Pooran C. Joshi

Low-Thermal-Budget Photonic Processing of Highly Conductive Cu Interconnects Based on CuO Nanoinks: Potential for Flexible Printed Electronics.

In the developing field of printed electronics, nanoparticle based inks such as CuO show great promise as a low-cost alternative to other metal-based counterparts (e.g., silver). In particular, CuO inks significantly eliminate the issue of particle oxidation before and during the sintering process that is prevalent in Cu-based formulations. We report here the scalable and low-thermal-budget photonic fabrication of Cu interconnects employing a roll-to-roll (R2R)-compatible pulse-thermal-processing (PTP) technique that enables phase reduction and subsequent sintering of ink-jet-printed CuO patterns onto flexible polymer templates. Detailed investigations of curing and sintering conditions were performed to understand the impact of PTP system conditions on the electrical performance of the Cu patterns. Specifically, the impact of energy and power of photonic pulses on print conductivity was systematically studied by varying the following key processing parameters: pulse intensity, duration, and sequence. Through optimization of such parameters, highly conductive prints were obtained in <1 s with resistivity values as low as 10 μΩ cm (corresponding to ∼17% of the International Annealed Copper Standard (IACS) conductivity) was achieved. It was also observed that the introduction of an initial ink-drying step in ambient atmosphere, after the printing and before sintering, leads to significant improvements in mechanical integrity and electrical performance of the printed Cu patterns. Moreover, the viability of CuO reactive inks, coupled with the PTP technology and pre-sintering ink-drying protocols, has also been demonstrated for the additive integration of a low-cost Cu temperature sensor onto a flexible polymer substrate.

Monolithic Graded-Refractive-Index Glass-based Antireflective Coatings: Broadband/Omnidirectional Light Harvesting and Self-Cleaning Characteristics

A revolutionary impact on the performance of many optical systems and components can come from the integrative design of multifunctional coatings. Such coatings should be mechanically robust, and combine user-defined optical and wetting functions with scalable fabrication formulations. By taking cues from the properties of some natural biological structures, we report here the formation of low-refractive index antireflective glass films that embody omni-directional optical properties over a wide range of wavelengths, while also possessing specific wetting capabilities. The coatings comprise an interconnected network of nanoscale pores surrounded by a nanostructured silica framework. These structures result from a novel fabrication method that utilizes metastable spinodal phase separation in glass-based materials. The approach not only enables design of surface microstructures with graded-index antireflection characteristics, where the surface reflection is suppressed through optical impedance matching between interfaces, but also facilitates self-cleaning ability through modification of the surface chemistry. Based on near complete elimination of Fresnel reflections (yielding >95% transmission through a single-side coated glass) and corresponding increase in broadband transmission, the fabricated nanostructured surfaces are found to promote a general and an invaluable ∼3–7% relative increase in current output of multiple direct/indirect bandgap photovoltaic cells. Moreover, these antireflective surfaces also demonstrate superior resistance against mechanical wear and abrasion. Unlike conventional counterparts, the present antireflective coatings are essentially monolithic, enabling simultaneous realization of graded index anti-reflectivity, self-cleaning capability, and mechanical stability within the same surface. The concept represents a fundamental basis for development of advanced coated optical quality products, especially where environmental exposure is required.

Low thermal budget, photonic-cured compact TiO2 layers for high-efficiency perovskite solar cells

Rapid advances in organometallic trihalide perovskite solar cells (PSCs) have positioned them to be one of the leading next generation photovoltaic technologies. However, most of the high-performance PSCs, particularly those using compact TiO2 as an electron transport layer, require a high-temperature sintering step, which is not compatible with flexible polymer-based substrates. Considering the materials of interest for PSCs and corresponding device configurations, it is technologically imperative to fabricate high-efficiency cells at low thermal budget so that they can be realized on low-temperature plastic substrates. We report on a new photonic curing technique that produces crystalline anatase-phase TiO2 films on indium tin oxide-coated glass and flexible polyethylene terephthalate (PET) substrates. The planar PSCs, using photonic-cured TiO2 films, exhibit PCEs as high as 15.0% and 11.2% on glass and flexible PET substrates, respectively, comparable to the device performance of PSCs incorporating furnace annealed TiO2 films.

Direct digital additive manufacturing technologies: Path towards hybrid integration

In the past decade, additive manufacturing and printed electronics technologies have expanded rapidly on a global scale. As the additive manufacturing techniques have become more capable and affordable, and able to work with a broader range of materials, the machines are increasingly being used to make advanced products at significantly lower costs and risks. The additive manufacturing industry is populated by a broad family of technologies, and the present paper provides an overview of key additive manufacturing technologies and their impact on materials processing, device applications, and future markets. Our R&D efforts on the development of core technologies for the realization of flexible electronics, and 3D microscale structures are also highlighted.

Scalable production of microbially mediated zinc sulfide nanoparticles and application to functional thin films

A series of semiconducting zinc sulfide (ZnS) nanoparticles were scalably, reproducibly, controllably and economically synthesized with anaerobic metal-reducing Thermoanaerobacter species. These bacteria reduced partially oxidized sulfur sources to sulfides that extracellularly and thermodynamically incorporated with zinc ions to produce sparingly soluble ZnS nanoparticles with ∼5nm crystallites at yields of ∼5gl(-1)month(-1). A predominant sphalerite formation was facilitated by rapid precipitation kinetics, a low cation/anion ratio and a higher zinc concentration compared to background to produce a naturally occurring hexagonal form at the low temperature, and/or water adsorption in aqueous conditions. The sphalerite ZnS nanoparticles exhibited narrow size distribution, high emission intensity and few native defects. Scale-up and emission tunability using copper doping were confirmed spectroscopically. Surface characterization was determined using Fourier transform infrared and X-ray photoelectron spectroscopies, which confirmed amino acid as proteins and bacterial fermentation end products not only maintaining a nano-dimensional average crystallite size, but also increasing aggregation. The application of ZnS nanoparticle ink to a functional thin film was successfully tested for potential future applications.

Peculiarity of two thermodynamically-stable morphologies and their impact on the efficiency of small molecule bulk heterojunction solar cells

Structural characteristics of the active layers in organic photovoltaic (OPV) devices play a critical role in charge generation, separation and transport. Here we report on morphology and structural control of p-DTS(FBTTh2)2:PC71BM films by means of thermal annealing and 1,8-diiodooctane (DIO) solvent additive processing, and correlate it to the device performance. By combining surface imaging with nanoscale depth-sensitive neutron reflectometry (NR) and X-ray diffraction, three-dimensional morphologies of the films are reconstituted with information extending length scales from nanometers to microns. DIO promotes the formation of a well-mixed donor-acceptor vertical phase morphology with a large population of small p-DTS(FBTTh2)2 nanocrystals arranged in an elongated domain network of the film, thereby enhancing the device performance. In contrast, films without DIO exhibit three-sublayer vertical phase morphology with phase separation in agglomerated domains. Our findings are supported by thermodynamic description based on the Flory-Huggins theory with quantitative evaluation of pairwise interaction parameters that explain the morphological changes resulting from thermal and solvent treatments. Our study reveals that vertical phase morphology of small-molecule based OPVs is significantly different from polymer-based systems. The significant enhancement of morphology and information obtained from theoretical modeling may aid in developing an optimized morphology to enhance device performance for OPVs.

Size tunable elemental copper nanoparticles: extracellular synthesis by thermoanaerobic bacteria and capping molecules

Bimodal sized elemental copper (Cu) nanoparticles (NPs) were synthesized from inexpensive oxidized copper salts by an extracellular metal-reduction process using anaerobic Thermoanaerobacter sp. X513 bacteria in aqueous solution. The bacteria nucleate NPs outside of the cell, and they control the Cu2+ reduction rate to form uniform crystallites with an average diameter of 1.75 ± 0.46 μm after 3 days incubation. To control the size and enhance the air stability of Cu NPs, the reaction mixtures were supplemented with nitrilotriacetic acid as a chelator, and the surfactant capping agents oleic acid, oleylamine, ascorbic acid, or L-cysteine. Time-dependent UV-visible absorption measurements and XPS studies indicated well-suspended, bimodal colloidal Cu NPs (70–150 and 5–10 nm) with extended air-stability up to 300 min and stable Cu NP film surfaces with 14% oxidation after 20 days. FTIR spectroscopy suggested that these capping agents were effectively adsorbed on the NP surface providing oxidation resistance under aqueous and dry conditions. Compared to previously reported Cu NP syntheses, this biological process substantially reduced the requirement for hazardous organic solvents and chemical reducing agents, while reducing the levels of Cu oxide impurities in the product. This process was highly reproducible and scalable from 0.01 to 1 L batches.

In situ capping for size control of monochalcogenide (ZnS, CdS and SnS) nanocrystals produced by anaerobic metal-reducing bacteria

Metal monochalcogenide quantum dot nanocrystals of ZnS, CdS and SnS were prepared by anaerobic, metal-reducing bacteria using in situ capping by oleic acid or oleylamine. The capping agent preferentially adsorbs on the surface of the nanocrystal, suppressing the growth process in the early stages, thus leading to production of nanocrystals with a diameter of less than 5 nm.

Vacuum-Assisted Low-Temperature Synthesis of Reduced Graphene Oxide Thin-Film Electrodes for High-Performance Transparent and Flexible All-Solid-State Supercapacitors

Simple and easily integrated design of flexible and transparent electrode materials affixed to polymer-based substrates hold great promise to have a revolutionary impact on the functionality and performance of energy storage devices for many future consumer electronics. Among these applications are touch sensors, roll-up displays, photovoltaic cells, health monitors, wireless sensors, and wearable communication devices. Here, we report an environmentally friendly, simple, and versatile approach to produce optically transparent and mechanically flexible all-solid-state supercapacitor devices. These supercapacitors were constructed on tin-doped indium oxide coated polyethylene terephthalate substrates by intercalation of a polymer-based gel electrolyte between two reduced graphene oxide (rGO) thin-film electrodes. The rGO electrodes were fabricated simply by drop-casting of graphene oxide (GO) films, followed by a novel low-temperature (≤250 °C) vacuum-assisted annealing approach for the in situ reduction of GO to rGO. A trade-off between the optical transparency and electrochemical performance is determined by the concentration of the GO in the initial dispersion, whereby the highest capacitance (∼650 μF cm-2) occurs at a relatively lower optical transmittance (24%). Notably, the all-solid-state supercapacitors demonstrated excellent mechanical flexibility with a capacity retention rate above 90% under various bending angles and cycles. These attributes underscore the potential of the present approach to provide a path toward the realization of thin-film-based supercapacitors as flexible and transparent energy storage devices for a variety of practical applications.

ZnO Doping and Defect Engineering—A Review

Demand for efficient solid-state lighting (SSL) devices has accelerated in recent years and will continue to grow in the foreseeable future. As a result, interest in developing advanced optoelectronic devices such as light-emitting diodes (LEDs), laser diodes, and photodetectors is increasing. These optoelectronic devices require the use of compound semiconductors with a direct bandgap. In the past, this role was mainly dominated by GaAs and InP compound semiconductors.