Mohammad S. M. Saifullah

Multiscale Ommatidial Arrays with Broadband and Omnidirectional Antireflection and Antifogging Properties by Sacrificial Layer Mediated Nanoimprinting

Moths eye inspired multiscale ommatidial arrays offer multifunctional properties of great significance in optoelectronic devices. However, a major challenge remains in fabricating these arrays on large-area substrates using a simple and scalable technique. Here we present the fabrication of these multiscale ommatidial arrays over large areas by a distinct approach called sacrificial layer mediated nanoimprinting, which involves nanoimprinting aided by a sacrificial layer. The fabricated arrays exhibited excellent pattern uniformity over the entire patterned area. Optimum dimensions of the multiscale ommatidial arrays determined by the finite-difference time domain simulations served as the design parameters for replicating the arrays on glass. A broadband suppression of reflectance to a minimum of ∼1.4% and omnidirectional antireflection for highly oblique angles of incidence up to 70° were achieved. In addition, superhydrophobicity and superior antifogging characteristics enabled the retention of optical properties even in wet and humid conditions, suggesting reliable optical performance in practical outdoor conditions. We anticipate that these properties could potentially enhance the performance of optoelectronic devices and minimize the influence of in-service conditions. Additionally, as our technique is solely nanoimprinting-based, it may enable scalable and high-throughput fabrication of multiscale ommatidial arrays.

A reliable scheme for fabricating sub-5 nm co-planar junctions for single-molecule electronics

We demonstrate a high yield production scheme to fabricate sub-5 nm co-planar metal–insulator–metal junctions. This involves determining the relationship between the actual gap between the metallic junctions for a given designed gap, and the use of weak developers with ultrasonic agitation to process the exposed resist. This results in an improved process to achieve narrow inter-electrode gaps. The gaps were imaged using an AFM equipped with a carbon nanotube tip to achieve a high degree of accuracy in measurement. The smallest gap unambiguously measured was ~ 2 nm. Gaps with ≤ 5 nm spacing were produced with a very high yield of about 75% for a designed inter-electrode distance of 0 nm. The leakage resistance of the gaps was found to be of the order of 1012 Ω. The entire junction structure was designed to be co-planar to better than 1 nm over 1 μ m2.

Metal hierarchical patterning by direct nanoimprint lithography

Three-dimensional hierarchical patterning of metals is of paramount importance in diverse fields involving photonics, controlling surface wettability and wearable electronics. Conventionally, this type of structuring is tedious and usually involves layer-by-layer lithographic patterning. Here, we describe a simple process of direct nanoimprint lithography using palladium benzylthiolate, a versatile metal-organic ink, which not only leads to the formation of hierarchical patterns but also is amenable to layer-by-layer stacking of the metal over large areas. The key to achieving such multi-faceted patterning is hysteretic melting of ink, enabling its shaping. It undergoes transformation to metallic palladium under gentle thermal conditions without affecting the integrity of the hierarchical patterns on micro- as well as nanoscale. A metallic rice leaf structure showing anisotropic wetting behavior and woodpile-like structures were thus fabricated. Furthermore, this method is extendable for transferring imprinted structures to a flexible substrate to make them robust enough to sustain numerous bending cycles.

Robust and durable polyhedral oligomeric silsesquioxane-based anti-reflective nanostructures with broadband quasi-omnidirectional properties

Polymer-based anti-reflective coatings (ARCs) on glass pose major challenges for outdoor photovoltaic applications due to their incompatible mechanical and thermal properties. Here we demonstrate durable, chemically and thermally stable polyhedral oligomeric silsesquioxane-based (POSS) anti-reflective moths eye nanostructures on glass fabricated by double-side nanoimprint lithography. These anti-reflective nanostructures exhibited excellent broadband and quasi-omnidirectional anti-reflective properties. An optimum resist composition for nanoimprinting was obtained by mixing a methacryl POSS cage mixture with 1,6-hexanediol diacrylate in a 1 : 12 molar ratio. Thermal free radical co-polymerization during nanoimprint lithography produced a uniform array of moths eye nanostructures on both sides of a glass substrate with yields ∼90 to 100%. The transmittance of the resulting glass was enhanced to 98.2% (reflectance 1.26%) with excellent quasi-omnidirectional transmittance observed from −50° to +50° of angles of incidence. Furthermore, a series of ASTM-based tests on the imprinted ARC structures showed strong adherence to glass, better hardness and mechanical strength with superior chemical and thermal stability, thus suggesting their strong potential for commercial applications.

Direct Patterning of TiO2 Using Step-and-Flash Imprint Lithography

Although step-and-flash imprint lithography, or S-FIL, has brought about tremendous advancement in wafer-scale fabrication of sub-100 nm features of photopolymerizable organic and organo-silicon-based resists, it has not been successful in direct patterning of inorganic materials such as oxides because of the difficulties associated with resist formulation and its dispensing. In this paper, we demonstrate the proof-of-concept S-FIL of titanium dioxide (TiO(2)) carried by an acrylate-based formulation containing an allyl-functionalized titanium complex. The prepolymer formulation contains 48 wt % metal precursor, but it exhibits low enough viscosity (∼5 mPa·s) to be dispensed by an automatic dispensing system, adheres and spreads well on the substrate, is insensitive to pattern density variations, and rapidly polymerizes when exposed to broadband UV radiation to give a yield close to 95%. Five fields, each measuring 1 cm × 1 cm, consisting of 100 nm gratings were successively imprinted. Heat-treatment of the patterned structures at 450 °C resulted in the loss of organics and their subsequent shrinkage without the loss of integrity or aspect ratio and converted them to TiO(2) anatase nanostructures as small as 30 nm wide. With this approach, wafer-scale direct patterning of functional oxides on a sub-100 nm scale using S-FIL can become a distinct possibility.

Flexible Palladium-Based H2 Sensor with Fast Response and Low Leakage Detection by Nanoimprint Lithography

Flexible palladium-based H2 sensors have a great potential in advanced sensing applications, as they offer advantages such as light weight, space conservation, and mechanical durability. Despite these advantages, the paucity of such sensors is due to the fact that they are difficult to fabricate while maintaining excellent sensing performance. Here, we demonstrate, using direct nanoimprint lithography of palladium, the fabrication of a flexible, durable, and fast responsive H2 sensor that is capable of detecting H2 gas concentration as low as 50 ppm. High resolution and high throughput patterning of palladium gratings over a 2 cm × 1 cm area on a rigid substrate was achieved by heat-treating nanoimprinted palladium benzyl mercaptide at 250 °C for 1 h. The flexible and robust H2 sensing device was fabricated by subsequent transfer nanoimprinting of these gratings into a polycarbonate film at its glass transition temperature. This technique produces flexible H2 sensors with improved durability, sensitivity, and response time in comparison to palladium thin films. At ambient pressure and temperature, the device showed a fast response time of 18 s at a H2 concentration of 3500 ppm. At 50 ppm concentration, the response time was found to be 57 s. The flexibility of the sensor does not appear to compromise its performance.

Direct writing of ZrO2 on a sub-10 nm scale using an electron beam

We describe a direct write technique using an electron beam to pattern ZrO2 on a sub-10 nm scale that bypasses the conventional method of sputtering and lift-off. This technique utilizes spin-coatable ZrO2 resist prepared by chemically reacting zirconium n-butoxide with benzoyl acetone in ethanol. The patterned resist has a sensitivity and contrast of and 3, respectively. Baking the resist at 85 °C increases the sensitivity to . The electron-beam-exposed regions become insoluble in acetone, thus yielding negative patterns. This property was exploited to write high-resolution patterns as small as 9 nm wide. Such negative patterns can be written with a pitch as close as 30 nm.

Direct nanoimprinting of metal oxides by in situ thermal co-polymerization of their methacrylates

The use of polymerization to solidify, strengthen and imprint liquid organic materials is the basis of ultraviolet (UV) nanoimprint lithography. In spite of these advantages, the use of polymerization to pattern materials in thermal nanoimprint lithography is almost non-existent. In this study, we demonstrate a facile and general method to directly imprint a host of unary metal oxides (Fe2O3, ZrO2, TiO2, Nb2O5 and Ta2O5) at a very high resolution viain situ thermal free radical co-polymerization of various metal methacrylates in the presence of cross-linker ethylene glycol dimethacrylate using a silicon mold. Polymerization during nanoimprinting rigidly shapes the patterns, traps the metal atoms, reduces the surface energy and strengthens the structures, thereby giving ∼100% yield after demolding. It was found that the higher oxidation state of metal resulted in excessive cracking of imprinted structures. This could be due to a higher degree of cross-linking of the precursor leading to shrinkage-related stress. Optimization of the resin composition by partially replacing ethylene glycol dimethacrylate with methyl methacrylate alleviated this problem. Heat-treatment of the imprinted structures resulted in the loss of organics, their subsequent shrinkage and converted the patterns to their corresponding metal oxides with line-widths as small as 25 nm.

Trapped charge dynamics in a sol-gel based TiO 2 high-k gate dielectric silicon metal-oxide-semiconductor field effect transistor

We have studied the response of a sol-gel based TiO(2), high k dielectric field effect transistor structure to microwave radiation. Under fixed bias conditions the transistor shows frequency dependent current fluctuations when exposed to continuous wave microwave radiation. Some of these fluctuations take the form of high Q resonances. The time dependent characteristics of these responses were studied by modulating the microwaves with a pulse signal. The measurements show that there is a shift in the centre frequency of these high Q resonances when the pulse time is varied. The measured lifetime of these resonances is high enough to be useful for non-classical information processing.

Large area, facile oxide nanofabrication via step-and-flash imprint lithography of metal-organic hybrid resins.

Step-and-flash imprint lithography (S-FIL) is a wafer-scale, high-resolution nanoimprint technique capable of expansion of nanoscale patterns via serial patterning of imprint fields. While S-FIL patterning of organic resins is well known, patterning of metal-organic resins followed by calcination to form structured oxide films remains relatively unexplored. However, with calcination shrinkage, there is tremendous potential utility in easing accessibility of arbitrary nanostructures at 20 nm resolution and below. However, barriers to commercial adoption exist due to difficulties in formulating polymerizable oxide precursors with good dispensability, long shelf life, and resistance to auto-homopolymerization. Here we propose a solution to these issues in the form of a versatile resin formulation scheme that is applicable to a host of functional oxides (Al2O3, HfO2, TiO2, ZrO2, Ta2O5, and Nb2O5). This scheme utilizes a reaction of metal alkoxides with 2-(methacryloyloxy)ethyl acetoacetate (MAEAA), a polymerizable chelating agent. Formation of these inorganic coordination complexes enables remarkable resistance to auto-homopolymerization, greatly improving dispensability and shelf life, thus enabling full scale-up of this facile nanofabrication approach. Results include successively imprinted fields consisting of 100 nm linewidth gratings. Isothermal calcination of these structures resulted in corresponding shrinkage of 75-80% without loss of mechanical integrity or aspect ratio, resulting in 20 nm linewidth oxide nanostructures.