Modulating Energetic Characteristics of Multicomponent 1D Coordination Polymers: Interplay of Metal-Ligand Coordination Modes.

The energetic properties of multicomponent explosive materials can be altered for high detonation capabilities and minimized safety risk by changing their building components. We synthesized energetic coordination polymers (ECPs) using a 5,5'-bis(tetrazole)-1,1'-diolate linker and a N,N-dimethylacetamide (DMA) solvent, together with Cu and Mn metal cations. The new compounds, ECP-1 and ECP-2, contain two different types of 1D chain structures, straight and helical. We have conducted comprehensive studies on these ECP structures, energetic properties, and sensitivity and found excellent insensitivity owing to the long chain-to-chain distances created by the DMA solvent molecules. The results indicate that the metals as well as solvents used are crucial components influencing both the structure and energetic properties.

Experimental and numerical evaluation of a genetically engineered M13 bacteriophage with high sensitivity and selectivity for 2,4,6-trinitrotoluene.

Selective and sensitive detection of desired targets is very critical in sensor design. Here, we report a genetically engineered M13 bacteriophage-based sensor system evaluated by quantum mechanics (QM) calculations. Phage display is a facile way to develop the desired peptide sequences, but the resulting sequences can be imperfect peptides for binding of target molecules. A TNT binding peptide (WHW) carrying phage was self-assembled to fabricate thin films and tested for the sensitive and selective surface plasmon resonance-based detection of TNT molecules at the 500 femtomole level. SPR studies performed with the WHW peptide and control peptides (WAW, WHA, AHW) were well-matched with those of the QM calculations. Our combined method between phage engineering and QM calculation will significantly enhance our ability to design selective and sensitive sensors.

High-Resolution p-Type Metal Oxide Semiconductor Nanowire Array as an Ultrasensitive Sensor for Volatile Organic Compounds.

The development of high-performance volatile organic compound (VOC) sensor based on a p-type metal oxide semiconductor (MOS) is one of the important topics in gas sensor research because of its unique sensing characteristics, namely, rapid recovery kinetics, low temperature dependence, high humidity or thermal stability, and high potential for p-n junction applications. Despite intensive efforts made in this area, the applications of such sensors are hindered because of drawbacks related to the low sensitivity and slow response or long recovery time of p-type MOSs. In this study, the VOC sensing performance of a p-type MOS was significantly enhanced by forming a patterned p-type polycrystalline MOS with an ultrathin, high-aspect-ratio (∼25) structure (∼14 nm thickness) composed of ultrasmall grains (∼5 nm size). A high-resolution polycrystalline p-type MOS nanowire array with a grain size of ∼5 nm was fabricated by secondary sputtering via Ar(+) bombardment. Various p-type nanowire arrays of CuO, NiO, and Cr2O3 were easily fabricated by simply changing the sputtering material. The VOC sensor thus fabricated exhibited higher sensitivity (ΔR/Ra = 30 at 1 ppm hexane using NiO channels), as well as faster response or shorter recovery time (∼30 s) than that of previously reported p-type MOS sensors. This result is attributed to the high resolution and small grain size of p-type MOSs, which lead to overlap of fully charged zones; as a result, electrical properties are predominantly determined by surface states. Our new approach may be used as a route for producing high-resolution MOSs with particle sizes of ∼5 nm within a highly ordered, tall nanowire array structure.

Controlling Smectic Liquid Crystal Defect Patterns by Physical Stamping-Assisted Domain Separation and Their Use as Templates for Quantum Dot Cluster Arrays.

Controlling the organization of self-assembling building blocks over a large area is crucial for lithographic tools based on the bottom-up approach. However, the fabrication of liquid crystal (LC) defect patterns with a particular ordering still remains a challenge because of the limited close-packed morphologies of LC defects. Here, we introduce a multiple-stamping domain separation method for the control of the dimensions and organization of LC defect structures. Prepatterns with various grid shapes on planar polyimide (PI) surfaces were fabricated by pressing a line-shaped stamp into the PI surfaces in two different directions, and then these surfaces were used to prepare LC defect structures confined to these grid domains. The dimensions of the LC defect structures, namely, the equilibrium diameter and the center to center spacing, are controlled by varying the line spacing of the stamps and the film thickness. A variety of arrangements of LC defects, including square, rhombic, hexagonal, and other oblique lattices, can be obtained by simply varying the stamping angle (Ω) between the first and second stamping directions. Furthermore, we demonstrate that the resulting controllable LC defect arrays can be used as templates for generating various patterns of nanoparticle clusters by trapping quantum dots (QDs) within the cores of the LC defects.

Macroscopic alignment of chromonic liquid crystals using patterned substrates.

We demonstrate an efficient technique to align lyotropic chromonic liquid crystals (LCLCs) using secondary sputtering lithography (SSL). Monodomains of LCLCs prepared using SSL maintained their stable alignment for days. A generalization of Berreman's theory was employed to determine the anchoring strength of LCLCs on tessellated surface patterns. The anchoring energy initially increases with the amplitude (A) of the grooves and excellent alignment of LCLCs was observed when the amplitude of the grooves is equal to half its wavelength (λ). We also note that the anchoring energy levels off above qA∼ 3 (where q = 2π/λ), which suggests that increasing qA beyond a certain value does not provide any further advantage for the alignment of LCLCs. This finding provides a useful optimization criterion for the fabrication of the patterned cells to achieve stable monodomain alignment of LCLCs. Our analysis also explains why good alignment of LCLCs has been a difficult task.

Ti(N5)4 as a Potential Nitrogen-Rich Stable High-Energy Density Material.

We have studied molecular structures and kinetic stabilities of M(N5)3 (M = Sc, Y) and M(N5)4 (M = Ti, Zr, Hf) complexes theoretically. All of these compounds are found to be stable with more than a 13 kcal/mol of kinetic barrier. In particular, Ti(N5)4 showed the largest dissociation energy of 173.0 kcal/mol and thermodynamic stability. This complex had a high nitrogen content (85% by weight), and a significantly high nitrogen to metal ratio (20:1) among the neutral M(N5)n species studied here and in the literature. Ti(N5)4 is thus forecasted to be a good candidate for a nitrogen-rich high-energy density material (HEDM). We reveal in further detail using ab initio molecular dynamics simulations that the dissociation pathways of M(N5)n involve the rearrangements of the bonding configurations before dissociation.

Highly Enhanced Fluorescence Signals of Quantum Dot-Polymer Composite Arrays Formed by Hybridization of Ultrathin Plasmonic Au Nanowalls.

Enhancement of the fluorescence intensity of quantum dot (QD)-polymer nanocomposite arrays is an important issue in QD studies because of the significant reduction of fluorescence signals of such arrays due to nonradiative processes in densely packed polymer chains in solid films. In this study, we enhance the fluorescence intensity of such arrays without significantly reducing their optical transparency. Enhanced fluorescence is achieved by hybridizing ultrathin plasmonic Au nanowalls onto the sidewalls of the arrays via single-step patterning and hybridization. The plasmonic Au nanowall induces metal-enhanced fluorescence, resulting in a maximum 7-fold enhancement of the fluorescence signals. We also prepare QD nanostructures of various shapes and sizes by controlling the dry etching time. In the near future, this facile approach can be used for fluorescence enhancement of colloidal QDs with plasmonic hybrid structures. Such structures can be used as optical substrates for imaging applications and for fabrication of QD-LED devices.

Well-defined and high resolution Pt nanowire arrays for a high performance hydrogen sensor by a surface scattering phenomenon.

Developing hydrogen (H2) sensors with a high sensitivity, rapid response, long-term stability, and high throughput is one of the critical issues in energy and environmental technology [Hübert et al. Sens. Actuators, B 2011, 157, 329]. To date, H2 sensors have been mainly developed using palladium (Pd) as the channel material because of its high selectivity and strong affinity to the H2 molecule [(Xu et al. Appl. Phys. Lett. 2005, 86, 203104), (Offermans et al. Appl. Phys. Lett. 2009, 94, 223110), (Yang et al. Nano Lett. 2009, 9, 2177), (Yang et al. ACS Nano 2010, 4, 5233), and (Zou et al. Chem. Commun. 2012, 48, 1033)]. Despite significant progress in this area, Pd based H2 sensors suffer from fractures on their structure due to hydrogen adsorption induced volumetric swelling during the α → ß phase transition, leading to poor long-term stability and reliability [(Favier et al. Science 2001, 293, 2227), (Walter et al. Microelectron. Eng. 2002, 61­62, 555), and (Walter et al. Anal. Chem. 2002, 74, 1546)]. In this study, we developed a platinum (Pt) nanostructure based H2 sensor that avoids the stability limitations of Pd based sensors. This sensor exhibited an excellent sensing performance, low limit of detection (LOD, 1 ppm), reproducibility, and good recovery behavior at room temperature. This Pt based H2 sensor relies on a highly periodic, small cross sectional dimension (10­40 nm) and a well-defined configuration of Pt nanowire arrays over a large area. The resistance of the Pt nanowire arrays significantly decreased upon exposure to H2 due to reduced electron scattering in the cross section of the hydrogen adsorbed Pt nanowires, as compared to the oxygen terminated original state. Therefore, these well-defined Pt nanowire arrays prepared using advanced lithographic techniques can facilitate the production of high performance H2 sensors.

Tunable volatile organic compounds sensor by using thiolated ligand conjugation on MoS2.

One of the most important issues in the development of gas sensors for breath analysis is the fabrication of gas sensor arrays that possess different responses for recognizing patterns for volatile organic compounds (VOCs). Here, we develop a high-performance chemiresistor with a tunable sensor response and high sensitivity for representative VOC groups by using molybdenum disulfide (MoS2) and by conjugating a thiolated ligand (mercaptoundecanoic acid (MUA)) to MoS2 surface. Primitive and MUA-conjugated MoS2 sensing channels exhibit distinctly different sensor responses toward VOCs. In particular, the primitive MoS2 sensor presents positive responses for oxygen-functionalized VOCs, while the MUA-conjugated MoS2 sensor presents negative responses for the same analytes. Such characteristic sensor responses demonstrate that ligand conjugation successfully adds functionality to a MoS2 matrix. Thus, this will be a promising approach to constructing a versatile sensor array, by conjugating a wide variety of thiolated ligands on the MoS2 surface. Furthermore, these MoS2 sensors in this study exhibit high sensitivity to representative VOCs down to a concentration of 1 ppm. This approach to fabricating a tunable and sensitive VOC sensor may lead to a valuable real-world application for lung cancer diagnosis by breath analysis.

The fabrication of highly ordered silver nanodot patterns by platinum assisted nanoimprint lithography.

Silver has been widely used for optical sensing and imaging applications which benefit from localized surface plasmon resonance (LSPR) in a nanoscale configuration. Many attempts have been made to fabricate and control silver nanostructures in order to improve the high performance in sensing and other applications. However, a fatal mechanical weakness of silver and a lack of durability in oxygen-rich conditions have disrupted the manufacturing of reproducible nanostructures by the top-down lithography approach. In this study, we suggest a steady fabrication strategy to obtain highly ordered silver nanopatterns that are able to provide tunable LSPR characteristics. By using a protecting layer of platinum on a silver surface in the lithography process, we successfully obtained large-area (2.7 × 2.7 mm(2)) silver nanopatterns with high reproducibility. This large-area silver nanopattern was capable of enhancing the low concentration of a Cy3 fluorescence signal (∼10(-10) M) which was labeled with DNA oligomers.

Polyelemental Nanolithography via Plasma Ion Bombardment: From Fabrication to Superior H2 Sensing Application.

The development of complex nanostructures containing a homo- and heteromixture of two or more metals is a considerable challenge in nanotechnology. However, previous approaches are considerably limited to the number of combinations of metals depending on the compatibility of elements, and to the complex shape control of the nanostructure. In this study, a significant step is taken toward resolving these limitations via the utilization of a low-energy argon-ion bombardment. The multilayer films are etched and re-sputtered on the sidewall of the pre-pattern, which is a secondary sputtering phenomenon. In contrast to the precursor mixing method, most metallic combinations can be fabricated. The degree of mixing is tuned by the control of the sequence and thickness of multilayers. In addition, the feature shape and dimensions are controlled by changing the pre-pattern or by controlling the ion-beam angle. Using this method, the shortest response time (2 s to 1% H2 ) in comparison with those of Pd-based H2 sensors reported previously and a limit of detection below 1 parts per million (ppm) for Pd/Au and Pd/Pt bimetallic line arrays are achieved. This study is expected to realize a family of polyelements that can be used in various applications.

Tunable Volatile-Organic-Compound Sensor by Using Au Nanoparticle Incorporation on MoS2.

Controlling the charge concentrations of two-dimensional (2D) materials is a critical requirement for realizing versatility and potential application of these materials in high-performance electronics and sensors. In order to exploit the novel chemical-sensing characteristics of 2D materials for sensitive and selective sensors, various functionalization methods are needed to ensure efficient doping of channels based on 2D materials. In the present study, the gas-sensing performance of MoS2 has been significantly enhanced by controlled Au nanoparticle functionalization. By using the difference in reduction potential between the Au precursor and MoS2 work functions, MoS2 prepared by chemical exfoliation process was decorated with nanoparticles with sizes of tens of nanometers. The n-doping effect of Au nanoparticles was observed, that is, these particles were found to have facilitated in electron charge transfer from Au to MoS2. The controlled n-doping effect enables the tuning of the sensing of hydrocarbon-based volatile organic compounds (VOCs) and oxygen-functionalized compounds by MoS2. A significant step has therefore been made with this study toward solving the limitations imposed by previous MoS2-based sensors, which mostly produce a single response to various VOC analytes. This controllable chemical doping process for tuning the VOC-sensing performance of MoS2 can eventually be used in early detection using multichannel sensing systems that have different responses and recognize patterns for target analytes.

Ultrafast Interfacial Self-Assembly of 2D Transition Metal Dichalcogenides Monolayer Films and Their Vertical and In-Plane Heterostructures.

Cost effective scalable method for uniform film formation is highly demanded for the emerging applications of 2D transition metal dichalcogenides (TMDs). We demonstrate a reliable and fast interfacial self-assembly of TMD thin films and their heterostructures. Large-area 2D TMD monolayer films are assembled at air-water interface in a few minutes by simple addition of ethyl acetate (EA) onto dilute aqueous dispersions of TMDs. Assembled TMD films can be directly transferred onto arbitrary nonplanar and flexible substrates. Precise thickness controllability of TMD thin films, which is essential for thickness-dependent applications, can be readily obtained by the number of film stacking. Most importantly, complex structures such as laterally assembled 2D heterostructures of TMDs can be assembled from mixture solution dispersions of two or more different TMDs. This unusually fast interfacial self-assembly could open up a novel applications of 2D TMD materials with precise tunability of layer number and film structures.

Superior Chemical Sensing Performance of Black Phosphorus: Comparison with MoS2 and Graphene.

Superior chemical sensing performance of black phosphorus (BP) is demonstrated by comparison with MoS2 and graphene. Dynamic sensing measurements of multichannel detection show that BP displays highly sensitive, selective, and fast-responsive NO2 sensing performance compared to the other representative 2D sensing materials.

Highly Enhanced Gas Adsorption Properties in Vertically Aligned MoS2 Layers.

In this work, we demonstrate that gas adsorption is significantly higher in edge sites of vertically aligned MoS2 compared to that of the conventional basal plane exposed MoS2 films. To compare the effect of the alignment of MoS2 on the gas adsorption properties, we synthesized three distinct MoS2 films with different alignment directions ((1) horizontally aligned MoS2 (basal plane exposed), (2) mixture of horizontally aligned MoS2 and vertically aligned layers (basal and edge exposed), and (3) vertically aligned MoS2 (edge exposed)) by using rapid sulfurization method of CVD process. Vertically aligned MoS2 film shows about 5-fold enhanced sensitivity to NO2 gas molecules compared to horizontally aligned MoS2 film. Vertically aligned MoS2 has superior resistance variation compared to horizontally aligned MoS2 even with same surface area exposed to identical concentration of gas molecules. We found that electrical response to target gas molecules correlates directly with the density of the exposed edge sites of MoS2 due to high adsorption of gas molecules onto edge sites of vertically aligned MoS2. Density functional theory (DFT) calculations corroborate the experimental results as stronger NO2 binding energies are computed for multiple configurations near the edge sites of MoS2, which verifies that electrical response to target gas molecules (NO2) correlates directly with the density of the exposed edge sites of MoS2 due to high adsorption of gas molecules onto edge sites of vertically aligned MoS2. We believe that this observation extends to other 2D TMD materials as well as MoS2 and can be applied to significantly enhance the gas sensor performance in these materials.

Fabrication of sub-20 nm nano-gap structures through the elastomeric nano-stamp assisted secondary sputtering phenomenon.

We describe a highly efficient method for fabricating controllable and reliable sub-20 nm scale nano-gap structures through an elastomeric nano-stamp with an embedded ultra-thin pattern. The stamp consists of ultrahigh resolution (approximately 10 nm) and high aspect ratio (ca. 15) metal nano-structures, which are obtained by secondary sputtering lithography (SSL). The nano-gap structures fabricated in this fashion achieve a high resolution and meet the requirements of minimal cost, high reliability, controllability, reproducibility, and applicability to different materials. Further, we demonstrate that this method enables the fabrication of SERS substrates for detection at the single-molecule level.

Fabrication of complex 3-dimensional patterned structures on a ∼10 nm scale from a single master pattern by secondary sputtering lithography.

We describe a highly efficient method for fabricating a variety of complex 3D nano-patterns from a single master pattern using secondary sputtering lithography, which is a 10 nm scale patterning method that we have developed. A rapid etching rate in the bottom part of the PS pillar during the RIE process can produce various nanostructure shapes and the PS residual layer thickness can influence various feature dimensions, due to the controlled RIE time leading to different PS layer thicknesses. This technique provides a highly effective method for producing various complex 3D patterns from a single master pattern. Thus, this method can serve as a new procedure for the cost-effective mass production of complex nanoscale patterns with high resolution.

Electrical conductivity of graphene films with a poly(allylamine hydrochloride) supporting layer.

The electrical conductivity of graphene oxide (GO) and reduced graphene oxide (RGO) films with poly(allylamine hydrochloride) (PAH) supporting layers is investigated. Graphene-PAH hybrid films were produced in a two-step procedure that consisted of vacuum filtration for GO (or RGO) dispersion to fabricate the graphene thin films on quartz substrates, followed by the deposition of PAH onto the graphene films via solution casting. Highly selective deposition of the PAH layer on the graphene sheets was confirmed through the detection of the fluorescence signals of hybridized Cy3-DNA onto the PAH-coated graphene surfaces. In this case, electrostatic interaction plays an important role in the selective deposition process. Interestingly, it was found that the electrical conductivity of RGO films was significantly enhanced by 120% after PAH treatment, whereas that of the GO films was reduced by 98% of its initial conductivity. This finding was interpreted in terms of the molecular structure and oxygen functionalities of GO and RGO films combined with the ionic conduction characteristics of hydrated PAH on the RGO film.