Formation of p-n junctions during solid-state chemical reactions involving superionic crystals

It is established that semiconducting heterojunctions can be formed in the AgI-Ag₂HgI₄-HgI₂ and CuI-Cu₂HgI₄-HgI₂ systems obtained as a result of diffusion-controlled solid-state chemical reactions. Concentration profiles of diffusant ions in the obtained structures have been determined using the exciton spectroscopy and electron-probe microanalysis techniques. The current-voltage characteristics of heteroboundaries between ternary compounds and binary crystals have been measured in the dark and under illumination.     

Electrochemical surface plasmon resonance measurement based on gold nanohole array fabricated by nanoimprinting technique

In this paper, we describe our development of an electrochemical surface plasmon resonance (EC-SPR) measurement device based on a bottom-filled gold nanohole array. The polymer based gold nanohole array was fabricated with a UV nanoimprint technique and electron beam gold deposition. Direct reflection mode measurement was used to monitor the SPR dip in the reflection spectra. A cyclic voltammogram was also operated by using the standard three electrodes containing working electrode having a gold nanohole array and counter and reference electrodes. The gold nanohole array was modified with an osmium-poly(vinylpyridine)-wired horseradish peroxidase (Os-gel-HRP) film, and its redox state induced by the change in potential was monitored simultaneously. The redox state of the local film was obtained simply by scanning the sample substrate stage. The substrate modified with Os-gel-HRP film was incorporated in a microfluidic chip, and then the hydrogen peroxide was determined in terms of the redox change in the Os complex mediator from the slope of the SPR dip shift. The linear relation of hydrogen peroxide from 10 to 250 μM was successfully monitored, and a high conversion efficiency was realized.     

Graphoepitaxy of block-copolymer self-assembly integrated with single-step ZnO nanoimprinting

A highly efficient, ultralarge-area nanolithography that integrates block-copolymer lithography with single-step ZnO nanoimprinting is introduced. The UV-assisted imprinting of a photosensitive sol-gel precursor creates large-area ZnO topographic patterns with various pattern shapes in a single-step process. This straightforward approach provides a smooth line edge and high thermal stability of the imprinted ZnO pattern; these properties are greatly advantageous for further graphoepitaxial block-copolymer assembly. According to the ZnO pattern shape and depth, the orientation and lateral ordering of self-assembled cylindrical nanodomains in block-copolymer thin films could be directed in a variety of ways. Significantly, the subtle tunability of ZnO trench depth enabled by nanoimprinting, generated complex hierarchical nanopatterns, where surface-parallel and surface-perpendicular nanocylinder arrays are alternately arranged. The stability of this complex morphology is confirmed by self-consistent field theory (SCFT) calculations. The highly ordered graphoepitaxial nanoscale assembly achieved on transparent semiconducting ZnO substrates offers enormous potential for photonics and optoelectronics.     

Inclined nanoimprinting lithography for 3D nanopatterning

We report a non-conventional shear-force-driven nanofabrication approach, inclined nanoimprint lithography (INIL), for producing 3D nanostructures of varying heights on planar substrates in a single imprinting step. Such 3D nanostructures are fabricated by exploiting polymer anisotropic dewetting where the degree of anisotropy can be controlled by the magnitude of the inclination angle. The feature size is reduced from micron scale of the template to a resultant nanoscale pattern. The underlying INIL mechanism is investigated both experimentally and theoretically. The results indicate that the shear force generated at a non-zero inclination angle induced by the INIL apparatus essentially leads to asymmetry in the polymer flow direction ultimately resulting in 3D nanopatterns with different heights. INIL removes the requirements in conventional nanolithography of either utilizing 3D templates or using multiple lithographic steps. This technique enables various 3D nanoscale devices including angle-resolved photonic and plasmonic crystals to be fabricated.     

Solid-state superionic stamping with silver iodide-silver metaphosphate glass

This paper demonstrates and analyzes the new use of the glassy solid electrolyte AgI-AgPO(3) for direct nanopatterning of thin silver films with feature resolutions of 30 nm. AgI-AgPO(3) has a high room temperature ionic conductivity with Ag( + ) as the mobile ion, leading to silver etch/patterning rates of up to 20 nm s( - 1) at an applied bias of 300 mV. The glass can be melt-processed at temperatures below 200?°C, providing a facile and economical pathway for creating large area stamps, including the 25 mm(2) stamps shown in this study. Further, the glass is sufficiently transparent to permit integration with existing tools such as aligners and imprint tools, enabling high overlay registration accuracy and facilitating insertion into multi-step fabrication recipes.     

A lithium superionic conductor

Batteries are a key technology in modern society. They are used to power electric and hybrid electric vehicles and to store wind and solar energy in smart grids. Electrochemical devices with high energy and power densities can currently be powered only by batteries with organic liquid electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems very complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10(-2) S cm(-1)) only at 50-80 °C, which is one order of magnitude lower than those of organic liquid electrolytes. Here, we report a lithium superionic conductor, Li(10)GeP(2)S(12) that has a new three-dimensional framework structure. It exhibits an extremely high lithium ionic conductivity of 12 mS cm(-1) at room temperature. This represents the highest conductivity achieved in a solid electrolyte, exceeding even those of liquid organic electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochemical properties (high conductivity and wide potential window).     

Diamond nanopatterns fabricated by room-temperature nanoimprinting technology with diamond molds using polysiloxane

Fabrication of diamond nanopatterns in room-temperature (RT) nanoimprint lithography (NIL) with chemical vapor deposited (CVD) diamond molds using polysiloxane as RT-imprint resist material was investigated. The diamond molds of a convex lattice with 1 μm line-width and 5 μm pitch, and a cylinder dot with 200 nm diameter and 1 μm pitch which has a height of 1 μm using RT-NIL process were fabricated with Bi₄Ti₃O₁₂ octylate (oxide) mask in electron beam lithography technology. The maximum radio frequency (RF) oxygen plasma-etching selectivity (diamond/polysiloxane) of 19 was obtained under the conditions of RF power of 100 W, oxygen gas flow rate of 10 sccm and background gas pressure of 30 Pa. It was found that the optimum imprinting pressure and its depth obtained after the press duration of 10 min were 0.8 MPa and about 0.5 μm, respectively. The resulting diamond nanopatterns of a concave lattice with 1 μm line-width and 5 μm pitch, and a concave cylinder dot with 200 nm diameter and 1 μm pitch which have a height of 1 μm after RF oxygen plasma-etching (100W, 10 sccm, 30 Pa, 40 min) were fabricated with diamond mold RT-NIL using polysiloxane.     

Thermowetting embossing nanoimprinting of the organic-inorganic hybrid materials

A new UV-based soft-lithographic technique for submicron patterns via thermowetting of organic-inorganic hybrid materials is described. Specifically, 300-nm scale patterns were replicated utilising this coating-free fabrication method. With thermowetting embossing nanoimprinting technique, a poly(dimethyl siloxane) (PDMS) mold with a submicron-scale relief was placed on a thermally wetted organic-inorganic hybrid material, which was then polymerized with UV light. The thermowetting embossing nanoimprinting technique can be applied universally to patternable organic-inorganic hybrid materials, such as methacrylic and vinylic organic-inorganic hybrid materials. Fabricated submicron patterns can also be applied to the nanoscale patterning, e.g., arrayed photonic band gap materials.     

Direct nanoimprinting of metal nanoparticles for nanoscale electronics fabrication

One-step direct nanoimprinting of metal nanoparticles was investigated to fabricate nano-/microscale metallic structures such as nanodot and nanowire arrays. This was done at low temperatures and pressures, utilizing the low melting temperature and viscosity of metal nanoparticle solutions. Through precise control of the fluidic properties of the nanoparticle solution and the mold design, high-quality nanoscale features with no or negligible residual layer were nanoimprinted. Nanoscale electronic devices were also demonstrated, including nanowire resistors and nanochannel organic field effect transistors with an air-stable semiconducting polymer.     

Morphology of new superionic pyrophosphates

New superionic pyrophosphates, Na₂H₃Al(P₂O₇)₂, Na₂CaMn₂(P₂O₇)₂, NaFeP₂O₇, Na₂M²⁺Zr(P₂O₇)₂ where M=Mn, Co, Ni and Zn, and (Na_0.66Zr_0.33)₂P₂O₇ were obtained by a hydrothermal method. The crystal growth, solubility and structure of these superionic pyrophosphates are discussed in brief. Detailed morphological studies were carried out with reference to the divalent/trivalent cations, degree of supersaturation, concentration of volatiles such as Na₂O, H₂O, P₂O₅ etc.     

Theoretical approaches to superionic conductivity

Recent theoretical approaches to the understanding of superionic conductivity in polycrystalline, glassy and polymeric materials are briefly reviewed. Phase transitions to the superionic conducting state in the AgI family are apparently triggered by cluster formation and strong mobile ion interaction within the clusters. Anomalous conductivity and related physical properties are explained in the cluster induced distortion model. Ionic composites such as AgX : Al₂O₃ (X = Cl, Br and I) involve conducting and non-conducting phases and the all-important interface between the two whose space charge enhances the conductivity and also trigger phase transitions to exotic polymorphic phases, for which the mechanisms are yet to be explored. Ion hopping dynamics controls the conductivity of superionic glasses. Mode coupling and jump relaxation theories account for the non-Debye relaxation observed in a.c. conductivity of these glasses. The theory of conductivity in polymer electrolytes—still in its infancy—involves their complex structure and glass transition behaviour. Preparative and thermal history, composition and crystallinity control ionic conductivity. New approaches to the synthesis of optimal polymer electrolytes such as rubbery electrolytes, crystalline polymers and nanocomposites must be considered before achieving a comprehensive theoretical understanding. Based on an invited talk given by the first author at the National Workshop on Solid State Ionics and its Applications, Bharatiar University, Coimbatore, 18–23 January 2002.     

An analytical modeling of heat transfer for laser-assisted nanoimprinting processes

Laser-assisted direct imprinting (LADI) technique has been proposed to utilize an excimer laser to irradiate and heat up the substrate surface through a highly-transparent quartz mold preloaded on this substrate for micro- to nano-scaled structure fabrications. While the melting depth and molten duration are key issues to achieve a satisfactory imprinting pattern transfer, many material property issues such as crystalline phase alteration, grain size change and induced film stress variation are strongly affected by transient thermal response. With one-dimensional simplification as a model for the LADI technique, the present paper has successfully derived an analytical solution for the arbitrary laser pulse distribution to predict the relevant imprinting parameters during the laser induced melting and solidification processes. The analytical results agree quite well with the experimental data in the literature and hence can be employed to further investigate the effects of LADI technique from laser characteristics (wavelength, fluence and pulse duration) and substrate materials (silicon and copper) on the molten duration, molten depth and temperature distributions. Three kinds of excimer laser sources, ArF (193 nm), KrF (248 nm) and XeCl (308 nm) were investigated in this study. For the silicon substrate, the melting duration and depth were significantly dictated by the wavelength of laser used, indicating that employing the XeCl excimer laser with longer pulse duration (30 ns in the present study) will achieve the longest molten duration and deepest melting depth. As for the copper substrate, the melting duration and depth are mainly affected by the laser pulse duration; however, the wavelength of laser still plays an insignificant role in LADI processing. Meanwhile, the laser fluence should properly be chosen, less than 1.4 J/cm² herein, so as to avoid the substrate temperature exceeding the softening point of the quartz mold (~1950 K) and to make sure that the mold can still maintain the original features.     

Effects of modulus and surface chemistry of thiol-ene photopolymers in nanoimprinting

Thiol-ene photopolymers were studied as patternable resins for nanocontact molding imprint lithography. Photopolymerizable thiol and ene monomer mixtures were used, and after molding, patterned thiol-ene polymer features the size and shape of the original molds were replicated. Adhesion and release were examined and controlled by manipulating the surface chemistry of the substrate and mold. A direct correlation between cured thiol-ene polymer modulus and pattern fidelity was observed.     

Large-area nanoimprinting on various substrates by reconfigurable maskless laser direct writing

Laser-assisted, one-step direct nanoimprinting of metal and semiconductor nanoparticles (NPs) was investigated to fabricate submicron structures including mesh, line, nanopillar and nanowire arrays. Master molds were fabricated with high-speed (200?mm?s(-1)) laser direct writing (LDW) of negative or positive photoresists on Si wafers. The fabrication was completely free of lift-off or reactive ion etching processes. Polydimethylsiloxane (PDMS) stamps fabricated from master molds replicated nanoscale structures (down to 200?nm) with no or negligible residual layers on various substrates. The low temperature and pressure used for nanoimprinting enabled direct nanofabrication on flexible substrates. With the aid of high-speed LDW, wafer scale 4?inch direct nanoimprinting was demonstrated.     

A functionally separated nanoimprinting material tailored for homeotropic liquid crystal alignment

In order to homeotropically align liquid crystals (LCs) at the nanosized surface grooves processed by nanoimprint lithography technology (NIL), we propose to design a hybrid-type homeotropic polymer material consisting of two distinct moieties with largely different thermo-mechanical properties and surface activity. Surface contact angle measurements and sum-frequency vibrational spectroscopy allow us to conclude that the polymer film is a functionally separated composite suitable for the homeotropic LC alignment processed by NIL. As one of the potential applications using the hybrid-type homeotropic polymer, we demonstrate that the nanoimprinted grooves at the polymer surface can achieve a zenithal nematic LC bistability.