Search

This paper presents current divisions and distributed Joule heating of two-dimensional (2D) grid microstructures. The current divisions on 2 × 2, 4 × 4, and n × n grid microstructures made of the same conductive beams are analyzed theoretically, and Kirchhoff’s voltage law (KVL) and Kirchhoff’s current law (KCL) are employed to determine the current division factors and directions under different voltage input cases. The equivalent resistances and Joule heating power are therefore derived. 2D 2 × 2 grid microstructures made of gold (60 nm in thickness) and those made of near-equiatomic NiTi (850 nm in thickness) for various independent voltage input cases are fabricated by electron-beam evaporation and co-sputtering, respectively. The equivalent resistances of these grid microstructures are measured by four-terminal resistance measurement at ambient conditions, which show a good agreement with the theoretical results. Further investigation on the electrical resistivities of evaporated gold layer (4.85 × 10–8 Ω m) and co-sputtered NiTi (1.23 × 10–5 Ω m) reveals that the influences of scale effect and fabrication process on the resistivity cannot be neglected. As such, it is found to be necessary to consider the materials’ resistivity in the fabricated grid microstructures before their electro-thermal analysis.

This paper presents thermo-mechanical modeling on multilayered metallic microstructures consisting of two bilayers that enable 3D deployment once being Joule heated. A representative design of such microstructures, as well as their working principle is introduced. A mathematical model is derived using Euler–Bernoulli beam theory, and analytical solutions describing out-of-plane displacement of the multilayered microstructures when uniformly heated, which is validated by finite element analysis. Parametric analysis on thermal load and dimensional change of beam shows a good agreement between the analytical solutions and results given by finite element analysis. The phases of the near-equiatomic NiTi layer are analyzed by EDS and XRD, which prove to be austenite during the Joule heating process. The mechanical properties of austenite NiTi are incorporated into the analytical solutions that provides a good estimation of 3D deployment of microstructures made of NiTi and aluminum. The experimental results provide an approximately 7 µm out-of-plane deployment by applying a uniform temperature increase of 132 K, and parametric analysis on the dimension of top aluminum beam offers another promising approach to larger 3D deployment. The proposed mathematical model provides an efficient tool for predicting the out-of-plane deployment of such multilayered microstructures.

Organic–inorganic halide perovskites feature excellent optoelectronic properties but poor chemical stability. While passivating perovskite grain boundary (GB) by polymers shows prospects on long-te...

Despite the promise of simple manufacturing via an entirely solution-based process at low temperature (

Amongst various gaseous pollutants, NO2 is one of the major exhausts originating from fossil fuel and gas combustions in vehicle engines and power plants at high temperature. Under such a scenario, in situ and real-time gas detection and monitoring solutions are largely limited, which hinders the energy-efficient and resource-saving operations of these advanced energy systems. In this report, a new type of perovskite-sensitized β-Ga2O3 nanorod-array has been successfully fabricated to detect NOx at high temperature selectively and sensitively. The demonstrated gas sensors are highly sensitive to NO2 at 800 °C, with excellent reversible and reproducible response characteristics. Through the surface decoration of perovskite-type La0.8Sr0.2CoO3 (LSCO) nanoparticles, the sensitivity of β-Ga2O3 nanorod array gas sensors is enhanced by nearly an order of magnitude, along with much faster response dynamics. A remarkable selectivity toward oxidative gases was also demonstrated with the robust differentiation of NO2.

Correction for ‘Conjugated polyelectrolytes for stable perovskite solar cells based on methylammonium lead triiodide’ by Yong Ryun Kim et al., J. Mater. Chem. A, 2022, 10, 3321–3329, https://doi.org/10.1039/D1TA10185D.

Organic-inorganic hybrids featuring tunable material properties can be readily generated by applying vapor- or liquid-phase infiltration (VPI or LPI) of inorganic materials into organic templates, with resulting properties controlled by type and quantity of infiltrated inorganics. While LPI offers more diverse choices of infiltratable elements, it tends to yield smaller infiltration amount than VPI, but the attempt to address the issue has been rarely reported. Here, we demonstrate a facile temperature-enhanced LPI method to control and drastically increase the quantity and kinetics of Pt infiltration into self-assembled polystyrene

We here report that adsorbed chains composed of one of the constituent blocks can be used as a new surface modification approach to induce perpendicularly oriented lamellar microdomains in block copolymer thin films. A nearly symmetric polystyrene-block-poly(methyl methacrylate) (PS-block-PMMA) diblock copolymer was used as a model. Densely packed PS- or PMMA-adsorbed chains of about 2–3 nm in thickness (“polymer nanocoatings”) were deposited on silicon (Si) substrates using a solvent-rinsing approach. Spin-cast films of 40 or 60 nm-thick PS-block-PMMA (equivalent to two or three interdomain spacings) were subsequently deposited onto the PS or PMMA nanocoatings. Grazing incidence small-angle X-ray scattering experiments revealed the formation of perpendicularly oriented lamellar microdomains within the entire films at 200 °C, where balanced interfacial interactions at the polymer–air interface were achieved. Additionally, X-ray photon correlation spectroscopy studies demonstrated the dynamics of the fully...

In situ wide-angle X-ray scattering together with infrared imaging was performed during three-dimensional material extrusion printing and correlated with the development of the crystalline structur...

A new, surfactant-free hydrothermal method has been developed for the growth of CeO2-based nanoflake arrays onto three-dimensional-channeled cordierite honeycomb substrates. Herein, a leaching-crystallization mechanism was proposed where the hydrothermal reaction, only involving cerium nitrate and water, leached the cordierite surface slightly and induced the formation of CeO2 nanoparticles subsequently. Further continued reaction reincorporated Al and Si atoms leached from cordierite into CeO2, finally recrystallizing Ce-Al-Si composite nanoflake structures. By using atomic layer deposition process, well-dispersed, size-controlled Pt nanoparticles were uniformly decorated on the CeO2-based nanoflakes to form the Pt/ CeO2 nano-array-based monolithic catalyst. Despite 5-50 times reduction in the active material usage compared with the traditional wash-coated catalyst, the Pt/CeO2 nano-array monolithic catalyst exhibited good catalytic oxidation activities over various individual gases, such as propylene, propane, CO, and NO oxidation, with 90% conversion efficiencies at temperatures below 200 °C. Under the simulated exhaust condition of low-temperature diesel combustion (LTC-D) developed by US DRIVE, the monolithic catalyst with low Pt loading (˜1 g/l) exhibits 90% conversion of catalytic oxidation over CO and hydrocarbonsat temperatures as low as ˜180 °C, much superior to the performance of traditional washcoated catalysts.

We have adapted the two-phase Brust method to synthesize large quantities of AuPd alloy nanoparticles with diameter of 1.86 ± 0.40 nm. When the particles were spread at the air/water interface of a Langmuir–Blodgett (LB) trough, they exhibited a distinct pressure area isotherm curve. The X-ray reflectivity (XRR) shows the formation of an incompressible monolayer with uniform thickness of 1.16 ± 0.02 nm at low pressures which collapses to form a second layer with 2.13 nm thickness at higher pressures. High resolution transmission electron microscopy (HRTEM) imaging of the monolayer indicates that the particles are highly crystalline, with well-defined atomic planes and self-assembly into a hexagonal structure. Extended X-ray absorption fine structure (EXAFS) analysis of the LB lift-off films only shows Au–Au and Au–Pd configurations, consistent with the formation of random alloy rather than core–shell structure. When the particle monolayer was lifted onto the Nafion membrane of a proton exchange membrane f...

Organic–inorganic hybrid resists are emerging as an effective way of addressing stringent process requirements for aggressive down-scaling of semiconducting devices. However, hybrid resists generally require complex chemical synthesis while being predominantly negative-tone with high dose requirements. For positive-tone processes and high-aspect-ratio pattern transfers, resist choices are limited to costly, non-hybrid alternatives, whose etch resistance is still inferior compared with hybrid resists. Here, we demonstrate a novel hybrid positive-tone resist platform utilizing simple ex situ vapor-phase inorganic infiltration into standard resist materials. A model system based on poly(methyl methacrylate) (PMMA) thin film hybridized with aluminum oxide has been demonstrated for electron-beam lithography patterning, featuring a fully controllable critical exposure dose, contrast, and etch resistance. The hybrid resist not only achieves contrast as high as ∼30, six-fold enhancement over standard PMMA, but also enables Si nanostructures with resolution down to ∼30 nm and an aspect ratio as high as ∼17, owing to enhancement of the Si etch selectivity to ∼70, with an estimated achievable maximum of ∼300, far exceeding known commercial positive-tone resist systems. The easy implementabilility, combined with versatile ex situ control of resist characteristics, makes this hybrid resist synthesis approach uniquely suited for addressing the resist performance and high throughput required for advanced nanolithography techniques, such as extreme ultraviolet lithography, potentially.

High performance of an ultra-low Pt loading diesel oxidation catalyst can be achieved by using a combination of novel nano-array structured support, precise control of ultrafine active Pt particles, and an addition of H2 as a promoter into the exhausts. Highly stable mesoporous rutile TiO2 nano-array was uniformly grown on three-dimensional (3-D) cordierite honeycomb monoliths using a solvothermal synthesis. Atomic layer deposition was employed for precise dispersion of ultrafine Pt particles (0.95 ± 0.24 nm) on TiO2 nano-array with a Pt loading of 1.1 g/ft3. Despite low Pt loading, the Pt/TiO2 nano-array catalyst shows impressive low-temperature oxidation reactivity, with the conversion of CO and total hydrocarbon (THC) reaching 50% at 224 and 285 °C, respectively, in the clean diesel combustion (CDC) simulated exhaust conditions. The excellent activity is attributed to the unique nano-array structure that promotes gas-solid interaction and ultra-small Pt particle dispersion that increase surface Pt atoms. We also demonstrate that addition of more H2 into the exhaust can lower light-off temperature for CO and THC by up to ∼60 °C and ∼30 °C, respectively.

Three-dimensional (3D) nanoarchitectures can offer enhanced material properties, such as large surface areas that amplify the structures' interaction with environments making them useful for various sensing applications. Self-assembled block copolymers (BCPs) can readily generate various 3D nanomorphologies, but their conversion to useful inorganic materials remains one of the critical challenges against the practical application of self-assembled BCPs. This work reports the vapor-phase infiltration synthesis of optoelectrically active, 3D ZnO nanomesh architectures by combining hierarchical successive stacking of self-assembled, lamellar-phase polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) BCP thin films and a modified block-selective vapor-phase material infiltration protocol. The 3D ZnO nanomesh exhibits optoelectrical functionality, featuring stack-layer-number-dependent electrical conductance resembling the percolative transport originating from the intrinsic morphological network connectivity of the lamellar BCP pattern with symmetric block ratio. The results not only illustrate the first demonstration of electrical functionality based on the ZnO nanoarchitecture directly generated by the infiltration synthesis in self-assembled BCP thin films but also present a new, large-area scalable, metal oxide thin film nanoarchitecture fabrication method utilizing industry-compatible polymer solution coating and atomic layer deposition. Given the large surface area, three-dimensional porosity, and readily scalable fabrication procedures, the generated ZnO nanomesh promises potential applications as an efficient active medium in chemical and optical sensors.

Vapor-phase infiltration (VPI) is an emerging organic-inorganic materials hybridization technique derived from atomic layer deposition (ALD) wherein gaseous organometallic precursors and co-reactants diffuse into starting organic templates in a sequential and cyclic manner and become hybridized with the organic matrix. The resulting hybrids feature uniquely enhanced materials properties, including but not limited to mechanical, chemical, dielectric, optical, and electrical properties, which are controllable by the type and amount of infiltrated inorganic species. When combined with polymer templates with either dimensional confinement (e.g., lithographically defined polymer patterns) or intrinsic spatial chemical contrast (e.g., self-assembled block copolymer (BCP) thin films), the technique also yields a site-specific infiltration, analogous to area-selective ALD, creating a spatially localized hybridization. Furthermore, the organic matrix of such infiltrated hybrids can be selectively removed by plasma ashing and thermal annealing to generate inorganic nanostructures that inherit the morphology of starting polymer templates, providing an alternative inorganic nanopatterning methodology. In this talk, I will showcase how these features of VPI can be utilized for the applications in microelectronics, including: (a) arbitrary patterning ultrahigh aspect-ratio metal oxide nanostructures; (b) generation of metal-oxide-based nanowire and nanomesh structures for conductometric sensing; and (c) VPI-derived metal-oxide-infiltrated hybrid photoresists for extreme ultraviolet (EUV) lithography.

A novel atomic layer method for encapsulating individual micro- and nano-particles with thin (sub-10-nm) dielectric films is presented. This method leverages the diffusion of vapor-phase precursors through an underlying inert polymer film to achieve growth of a metal oxide film on all sides of the particle simultaneously; even on the side that is in contact with the substrate. Crucially, the deposition is performed on stationary particles and does not require an agitation mechanism or a special reaction chamber. Here, conformal coatings of alumina are shown to improve stability in aqueous environments for two optically-relevant particles: compound semiconductor laser microparticles and lead halide perovskite nanocrystals.

Recently, ultrathin metal-oxide thin film transistors (TFTs) have shown very high on-off ratio and ultra-sharp subthreshold swing, making them promising candidates for applications beyond conventional large-area electronics. While the on-off operation in typical TFTs results primarily from the modulation of charge carrier density by gate voltage, the high on-off ratio in ultrathin oxide TFTs can be associated with a large carrier mobility modulation, whose origin remains unknown. We investigate 3.5 nm-thick TiOx-based ultrathin TFTs exhibiting on-off ratio of ~106, predominantly driven by ~6-decade gate-induced mobility modulation. The power law behavior of the mobility features two regimes, with a very high exponent at low gate voltages, unprecedented for oxide TFTs. We find that this phenomenon is well explained by the presence of high-density tail states near the conduction band edge, which supports carrier transport via variable range hopping. The observed two-exponent regimes reflect the bi-exponential distribution of the density of band-tail states. This improved understanding would be significant in fabricating high-performance ultrathin oxide devices. The origin of large mobility modulation in ultrathin oxide transistors, promising for their high on-off ratio, remains mostly unknown. Here, a 106 gate-induced mobility modulation in 3.5 nm-thick TiOx transistors is explained by a high density of tail states, mediating variable range hopping of carriers.

Energy transfer (ET) from nanocrystals (NCs) has shown potential to enhance the optoelectronic performance of ultrathin semiconductor devices such as ultrathin Si solar cells, but the experimental identification of optimal device geometries for maximizing the performance enhancement is highly challenging due to a large parameter space. Here, we have demonstrated a general theoretical framework combining transfer matrix method (TMM) simulations and energy transfer (ET) calculations to reveal critical device design guidelines for developing an efficient, NC-based ET sensitization of ultrathin Si solar cells, which are otherwise infeasible to identify experimentally. The results uncover that the ET-driven NC sensitization is highly effective in enhancing the short circuit current (JSC) in sub-100 nm-thick Si layers, where, for example, the ET contribution can account for over 60% of the maximum achievable JSC in 10 nm-thick ultrathin Si. The study also reveals the limitation of the ET approach, which becomes ineffective for Si active layers thicker than 5 μm, being dominated by conventional optical coupling. The demonstrated simulation approach not only enables the development of efficient ultrathin Si solar cells but also should be applicable to precisely assessing and analyzing diverse experimental device geometries and configurations for developing new efficient ET-based ultrathin semiconductor optoelectronic devices.

The spontaneous formation of well-organized three-dimensional (3D) nanostructures from self-assembled block copolymers (BCPs) holds promise for nanofabrication and lithography. The addition of a th...

We demonstrate a simple ex-situ inorganic infiltration route for transforming standard organic resists into high-performance positive tone hybrid resist platform. A model thin film PMMA-AlOx hybrid resist system has been synthesized by hybridization of PMMA with AlOx and investigated for electron beam lithography. The approach possesses full controllability of the resist performance in terms of critical does, patterning contrast reaching up to 30 and etch resistance for plasma-based pattern transfer processes. The high selectivity Si etching capability demonstrated using a low-temperature cryo-Si etch process, based on the controlled infiltration outperforms commercial resists and typical hard mask material thermal SiO2, with estimated achievable selectivity in excess of ~300. Si nanostructures down to ~30 nm with aspect ratio up to ~17 are also transferred into the Si substrate. Easy implementation and adaptability for different inorganic infiltrations, this platform is well capable of potentially delivering the resist performance and throughput necessary for EUV lithography.

We here report the self-organization process of poly(styrene-b-ethylene/butadiene-b-styrene) (SEBS) triblock copolymer chains physically adsorbed on a non-neutral surface. Spin-cast SEBS thin films were prepared on silicon (Si) substrates and then annealed at a high temperature far above the bulk glass transition temperatures of the two constituent blocks. To reveal the buried interfacial structure, we utilized solvent rinsing processes and a suite of surface-sensitive techniques including ellipsometry, X-ray reflectivity, atomic force microscopy, and grazing incidence small angle X-ray scattering. We revealed that the SEBS chains form two different chain structures on the substrate simultaneously: (i) “flattened chains” with the average height of 2.5 nm but without forming microdomain structures; (ii) “loosely adsorbed chains” with the average height of 11.0 nm and the formation of perpendicularly oriented cylindrical microdomains to the substrate surface. In addition, the kinetics to form the perpendicular-oriented cylinder was sluggish (∼200 h) and proceeded via multistep processes toward the equilibrium state. We also found that the lateral microdomain structures were distorted, and the characteristic lengths of the microdomains were slightly different from the bulk even after reaching “quasiequilibrium” state within the observed time window. Furthermore, we highlight the vital role of the adsorbed chains in the self-assembling process of the entire SEBS thin film: a long-range perturbation associated with the adsorbed chains propagates into the film interior, overwhelming the free surface effect associated with surface segregation of the lower surface tension of polystyrene blocks.

ipso-Arylative ring-opening polymerization of 2-bromo-8-aryl-8H-indeno[2,1-b]thiophen-8-ol monomers proceeds to Mn up to 9 kg mol-1 with conversion of the monomer diarylcarbinol groups to pendent conjugated aroylphenyl side chains (2-benzoylphenyl or 2-(4-hexylbenzoyl)phenyl), which influence the optical and electronic properties of the resulting polythiophenes. Poly(3-(2-(4-hexylbenzoyl)phenyl)thiophene) was found to have lower frontier orbital energy levels (HOMO/LUMO=-5.9/-4.0 eV) than poly(3-hexylthiophene) owing to the electron-withdrawing ability of the aryl ketone side chains. The electron mobility (ca. 2×10-3 cm2 V-1 s-1 ) for poly(3-(2-(4-hexylbenzoyl)phenyl)thiophene) was found to be significantly higher than the hole mobility (ca. 8×10-6 cm2 V-1 s-1 ), which suggests such polymers are candidates for n-type organic semiconductors. Density functional theory calculations suggest that backbone distortion resulting from side-chain steric interactions could be a key factor influencing charge mobilities.

Polymer–inorganic hybrid nanocomposites exhibit enhanced material properties, combining the advantages of both their organic and inorganic subcomponents. Extensive research is being carried out to functionalize polymers towards various improved physicochemical characteristics such as electrical, optical, and mechanical properties for various applications. Vapor-phase material infiltration is an emerging hybridization route, derived from atomic layer deposition, which facilitates uniform incorporation of inorganic entities into a polymer matrix, leading to novel applications in fields such as microelectronics, energy storage, smart coatings, and smart fabrics. In this article, recent advances in employing vapor-phase material infiltration as a hybridization and nanopatterning technique for various application avenues are reviewed.

Oxygen and water vapor sensing properties are investigated in metal-oxide-hybrid polymer nanocomposite thin films generated by infiltration synthesis, which incorporates molecular ZnO into the matrix of SU-8 polymer, a common negative-tone photoresist. The hybrid thin films display 20-fold higher gravimetric responses to oxygen and water vapor than those of control ZnO thin films in the dark. An additional 50-500% enhanced responses are detected under UV irradiation. The overall enhanced gravimetric response in the hybrid film is attributed to the ZnO molecules distributed in the polymer matrix, whereas the UV enhancement is explained by the light-induced, reversible generation of hydrophilic fluoroantimonic acid from triarylsulfonium hexafluoroantimonate photoacids, which leads to the increased surface potential and adsorption energies for oxygen and water. A gravimetric sensor based on a series of ZnO-infiltrated SU-8 films under UV excitation enables 96% accurate classification of water and oxygen environment with sub 10 mTorr detection limits. The results demonstrate UV-induced fully reversible surface hydrophilicity of ZnO/SU-8 hybrid nanocomposites.

Solution-processable organic semiconductors have potentials as visible photoelectrochemical (PEC) water splitting photoelectrodes due to their tunable small band gap and electronic energy levels, but they are typically limited by poor stability and photocatalytic activity. Here, we demonstrate the direct visible PEC water oxidation on solution-processed organic semiconductor thin films with improved stability and performance by ultrathin metal oxide passivation layers. N-type fullerene-derivative thin films passivated by sub-2 nm ZnO via atomic layer deposition enabled the visible PEC water oxidation at wavelengths longer than 600 nm in harsh alkaline electrolyte environments with up to 30 μA/cm2 photocurrents at the thermodynamic water-oxidation equilibrium potential and the photoanode half-lifetime extended to ∼1000 s. The systematic investigation reveals the enhanced water oxidation catalytic activity afforded by ZnO passivation and the charge tunneling governing the hole transfer through passivation l...

Patterning materials efficiently at the smallest length scales is a longstanding challenge in nanotechnology. Electron-beam lithography (EBL) is the primary method for patterning arbitrary features, but EBL has not reliably provided sub-4 nm patterns. The few competing techniques that have achieved this resolution are orders of magnitude slower than EBL. In this work, we employed an aberration-corrected scanning transmission electron microscope for lithography to achieve unprecedented resolution. Here we show aberration-corrected EBL at the one nanometer length scale using poly(methyl methacrylate) (PMMA) and have produced both the smallest isolated feature in any conventional resist (1.7 ± 0.5 nm) and the highest density patterns in PMMA (10.7 nm pitch for negative-tone and 17.5 nm pitch for positive-tone PMMA). We also demonstrate pattern transfer from the resist to semiconductor and metallic materials at the sub-5 nm scale. These results indicate that polymer-based nanofabrication can achieve feature sizes comparable to the Kuhn length of PMMA and ten times smaller than its radius of gyration. Use of aberration-corrected EBL will increase the resolution, speed, and complexity in nanomaterial fabrication.

Nanodiamonds hosting colour centres are a promising material platform for various quantum technologies. The fabrication of non-aggregated and uniformly-sized nanodiamonds with systematic integration of single quantum emitters has so far been lacking. Here, we present a top-down fabrication method to produce 30.0$\pm$5.4 nm uniformly-sized single-crystal nanodiamonds by block copolymer self-assembled nanomask patterning together with directional and isotropic reactive ion etching. We show detected emission from bright single nitrogen vacancy centres hosted in the fabricated nanodiamonds. The lithographically precise patterning of large areas of diamond by self-assembled masks and their release into uniformly sized nanodiamonds open up new possibilities for quantum information processing and sensing., Comment: 15 pages, 2 figures

The change in the interplanar spacing (d-spacing) including the ferroelectric orthorhombic (O) phase in the low-temperature fabricated HfxZr1−xO2 (HZO) films was studied using synchrotron grazing-incidence wide-angle x-ray scattering analysis. The 10-nm-thick HZO films were fabricated by thermal and plasma-enhanced atomic layer deposition (TH- and PE-ALD) methods using H2O gas and O2 plasma as oxidants, respectively, and a post-metallization annealing (PMA) was performed at 300–400 °C. The d-spacing of the mixture of (111)-, (101)-, and (111)-planes of O, tetragonal (T), and cubic (C) phases, respectively, for the TH- and PE-ALD HZO films increased up to 2.99 Å with an increase in PMA temperature, while the d-spacing estimated by conventional x-ray diffraction was 2.92 Å regardless of the PMA temperature. The remanent polarization (2Pr = Pr+ − Pr−) of the HZO films increased as the PMA temperature increased. It is clear that the 2Pr value satisfied a linear relationship as a function of the d-spacing of O(111)/T(101)/C(111) phases. Furthermore, the wake-up effect was found to depend on the ferroelectric O phase formation. The wake-up effect was significantly reduced in both the TH- and PE-ALD HZO films after the PMA at 400 °C due to the increase in the ferroelectric O phase formation. The leakage current density (J)–electric field properties of the PE-ALD HZO film with the lowest d-spacing were divided into three steps, such as low, middle, and large J values, in the wake-up (103 cycles), pristine (100 cycle), and fatigue (107 cycles) states, respectively. Therefore, an analysis of the ferroelectric O phase is very important for understanding the ferroelectricity including endurance.

We report the effects of compressed CO, molecules as a novel plasticization agent for poly(3-hexylthiophene) (P3HT)-conjugated polymer thin films. In situ neutron reflectivity experiments demonstrated the excess sorption of CO, molecules in the P3HT thin films (about 40 nm in thickness) at low pressure (P = 8.2 MPa) under the isothermal condition of T = 36 degrees C, which is far below the polymer bulk melting point. The results proved that these CO2, molecules accelerated the crystallization process of the polymer on the basis of ex situ grazing incidence X-ray diffraction measurements after drying the films-via rapid depressurization to atmospheric pressure: both the out-of-plane lamellar ordering of the backbone chains and the intraplane pi-pi stacking of the side chains were significantly improved, when compared with those in the control P3HT films subjected to conventional thermal annealing (at T = 170 degrees C). Electrical measurements elucidated that the CO2-annealed P3HT thin films exhibited enhanced charge carrier mobility along with decreased background charge carrier concentration and trap density compared with those in the thermally annealed counterpart. This is attributed to the CO2-induced increase in polymer chain mobility that can drive the detrapping of molecular oxygen and healing of conformational defects in the polymer thin film. Given the universality of the excess sorption of CO2 regardless of the type of polymers, the present findings suggest that CO2 annealing near the critical point can be useful as a robust processing strategy for improving the structural and electrical characteristics of other semiconducting conjugated polymers and related systems such as polymer:fullerene bulk heterojunction films.

Infiltration synthesis is a process technique derived from atomic layer deposition (ALD), where polymeric templates, such as those lithographically patterned and self-assembled, are infiltrated by vapor-phase inorganic precursors to form novel organic-inorganic hybrids with enhanced materials properties. These hybrids can be further transformed by selectively removing the organic matrix to finally form metal oxide nanostructures with morphology and positional registry as dictated and designed by the starting polymer templates. In this talk, I will highlight a few examples of our recent efforts to generate functional inorganic nanostructures by using infiltration synthesis including, patterning arbitrary metal oxide nanostructures with sub-40 nm linewidth and over 15 aspect ratio, structural characteristics extremely difficult to achieve by conventional microfabrication techniques; fully CMOS compatible, wafer-scale synthesis and integration of in-plane aligned ZnO nanowire array phototransistors; and three-dimensional (3D) ZnO nanomesh structures derived from self-assembled block copolymer (BCP) templates with layer-number-dependent percolative electrical conductance.

This paper describes the design and construction of a compact, “user-friendly” polarization-modulation infrared reflection absorption spectroscopy (PM-IRRAS) instrument at the Center for Functional Nanomaterials (CFN) of Brookhaven National Laboratory, which allows studying surfaces at pressures ranging from ultra-high vacuum to 100 Torr. Surface infrared spectroscopy is ideally suited for studying these processes as the vibrational frequencies of the IR chromophores are sensitive to the nature of the bonding environment on the surface. Relying on the surface selection rules, by modulating the polarization of incident light, it is possible to separate the contributions from the isotropic gas or solution phase, from the surface bound species. A spectral frequency range between 1000 cm−1 and 4000 cm−1 can be acquired. While typical spectra with a good signal to noise ratio can be obtained at elevated pressures of gases in ∼2 min at 4 cm−1 resolution, we have also acquired higher resolution spectra at 0.25 c...

Modulus of resilience, the measure of a material’s ability to store and release elastic strain energy, is critical for realizing advanced mechanical actuation technologies in micro/nanoelectromechanical systems. In general, engineering the modulus of resilience is difficult because it requires asymmetrically increasing yield strength and Young’s modulus against their mutual scaling behavior. This task becomes further challenging if it needs to be carried out at the nanometer scale. Here, we demonstrate organic–inorganic hybrid composite nanopillars with one of the highest modulus of resilience per density by utilizing vapor-phase aluminum oxide infiltration in lithographically patterned negative photoresist SU-8. In situ nanomechanical measurements reveal a metal-like high yield strength (∼500 MPa) with an unusually low, foam-like Young’s modulus (∼7 GPa), a unique pairing that yields ultrahigh modulus of resilience, reaching up to ∼24 MJ/m3 as well as exceptional modulus of resilience per density of ∼13....

We report that the addition of a non-photoactive tertiary polymer phase in the binary bulk heterojunction (BHJ) polymer solar cell leads to a self-assembled columnar nanostructure, enhancing the charge mobilities and photovoltaic efficiency with surprisingly increased optimal active blend thicknesses over 300 nm, 3–4 times larger than that of the binary counterpart. Using the prototypical poly(3-hexylthiophene) (P3HT):fullerene blend as a model BHJ system, we discover that the inert poly(methyl methacrylate) (PMMA) added in the binary BHJ blend self-assembles into vertical columns, which not only template the phase segregation of electron acceptor fullerenes but also induce the out-of-plane rotation of the edge-on-orientated crystalline P3HT phase. Using complementary interrogation methods including neutron reflectivity, X-ray scattering, atomic force microscopy, transmission electron microscopy, and molecular dynamics simulations, we show that the enhanced charge transport originates from the more randomized molecular stacking of the P3HT phase and the spontaneous segregation of fullerenes at the P3HT/PMMA interface, driven by the high surface tension between the two polymeric components. The results demonstrate a potential method for increasing the thicknesses of high-performance polymer BHJ solar cells with improved photovoltaic efficiency, alleviating the burden of stringently controlling the ultrathin blend thickness during the roll-to-roll-type large-area manufacturing environment.

Cobalt oxide (Co3O4), a low-cost transitional metal oxide, has been widely studied for catalytic total oxidation of CO and hydrocarbons. However, much less attention has been paid to the poisoning effect due to alkali metals in such oxidation catalysts despite the ease of access to such poisons in both mobile and stationary combustion sources. In this study, the alkali metals such as Na, K and Li were readily deposited onto a Co3O4 catalyst to study their poisoning effect on CO and propane oxidation. 1% doping onto Co3O4 was found to increase the light-off temperature by 50 °C in CO oxidation and over 160 °C in propane oxidation. It is also noted that alkali metals exhibited a ‘locking-effect’ on oxygen of Co3O4, leading to poor oxygen mobility of alkali metal doped catalysts. During the reaction, alkali metals can significantly promote the adsorption of CO2 to form robust surface carbonate species even at high temperature, another reason for the poisoning effect of alkali metals on Co3O4 nanocatalysts for catalytic oxidation.

Noble metal nanoparticles are extensively used for sensitizing metal oxide chemical sensors through the catalytic spillover mechanism. However, due to earth-scarcity and high cost of noble metals, finding replacements presents a great economic benefit. Besides, high temperature and harsh environment sensor applications demand material stability under conditions approaching thermal and chemical stability limits of noble metals. In this study, we employed thermally stable perovskite-type La(0.8)Sr(0.2)FeO3 (LSFO) nanoparticle surface decoration on Ga2O3 nanorod array gas sensors and discovered an order of magnitude enhanced sensitivity to carbon monoxide at 500 °C. The LSFO nanoparticle catalysts was of comparable performance to that achieved by Pt nanoparticles, with a much lower weight loading than Pt. Detailed electron microscopy and X-ray photoelectron spectroscopy studies suggested the LSFO nanoparticle sensitization effect is attributed to a spillover-like effect associated with the gas-LSFO-Ga2O3 triple-interfaces that spread the negatively charged surface oxygen ions from LSFO nanoparticles surfaces over to β-Ga2O3 nanorod surfaces with faster surface CO oxidation reactions.