Patterning at the Resolution Limit of Commercial Electron Beam Lithography.

It has been long known that low molecular weight resists can achieve a very high resolution, theoretically close to the probe diameter of the electron beam lithography (EBL) system. Despite technological improvements in EBL systems, the advances in resists have lagged behind. Here we demonstrate that a low-molecular-mass single-source precursor resist (based on cadmium(II) ethylxanthate complexed with pyridine) is capable of a achieving resolution (4 nm) that closely matches the measured probe diameter (∼3.8 nm). Energetic electrons enable the top-down radiolysis of the resist, while they provide the energy to construct the functional material from the bottom-up─unit cell by unit cell. Since this occurs only within the volume of resist exposed to primary electrons, the minimum size of the patterned features is close to the beam diameter. We speculate that angstrom-scale patterning of functional materials is possible with single-source precursor resists using an aberration-corrected electron beam writer with a spot size of ∼1 Å.

1T and 2H heterophase MoS2for enhanced sensitivity of GaN transistor-based mercury ions sensor.

We report significantly enhanced sensitivity of AlGaN/GaN-based high electron mobility transistor (HEMT) sensor by the targeted synthesis of IT and 2H coexisting phase MoS2and applying the gate bias voltage. The HEMT structures on Si (111) substrates were used for the detection of Hg2+ions. The optimum sensitive regime in terms ofVGSandVDSof the sensor was investigated by keeping the drain source voltageVDSconstant at 2 V and by only varying the gate bias voltageVGSfrom 0 to 3 V. The strongest sensing response obtained from the device was around 0.547 mA ppb-1atVGS = 3 V, which is 63.7% higher in comparison to the response achieved at 0 V which shows a sensing response of around 0.334 mA ppb-1. The current response depicts that the fabricated device is very sensitive and selective towards Hg2+ions. Moreover, the detection limit of our sensor at 3 V was calculated around 6.21 ppt, which attributes to the strong field created between the gate electrode and the HEMT channel due to the presence of 1T metallic phase in synthesized MoS2, indicating that the lower detection limits are achievable in adequate strong fields.

Angstrom-Scale Transparent Overcoats: Interfacial Nitrogen-Driven Atomic Intermingling Promotes Lubricity and Surface Protection of Ultrathin Carbon.

Lubricity, a phenomenon which enables the ease of motion of objects, and wear resistance, which minimizes material damage or degradation, are important fundamental characteristics for sustainable technology developments. Ultrathin coatings that promote lubricity and wear resistance are of huge importance for a number of applications, including magnetic storage and micro-/nanoelectromechanical systems. Conventional ultrathin coatings have, however, reached their limit. Graphene-based materials that have shown promise to reduce friction and wear have many intrinsic limitations such as high temperature and substrate-specific growth. To address these concerns, a great deal of research is currently ongoing to optimize graphene-based materials. Here we discover that angstrom-thick carbon (8 Å) significantly reduces interfacial friction and wear. This lubricant shows ultrahigh optical transparency and can be directly deposited on a wide range of surfaces at room temperature. Experiments combined with molecular dynamics simulations reveal that the lubricating efficacy of 8 Å carbon is further improved via interfacial nitrogen.

Slippery and Wear-Resistant Surfaces Enabled by Interface Engineered Graphene.

Friction and wear remain the primary cause of mechanical energy dissipation and system failure. Recent studies reveal graphene as a powerful solid lubricant to combat friction and wear. Most of these studies have focused on nanoscale tribology and have been limited to a few specific surfaces. Here, we uncover many unknown aspects of graphene's contact-sliding at micro- and macroscopic tribo-scales over a broader range of surfaces. We discover that graphene's performance reduces for surfaces with increasing roughness. To overcome this, we introduce a new type of graphene/silicon nitride (SiNx, 3 nm) bilayer overcoats that exhibit superior performance compared to native graphene sheets (mono and bilayer), that is, display the lowest microscale friction and wear on a range of tribologically poor flat surfaces. More importantly, two-layer graphene/SiNx bilayer lubricant (<4 nm in total thickness) shows the highest macroscale wear durability on tape-head (topologically variant surface) that exceeds most previous thicker (∼7-100 nm) overcoats. Detailed nanoscale characterization and atomistic simulations explain the origin of the reduced friction and wear arising from these nanoscale coatings. Overall, this study demonstrates that engineered graphene-based coatings can outperform conventional coatings in a number of technologies.

Plasphonics: local hybridization of plasmons and phonons.

We show that the interaction between localized surface plasmons sustained by a metallic nano-antenna and delocalized phonons lying at the surface of an heteropolar semiconductor can generate a new class of hybrid electromagnetic modes. These plasphonic modes are investigated using an analytical model completed by accurate Green dyadic numerical simulations. When surface plasmon and surface phonon frequencies match, the optical resonances exhibit a large Rabi splitting typical of strongly interacting two-level systems. Based on numerical simulations of the electric near-field maps, we investigate the nature of the plaphonic excitations. In particular, we point out a strong local field enhancement boosted by the phononic surface. This effect is interpreted in terms of light harvesting by the plasmonic antenna from the phononic surface. We thus introduce the concept of active phononic surfaces that may be exploited for far-infared optoelectronic devices and sensors.

Damping of the acoustic vibrations of individual gold nanoparticles.

In this letter, the ultrafast vibrational dynamics of individual gold nanorings has been investigated by femtosecond transient absorption spectroscopy. Two acoustic vibration modes have been detected and identified. The influence of the mechanical coupling at the nanoparticle/substrate interface on the acoustic vibrations of the nano-objects is discussed. Moreover, by changing the environment of the nanoring, we provide a clear evidence of the impact of the surrounding medium on the damping of the acoustic vibrations. Such results are reported here for the first time on individual nanoparticles. This work points out a new sensing method based on the sensitivity of the acoustic vibration damping to the surrounding medium.

Acousto-plasmonic and surface-enhanced Raman scattering properties of coupled gold nanospheres/nanodisk trimers.

This work is devoted to the fundamental understanding of the interaction between acoustic vibrations and surface plasmons in metallic nano-objects. The acoustoplasmonic properties of coupled spherical gold nanoparticles and nanodisk trimers are investigated experimentally by optical transmission measurements and resonant Raman scattering experiments. For excitation close to resonance with the localized surface plasmons of the nanodisk trimers, we are able to detect several intense Raman bands generated by the spherical gold nanoparticles. On the basis of both vibrational dynamics calculations and Raman selection rules, the measured Raman bands are assigned to fundamental and overtones of the quadrupolar and breathing vibration modes of the spherical gold nanoparticles. Simulations of the electric near-field intensity maps performed at the Raman probe wavelengths showed strong localization of the optical energy in the vicinity of the nanodisk trimers, thus corroborating the role of the interaction between the acoustic vibrations of the spherical nanoparticles and the surface plasmons of the nanodisk trimers. Acoustic phonons surface enhanced Raman scattering is here demonstrated for the first time for such coupled plasmonic systems. This work paves the way to surface plasmon engineering for sensing the vibrational properties of nanoparticles.

Plasmonic properties of gold ring-disk nano-resonators: fine shape details matter.

Using numerical simulations, we demonstrate that fine shape details of gold nanoring-disks are responsible for significant modifications of their localized surface plasmon properties. The numerical results are supported by optical transmission measurements and by atomic force microscopy. In particular, we found that, depending on the ring wall sharpness, the spectral shift of the ring-like localized surface plasmon resonance can be as large as few hundred nanometers. These results shed the light on the strong sensitivity of the surface plasmon properties to very small deviations of the ring and disk shapes from the ideally flat surfaces and sharp edges. This effect is particularly important for tailoring the surface plasmon properties of metallic nanostructures presenting edges and wedges for applications in bio- and chemical sensing and for enhancement of light scattering.

Gold nanoring trimers: a versatile structure for infrared sensing.

In this work we report on the observation of surface plasmon properties of periodic arrays of gold nanoring trimers fabricated by electron beam lithography. It is shown that the localized surface plasmon resonances of such gold ring trimers occur in the infrared spectral region and are strongly influenced by the nanoring geometry and their relative positions. Based on numerical simulations of the optical extinction spectra and of the electric near-field intensity maps, the resonances are assigned to surface plasmon states arising from the strong intra-trimer electromagnetic interaction. We show that the nanoring trimer configuration allows for generating infrared surface plasmon resonances associated with strongly localized electromagnetic energy, thus providing plasmonic nanoresonators well-suited for sensing and surface enhanced near-infrared Raman spectroscopy.

Dual wavelength sensing based on interacting gold nanodisk trimers.

Fabrication and surface plasmon properties of gold nanostructures consisting of periodic arrays of disk trimers are reported. Using electron beam lithography, disk diameters as small as 96 nm and gaps between disks as narrow as 10 nm have been achieved with an unprecedented degree of control and reproducibility. The disk trimers exhibit intense visible and infrared surface plasmon resonances which are studied as a function of the disk diameter and of the pitch between trimers. Based on simulations of the optical extinction spectra and of the electric near-field intensity maps, the resonances are assigned to a single trimer response and to collective surface plasmon excitations involving electromagnetic interaction between the trimers. The sensing properties of the disk trimers are investigated using various coating media. The reported results demonstrate the possible use of gold disk trimers for dual wavelength chemical sensing.

Photodegradation of 4-nitrophenol over B-doped TiO2 nanostructure: effect of dopant concentration, kinetics, and mechanism.

The 4-nitrophenol (4-NP) is one of the carcinogenic pollutants listed by US EPA and has been detected in industrial wastewater. This study investigates the photocatalytic degradation of 4-NP with TiO2 and boron (B)-doped TiO2 nanostructures. The degradation on undoped and B-doped TiO2 with various boron loadings (1-7%) was studied to establish a relationship between structure, interface, and photo-catalytic properties. The results of XRD, micro Raman, FTIR, and HRTEM show that the B doping has improved the crystallinity and induces rutile phase along with anatase (major phase). The N2 adsorption-desorption, SEM-EDX, and XPS indicated that the B induced the formation of mesoporous nanostructures in TiO2 and occupies interstitial sites by forming Ti-O-B type linkage. The surface area of pure TiO2 was decreased from 235.4 to 63.3 m2/g in B-TiO2. The photo-physical properties were characterized by UV-Vis DRS, which showed decrease in the optical band-gap of pure TiO2 (2.98 eV) to B-TiO2 (2.95 eV). The degradation results demonstrated that the B doping improved the photocatalytic activity of TiO2; however, this improvement depends on the B concentration in doped TiO2. B-doped TiO2 (> 5% B) showed 90 % degradation of 4-NP, whereas the undoped TiO2 can degrade only 79 % of 4-NP. The degradation followed pseudo-first-order kinetics with rate constant values of 0.006 min-1 and 0.0322 min-1 for pure TiO2 and B-TiO2 respectively. The existence of a reduced form of Ti3+ on the surface of TiO2 (as evidence from XPS) was found responsible for enhancement in photocatalytic activity.

Thermoelectric Properties of Substoichiometric Electron Beam Patterned Bismuth Sulfide.

Direct patterning of thermoelectric metal chalcogenides can be challenging and is normally constrained to certain geometries and sizes. Here we report the synthesis, characterization, and direct writing of sub-10 nm wide bismuth sulfide (Bi2S3) using a single-source, spin-coatable, and electron-beam-sensitive bismuth(III) ethylxanthate precursor. In order to increase the intrinsically low carrier concentration of pristine Bi2S3, we developed a self-doping methodology in which sulfur vacancies are manipulated by tuning the temperature during vacuum annealing, to produce an electron-rich thermoelectric material. We report a room-temperature electrical conductivity of 6 S m-1 and a Seebeck coefficient of -21.41 µV K-1 for a directly patterned, substoichiometric Bi2S3 thin film. We expect that our demonstration of directly writable thermoelectric films, with further optimization of structure and morphology, can be useful for on-chip applications.

Nanoengineered Advanced Materials for Enabling Hydrogen Economy: Functionalized Graphene-Incorporated Cupric Oxide Catalyst for Efficient Solar Hydrogen Production.

Cupric oxide (CuO) is a promising candidate as a photocathode for visible-light-driven photo-electrochemical (PEC) water splitting. However, the stability of the CuO photocathode against photo-corrosion is crucial for developing CuO-based PEC cells. This study demonstrates a stable and efficient photocathode through the introduction of graphene into CuO film (CuO:G). The CuO:G composite electrodes are prepared using graphene-incorporated CuO sol-gel solution via spin-coating techniques. The graphene is modified with two different types of functional groups, such as amine (-NH2) and carboxylic acid (-COOH). The -COOH-functionalized graphene incorporation into CuO photocathode exhibits better stability and also improves the photocurrent generation compare to control CuO electrode. In addition, -COOH-functionalized graphene reduces the conversion of CuO phase into cuprous oxide (Cu2O) during photo-electrochemical reaction due to effective charge transfer and leads to a more stable photocathode. The reduction of CuO to Cu2O phase is significantly lesser in CuO:G-COOH as compared to CuO and CuO:G-NH2 photocathodes. The photocatalytic degradation of methylene blue (MB) by CuO, CuO:G-NH2 and CuO:G-COOH is also investigated. By integrating CuO:G-COOH photocathode with a sol-gel-deposited TiO2 protecting layer and Au-Pd nanostructure, stable and efficient photocathode are developed for solar hydrogen generation.

Room-Temperature Patterning of Nanoscale MoS2 under an Electron Beam.

Molybdenum disulfide (MoS2) is traditionally grown at a high temperature and subsequently patterned to study its electronic properties or make devices. This method imposes severe limitations on the shape and size of MoS2 crystals that can be patterned precisely at required positions. Here, we describe a method of direct nanoscale patterning of MoS2 at room temperature by exposing a molybdenum thiocubane single-source precursor to a beam of electrons. Molybdenum thiocubanes with various alkylxanthate moieties [Mo4S4(ROCS2)6, where R = alkyl] were prepared using a "self-assembly" approach. Micro-Raman and micro-FTIR spectroscopic studies suggest that exposure to a relatively smaller dose of electrons results in the breakdown of xanthate moieties, leading to the formation of MoS2. High-resolution transmission electron micrographs suggest that the growth of MoS2 most likely happens along (100) planes. An electron-beam-induced chemical transformation of a molybdenum thiocubane resist was exploited to fabricate sub-10 nm MoS2 lines and dense dots as small as 13 nm with a pitch of 33 nm. Since this technique does not require the liftoff and etching steps, patterning of MoS2 with interesting shapes, sizes, and thicknesses potentially leading to tunable band gap is possible.

Ultrasmall Designed Plasmon Resonators by Fused Colloidal Nanopatterning.

This work presents a procedure for large-area patterning of designed plasmon resonators that are much smaller than possible with conventional lithography techniques. Fused Colloidal Nanopatterning combines directed self-assembly and controlled fusing of spherical colloidal nanoparticles. The two-step approach first patterns a surface covered with hydrogen silsesquioxane, an electron beam resist, forming traps into which the colloidal gold nanoparticles self-assemble. Second, the patterned nanoparticles are controllably fused to form plasmon resonators of any 2D designed shape. The heights and widths of the plasmon resonators are determined by the diameter of the nanoparticle building blocks, which can be well below 10 nm. By performing the fusing step with UV ozone and heat exposure, we demonstrate that the process is easily scalable to cover large areas on silicon wafers with designed gold nanostructures. The procedure neither requires adhesion layers nor a lift-off process, making it ideally suited for plasmonics, in comparison with regular electron beam lithography. We use monochromated electron energy loss spectroscopy (EELS) in scanning transmission electron microscopy and boundary element method simulations to demonstrate that the designed plasmon resonators are directly tunable via the pattern design. We foresee future expansion of this approach for applications such as plasmon-enhanced photocatalysis and for large-scale patterning where chemical, optical, or confinement properties require sub-10 nm metal lines.

Boosting contact sliding and wear protection via atomic intermixing and tailoring of nanoscale interfaces.

Friction and wear cause energy wastage and system failure. Usually, thicker overcoats serve to combat such tribological concerns, but in many contact sliding systems, their large thickness hinders active components of the systems, degrades functionality, and constitutes a major barrier for technological developments. While sub-10-nm overcoats are of key interest, traditional overcoats suffer from rapid wear and degradation at this thickness regime. Using an enhanced atomic intermixing approach, we develop a ~7- to 8-nm-thick carbon/silicon nitride (C/SiN x ) multilayer overcoat demonstrating extremely high wear resistance and low friction at all tribological length scales, yielding ~2 to 10 times better macroscale wear durability than previously reported thicker (~20 to 100 nm) overcoats on tape drive heads. We report the discovery of many fundamental parameters that govern contact sliding and reveal how tuning atomic intermixing at interfaces and varying carbon and SiN x thicknesses strongly affect friction and wear, which are crucial for advancing numerous technologies.

Superior wear resistance and low friction in hybrid ultrathin silicon nitride/carbon films: synergy of the interfacial chemistry and carbon microstructure.

Amorphous carbon-based films are commonly investigated as protective nanocoatings in macro- to nano-scale devices due to their exceptional tribological and mechanical properties. However, with further device miniaturization where even thinner coatings are required, the wear durability of the nanocoating rapidly degrades at the expense of lower thickness. Here we discover that for sub-10 nm coating thicknesses, a hybrid bi-layer film structure, comprising a high sp3-bonded amorphous carbon top layer and a silicon nitride (SiNx) bottom layer, consistently outperforms its single-layer amorphous carbon counterpart in terms of wear durability on a commercial tape drive head, while exhibiting low, stable friction and excellent wear resistance on a flat ceramic substrate. The superior performance of the hybrid film is attributed to the constructive synergy of the sp3-rich carbon microstructure and an enhanced interfacial chemistry arising from additional interfacial bonding. Moreover, a high energy C+ ion treatment step, introduced either directly to the substrate or to the SiNx layer before carbon deposition, also aids in increasing atomic mixing that contributes to further improvement in the wear resistance. This study highlights the importance of both the carbon microstructure and interfacial chemistry in the design of wear-durable nanocoatings at few-nanometer thicknesses, particularly for aggressive wear conditions.

Direct Patterning of Zinc Sulfide on a Sub-10 Nanometer Scale via Electron Beam Lithography.

Nanostructures of metal sulfides are conventionally prepared via chemical techniques and patterned using self-assembly. This poses a considerable amount of challenge when arbitrary shapes and sizes of nanostructures are desired to be placed at precise locations. Here, we describe an alternative approach of nanoscale patterning of zinc sulfide (ZnS) directly using a spin-coatable and electron beam sensitive zinc butylxanthate resist without the lift-off or etching step. Time-resolved electron beam damage studies using micro-Raman and micro-FTIR spectroscopies suggest that exposure to a beam of electrons leads to quick disappearance of xanthate moieties most likely via the Chugaev elimination, and further increase of electron dose results in the appearance of ZnS, thereby making the exposed resist insoluble in organic solvents. Formation of ZnS nanocrystals was confirmed by high-resolution transmission electron microscopy and selected area electron diffraction. This property was exploited for the fabrication of ZnS lines as small as 6 nm and also enabled patterning of 10 nm dots with pitches as close as 22 nm. The ZnS patterns fabricated by this technique showed defect-induced photoluminescence related to sub-band-gap optical transitions. This method offers an easy way to generate an ensemble of functional ZnS nanostructures that can be arbitrarily patterned and placed in a precise way. Such an approach may enable programmable design of functional chalcogenide nanostructures.

Impact of molybdenum out diffusion and interface quality on the performance of sputter grown CZTS based solar cells.

We have investigated the impact of Cu2ZnSnS4-Molybdenum (Mo) interface quality on the performance of sputter-grown Cu2ZnSnS4 (CZTS) solar cell. Thin film CZTS was deposited by sputter deposition technique using stoichiometry quaternary CZTS target. Formation of molybdenum sulphide (MoSx) interfacial layer is observed in sputter grown CZTS films after sulphurization. Thickness of MoSx layer is found ~142 nm when CZTS layer (550 nm thick) is sulphurized at 600 °C. Thickness of MoSx layer significantly increased to ~240 nm in case of thicker CZTS layer (650 nm) under similar sulphurization condition. We also observe that high temperature (600 °C) annealing suppress the elemental impurities (Cu, Zn, Sn) at interfacial layer. The amount of out-diffused Mo significantly varies with the change in sulphurization temperature. The out-diffused Mo into CZTS layer and reconstructed interfacial layer remarkably decreases series resistance and increases shunt resistance of the solar cell. The overall efficiency of the solar cell is improved by nearly five times when 600 °C sulphurized CZTS layer is applied in place of 500 °C sulphurized layer. Molybdenum and sulphur diffusion reconstruct the interface layer during heat treatment and play the major role in charge carrier dynamics of a photovoltaic device.

High-density arrays of InGaN nanorings, nanodots, and nanoarrows fabricated by a template-assisted approach.

Dense, crystalline arrays of InGaN nanorings, nanodots, and nanoarrows have been fabricated on GaN substrates by template-assisted nano-area selective growth. To create the nanostructures, we have used nanoporous anodic alumina films as templates to pattern nanopores in an SiO2 transfer layer, and then used this patterned SiO2 layer as a template for nitride growth by metalorganic chemical vapor deposition. We have varied the diameter of the deposited nitride nanostructures from 35 to 250 nm by changing the initial anodic alumina template structure. In addition, by controlling the nitride growth time we have created various types of nanostructures, from nanorings to nanoarrows. This structural evolution begins with the nucleation and formation of a nanoring structure, followed by coalescence and growth to form faceted nanodots, and finally lateral overgrowth to form faceted nanoarrows.