An Optically Anisotropic Crystal with Large Birefringence Arising from Cooperative π Orbitals.

Birefringent materials are highly demanded for high-performance polarized optics. As compared with artificial anisotropic metamaterials, anisotropic crystals have advantages of low optical losses and easy processing, but their birefringence is still limited. Herein, based on first-principles studies, we identified a new type of functional anion units, (Hx C6 N9 )(3-x)- (x=0, 1, 2), and then successfully synthesized a new anisotropic crystal, namely, CsH2 C6 N9 ⋅H2 O (I), whose crystal structure consists of (H2 C6 N9 )- anions. Remarkably, I is ultraviolet transparent and exhibits very large birefringence of about 0.55@550 nm, which is much larger than those of commercial birefringent crystals. These results make I a candidate for highly efficient manipulation of optics and light in optical modulation devices. Theoretical calculations reveal that large birefringence mainly arises from the cooperative π orbitals in (H2 C6 N9 )- anions. This work provides a new insight on the underlying structure-property relationships of anisotropic crystals.

Spectral Engineering of Optical Microresonators in Anisotropic Lithium Niobate Crystal.

On-chip optical microresonators are essential building blocks in integrated optics. The ability to arbitrarily engineer their resonant frequencies is crucial for exploring novel physics in synthetic frequency dimensions and practical applications like nonlinear optical parametric processes and dispersion-engineered frequency comb generation. Photonic crystal ring (PhCR) resonators are a versatile tool for such arbitrary frequency engineering, by controllably creating mode splitting at selected resonances. To date, these PhCRs have mostly been demonstrated in isotropic photonic materials, while such engineering can be significantly more complicated in anisotropic platforms that often offer more fruitful optical properties. Here, the spectral engineering of chip-scale optical microresonators is realized in the anisotropic lithium niobate (LN) crystal by a gradient design that precisely compensates for variations in both refractive index and perturbation strength. Controllable frequency splitting is experimentally demonstrated at single and multiple selected resonances in LN PhCR resonators with different sizes, while maintaining high quality-factors up to 1 × 106. Moreover, a sharp boundary is experimentally constructed in the synthetic frequency dimension based on an actively modulated x-cut LN gradient-PhCR, opening up new paths toward the arbitrary control of electro-optic comb spectral shapes and exploration of novel physics in the frequency degree of freedom.

Tunable Hypersonic Bandgap Formation in Anisotropic Crystals of Dumbbell Nanoparticles.

Phononic materials exhibit mechanical properties that alter the propagation of acoustic waves and are widely useful for metamaterials. To fabricate acoustic materials with phononic bandgaps, colloidal nanoparticles and their assemblies allow access to various crystallinities in the submicrometer scale. We fabricated anisotropic crystals with dumbbell-shaped nanoparticles via field-directed self-assembly. Brillouin light spectroscopy detected the formation of direction-dependent hypersonic phononic bandgaps that scale with the lattice parameters. In addition, the local resonances of the constituent nanoparticles enable metamaterial behavior by opening hybridization gaps in disordered structures. Unexpectedly, this bandgap frequency is robust to changes in the dumbbell aspect ratio. Overall, this study provides a structure-property relationship for designing anisotropic phononic materials with targeted phononic bandgaps.

Anisotropic Electrical Conductivity of Oxygen-Deficient Tungsten Oxide Films with Epitaxially Stabilized 1D Atomic Defect Tunnels.

Materials having an anisotropic crystal structure often exhibit anisotropy in the electrical conductivity. Compared to complex transition-metal oxides (TMOs), simple TMOs rarely show large anisotropic electrical conductivity due to their simple crystal structure. Here, we focus on the anisotropy in the electrical conductivity of a simple TMO, oxygen-deficient tungsten oxide (WOx) with an anisotropic crystal structure. We fabricated several WOx films by the pulsed laser deposition technique on the lattice-matched (110)-oriented LaAlO3 substrate under a controlled oxygen atmosphere. The crystallographic analyses of the WOx films revealed that highly dense atomic defect tunnels were aligned one-dimensionally (1D) along [001] LaAlO3. The electrical conductivity along the 1D atomic defect tunnels was ∼5 times larger than that across the tunnels. The present approach, introduction of 1D atomic defect tunnels, might be useful to design simple TMOs exhibiting anisotropic electrical conductivity.

Incorporation of an N-methyl Amino Acid into a Template Peptide Alters Anisotropy in the Crystal Growth of Gold Nanoparticles Synthesized by the Peptide Template Method.

BACKGROUND: Gold nanocrystals have unique physicochemical and biocompatible properties, and hold promise for use as catalysts and in the fields of electronics, photonic and/or plasmonic devices, sensing and/or imaging systems, targeted drug delivery, and photothermal therapies. A variety of organic templates have been used to control the size, shape, and structure of gold nanocrystals, and to modify their surfaces. For the control of the shape of gold nanocrystals, we previously designed and synthesized a ß-sheet-forming nonapeptide (RU006: Ac- AIAKAXKIA-NH2, X = L-2-naphthylalanine, Nal). A mixture of RU006 and HAuCl4 in water produced ultrathin gold nanoribbons with 50-100 nm wide, several nanometers high, and microns long. OBJECTIVES: The main objective of this study is the control of the nanoribbon crystal growth by designing and synthesizing RU006 analogs containing an N-methyl-L-alanine residue. METHODS: We report (i) the design and synthesis of four RU006 analogs in which an L-alanine (Ala) at four positions in the RU006 sequence (N-methylated RU006 analogs) is replaced with an N-methyl alanine, (ii) conformational and morphological analyses of the self-assembled Nmethylated RU006 analogs, (iii) gold nanocrystal synthesis by the peptide templating method with N-methylated RU006 analogs, and (iv) the roles of peptide self-assembly in anisotropic gold crystal growth. RESULTS: RU006 with an N-methyl moiety at the center position resulted in flattened/platelet gold nanocrystals. It was also found that decreasing the mole fraction of RU006 in mixtures with Nmethylated RU006 analogs afforded significantly different absorption spectra compared to that obtained using RU006 alone under gold nanocrystal synthesis conditions. CONCLUSION: We found that morphology of gdd nanocrystals is significantly affected by electron transfer from the naphthalene rings to HAuCl4, accompanied by cross-linking reactions between spatially adjacent naphthalene rings within the hydrophobic cavity of a template assembly.

Anisotropic Growth of Hydroxyapatite in Stretched Double Network Hydrogel.

Bone tissues possess excellent mechanical properties such as compatibility between strength and flexibility and load bearing owing to the hybridization of organic/inorganic matters with anisotropic structure. To synthetically mimic such an anisotropic structure of natural organic/inorganic hybrid materials, we carried out hydroxyapatite (HAp) mineralization in stretched tough double network (DN) hydrogels. Anisotropic mineralization of HAp took place in stretched hydrogels, as revealed by high brightness synchrotron X-ray scattering and transmission electron microscopic observation. The c-axis of mineralized HAp aligned along the stretching direction, and the orientation degree S calculated from scattering profiles increased with increasing in the elongation ratio λ of the DN gel, and S at λ = 4 became comparable to that of rabbit tibial bones. The morphology of HAp polycrystal gradually changed from spherical to unidirectional rod-like shape with increased elongation ratio. A possible mechanism for the anisotropic mineralization is proposed, which would be one of the keys to develop mechanically anisotropic organic/inorganic hybrid materials.

Controlling Shape Anisotropy of ZnS-AgInS2 Solid Solution Nanoparticles for Improving Photocatalytic Activity.

Independently controlling the shape anisotropy and chemical composition of multinary semiconductor particles is important for preparing highly efficient photocatalysts. In this study, we prepared ZnS-AgInS2 solid solution ((AgIn)xZn2(1-x)S2, ZAIS) nanoparticles with well-controlled anisotropic shapes, rod and rice shapes, by reacting corresponding metal acetates with a mixture of sulfur compounds with different reactivities, elemental sulfur, and 1,3-dibutylthiourea, via a two-step heating-up process. The chemical composition predominantly determined the energy gap of ZAIS particles: the fraction of Zn2+ in rod-shaped particles was tuned by the ratio of metal precursors used in the nanocrystal formation, while postpreparative Zn2+ doping was necessary to increase the Zn2+ fraction in the rice-shaped particles. The photocatalytic H2 evolution rate with irradiation to ZAIS particles dispersed in an aqueous solution was significantly dependent on the chemical composition in the case of using photocatalyst particles with a constant morphology. In contrast, photocatalytic activity at the optimum ZAIS composition, x of 0.35-0.45, increased with particle morphology in the order of rice (size: ca. 9 × ca. 16 nm) < sphere (diameter: ca. 5.5 nm) < rod (size: 4.6 × 27 nm). The highest apparent quantum yield for photocatalytic H2 evolution was 5.9% for rod-shaped ZAIS particles, being about two times larger than that obtained with spherical particles.

Thermal Expansion of Rutile from 100 to 700 °K.

The thermal expansion of a single crystal of rutile (TiO2) was determined in directions parallel to its crystallographic axes. A unique macroscopic technique was used wherein a cube-shaped specimen was cut from the anisotropic crystal, each of its six faces polished flat and nearly parallel to the face opposite it, and the expansion measured along each of its three body axes with an Abbe-Pulfrich interferometer. The relationship between the expansion along the body axes of the specimen and that in the crystallographic directions was determined from a Laue x-ray pattern. The unusual behavior of the thermal expansion that was observed can be explained by assuming an acoustical and optical contribution where the corresponding Grüneisen constants are 2.80 and 0.75 respectively.