrene.

Organic molecular crystals have a variety of low frequency vibrational modes composed of intra- and inter-molecular oscillations. They are mixed intricately in the terahertz (THz) region. We are interested in the controllability of the vibrational energy distribution among such THz vibrational modes based on the femtosecond double-pulse excitation scheme. Single crystalline rubrene is prepared by physical vapor transport. The optical response of vibrational modes in the electric ground state of rubrene is detected by the ultrafast pump-probe reflectivity measurement at 90 K. Three oscillation modes at 3.20, 3.67, and 4.18 THz are detected, and we demonstrate selective enhancement and depletion of each mode by properly tuning the double-pulse delay. The amplitude of the selected vibrational mode is modulated between 0.149 and 1.87, where 1.0 corresponds to the amplitude excited with a single pump pulse. The double-pulse delay dependence of the observed vibrational amplitude is simulated based on the classical driven harmonic oscillator model, and the results reasonably reproduce our experimental signals. Such selective manipulation of the vibrational amplitude can be a potential tool to investigate the vibronic and electron-phonon couplings which plays an important role for the charge transport characteristics and various optoelectronic properties in organic molecular crystals.

Quantitative evaluation of light-matter interaction parameters in organic single-crystal microcavities.

Investigation of physics on light-matter interaction and strong coupling formation in organic microcavities is important to characterize the device structure enabling efficient room-temperature polariton condensation. In this study, we evaluate quantitatively the light-matter interaction parameters for three types of organic single-crystal microcavities and discuss the effects of microcavity structures on the strong coupling formation. We found that improvement in cavity quality factor causes a reduction in the photon damping constant, which results in an increase in the Rabi splitting energy. Moreover, when we used a metal thin film as the cavity mirror, it was revealed that the exciton damping became 30 times stronger than that in a dielectric mirror cavity. These experimental findings are very intriguing to achieve low-threshold or electrically pumped organic polariton devices.

Magnetic Properties of Fibonacci-Modulated Fe-Au Multilayer Metamaterials.

Herein we experimentally study magnetic multilayer metamaterials with broken translational symmetry. Epitaxially-grown iron-gold (Fe-Au) multilayers modulated using Fibonacci sequence-referred to as magnetic inverse Fibonacci-modulated multilayers (IFMs)-are prepared using ultra-high-vacuum vapor deposition. Experimental results of in-situ reflection high-energy electron diffraction, magnetization curves, and ferromagnetic resonance demonstrate that the epitaxially-grown Fe-Au IFMs have quasi-isotropic magnetization, in contrast to the in-plane magnetization easy axis in the periodic multilayers.

Organic Light-Emitting Diodes with Heterojunction of Thiophene/Phenylene Co-Oligomer Derivatives.

Organic light-emitting diodes are fabricated by heterojunction of thiophene/phenylene co-oligomer films using biphenyl-capped bithiophene (BP2T) and its cyano-substituted derivative (BP2T-CN). Strong electron-withdrawing cyano-groups in BP2T-CN transform the p-type BP2T into n-type. Photoluminescence and electroluminescence from their bilayered films dominantly result from the BP2T-CN layer since the lying molecular orientation of BP2T-CN facilitates surface emission while the standing orientation of BP2T is not suitable for the device configuration. The current density and electroluminescence intensity are considerably increased by carrier doping with MoO3 and Cs2CO3 into the BP2T and BP2T-CN films, respectively.

Amplified Emission and Field-Effect Transistor Characteristics of One-Dimensionally Structured 2,5-Bis(4-biphenylyl)thiophene Crystals.

One-dimensional (1D) structures of 2,5-bis(4-biphenylyl)thiophene (BP1T) crystals are fabricated for light amplification and field-effect transistor (FET) measurements. A strip-shaped 1D structure (10 µm width) made by photolitography of a vapor-deposited polycrystalline film shows amplified spontaneous emission and lasing oscillations under optical pumping. An FET fabricated with this 1D structure exhibits hole-conduction with a mobility of µh = 8.0 x 10(-3) cm2/Vs. Another 1 D-structured FET is fabricated with epitaxially grown needle-like crystals of BP1T. This needle-crystal FET exhibits higher mobility of µh = 0.34 cm2/Vs. This improved hole mobility is attributed to the single-crystal channel of epitaxial needles while the grain boudaries in the polycrystalline 1 D-structure decrease the carrier transport.

Hybrid Organic-Inorganic Solar Cells with Electrodeposited Al-Doped Zinc Oxide.

Hybrid solar cells were fabricated using aluminum-doped zinc oxide (AZO) grown by electrochemical deposition from chloride electrolyte solutions with Al/Zn molar ratios of 0.5, 2.5, and 5.0%. The substrates were AZO- and ZnO-seeded ITO. Ordered nanorod structures with high optical transmittance were grown at 0.5% Al/Zn ratio while interconnected micron-sized flakes were grown at 2.5% and 5.0%. The estimated band gap energies increase for higher Al dopant content, showing Burstein-Moss effect. EDX analysis detected high aluminum content in the 5.0% samples suggesting that insulating aluminum oxide phases were formed thus causing reduced solar cell efficiencies. The highest power conversion efficiency of 1.71%, from the 0.5% sample grown on ZnO-seeded ITO, can be attributed to the presence of AZO nanorods which provide a large interfacial area and effective charge transport.

Chiral meta-molecules consisting of gold nanoparticles and genetically engineered tobacco mosaic virus.

We demonstrate a chiral meta-molecule in the ultraviolet (UV) and visible (VIS) regions using a complex of Au nanoparticles (NPs) and rod-shaped tobacco mosaic virus (TMV). Au NPs five nm in diameter are uniformly formed on peptide-modified TMV. The peptide-modified TMV with uniform-sized Au NPs has improved dispersion in solution. A negative circular dichroism (CD) peak is produced around 540 nm, at plasmonic resonance wavelength of Au NPs. Additionally, modification of a CD peak in the UV region is observed. Attaching NPs to a virus causes the enhancement and modification of CD peaks in both the UV and VIS regions. Our results open a new avenue for the preparation of three dimensional chiral metamaterials at optical frequencies.

Single crystals of 5,5'-Bis(4'-methoxybiphenyl-4-yl)-2,2'-bithiophene for organic laser media.

Room temperature lasing was stably observed in air from an orthorhombic crystal of 5,5'-bis(4'-methoxybiphenyl-4-yl)-2,2'-bithiophene (BP2T-OMe). A pair of parallel {110} facets of the single crystal acted as effective Fabry-Pérot mirrors. This prominent lasing is based on high group refractive index (3.5) and Q factor (4500) of the orthorhombic crystal resonator indicating a promising potential of BP2T-OMe for organic laser media.

Lasing from epitaxially oriented needle crystals of a thiophene/phenylene co-oligomer.

Optically pumped lasing of epitaxially oriented molecular crystals is presented. Needle-like crystals of a thiophene/phenylene co-oligomer is grown along the [110] direction of a KCl substrate. The fluorescence light is one-dimensionally confined and amplified by the self-waveguiding effect in the elongated needles. The Fabry-Pérot resonation by the terminated ends results in laser oscillations corresponding to the needle length.

Gold nanoparticle-induced formation of artificial protein capsids.

Gold nanoparticles are generally considered to be biologically inactive. However, in this study we show that the addition of 1.4 nm diameter gold nanoparticle induces the remodeling of the ring-shaped protein TRAP into a hollow, capsid-like configuration. This structural remodeling is dependent upon the presence of cysteine residues on the TRAP surface as well as the specific type of gold nanoparticle. The results reveal an apparent novel catalytic role of gold nanoparticles.

Array of a dye-doped polymer-based microlaser with multiwavelength emission.

This Letter reports a convenient method of fabricating a polymer-based microlaser array. Laterally aligned plastic micropillars equipped with an optical resonator were fabricated by using a lithographic technique with an organic-dye-doped photopolymer, which operated as a laser element with a vertical cavity. Under optical pumping, very fine emission spectra showing a Fabry-Perot-type lasing oscillation were observed. Using this technique, integrated laser cavities with desired operation wavebands can be produced easily.

Simultaneous RGB lasing from a single-chip polymer device.

This Letter describes the fabrication and operation of a single-chip white-laser device. The laser device has a multilayered structure consisting of three laser layers. Each laser layer comprises polymer claddings and a waveguide core doped with organic dye. In each laser layer, grating corrugations were fabricated by UV-nanoimprint lithography that act as distributed-feedback cavity structures. Under optical pumping, lasing output with red, green, and blue colors was simultaneously obtained from the sample edge.