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Abstract Conjugated polymers (CPs) play a central role in electronic applications due to their easily tuned electronic and ionic conductivities via chemical or electrochemical doping. Although doping improves charge conduction by introducing high densities of carriers into the CP, the accompanying structural changes and their impact on carrier mobility remain elusive. Methods capable of probing carrier distributions and their dependence on polymer morphology are needed to better understand how to improve conductivity. Here, a transient absorption (TA) spectroscopy approach is demonstrated, capable of directly probing mobile and trapped carriers in doped CPs and that is also sensitive to polymer nanostructure by using a model polythiophene system with tuned crystallinity. Exciting polarons in the polymer films produces distinct photoinduced absorption signals in the near‐infrared spectrum that decay during the picosecond timescale in the form of biphasic, stretched exponential kinetics, which reflect a distribution of mobile (free) and trapped polarons. The kinetic analysis provides evidence for mobile polarons irrespective of polymer film crystallinity, whereas polarons located in impure amorphous phases with reduced chain ordering exist within a deeper distribution of trap states. Altogether, these observations suggest a stronger correlation of carrier trapping with local chain ordering (planarity or aggregation) rather than polymer crystallinity. 

Perovskite oxide heterostructures host a large number of interesting phenomena such as ferroelectricity, which are often driven by octahedral distortions in the crystal that may induce polarization. SrHfO3 (SHO) is a perovskite oxide with a pseudocubic lattice parameter of 4.08 Å that previous density functional theory (DFT) calculations suggest can be stabilized in a ferroelectric P4mm phase when stabilized with sufficient compressive strain. Additionally, it is insulating and possesses a large band gap and a high dielectric constant, making it an ideal candidate for oxide electronic devices. To test the viability of epitaxial strain as a driver of ferroic phase transitions, SHO films were grown by hybrid molecular beam epitaxy (hMBE) with a tetrakis(ethylmethylamino)hafnium(IV) source on GdScO3 and TbScO3 substrates. Strained SHO phases were characterized using X-ray diffraction, X-ray absorption spectroscopy, and scanning transmission electron microscopy to determine the space group of the strained films, with the results compared to those of DFT-optimized models of phase stability versus strain. Contrary to past reports, we find that compressively strained SrHfO3 undergoes octahedral tilt distortions without associated ferroelectric polarization and most likely takes on the I4/mcm phase with the a0a0c– tilt pattern. 

Printed electronics are gaining significant interest due to their design flexibility, low fabrication cost, and rapid design-to-manufacturing turnaround. Conventional substrates for printed electronics are often based on nonbiodegradable polymers such as polyimide that pose high environmental challenges by creating massive e-waste and pollution. As the demand for printed electronics and sensors increases, the ability to print such devices on biodegradable substrates can provide a solution to such environmental problems. However, current printing technologies are based on liquids and inks that are incompatible with biodegradable substrates, such as paper. Here, we present a dry-printing process, namely, a dry additive nanomanufacturing (Dry-ANM) technique, for printing conductive silver lines and patterns on biodegradable papers for flexible hybrid papertronics. Pure and dry nanoparticles are generated by pulsed laser ablation of a silver target that is then transported through a nozzle and directed onto paper substrates, where they are deposited and laser-sintered in real time to form the desired pattern without damaging the paper. The effects of different printing parameters on the paper-burning threshold are investigated, and the electrical properties of the lines are characterized by using different line thicknesses and sintering laser power densities. In addition, the mechanical and electrical properties of the printed lines and patterns are evaluated by bending and twisting tests. Furthermore, the feasibility of printing silver on different paper types is demonstrated. This research can potentially lead to biodegradable and environmentally friendly printed electronics and sensors. 

Transition metal spinel oxides comprised of earth-abundant Mn and Co have long been explored for their use in catalytic reactions and energy storage. However, understanding functional properties can be challenging due to differences in sample preparation and the ultimate structural properties of the materials. Epitaxial thin film synthesis provides a novel means of producing precisely controlled materials to explore the variations reported in the literature. In this work, MnxCo3−xO4 samples from x = 0 to x = 1.28 were synthesized through molecular beam epitaxy and characterized to develop a material properties map as a function of stoichiometry. Films were characterized via in situ x-ray photoelectron spectroscopy, x-ray diffraction, scanning transmission electron microscopy, and polarized K-edge x-ray absorption spectroscopy. Mn cations within this range were found to be octahedrally coordinated, in line with an inverse spinel structure. Samples largely show mixed Mn3+ and Mn4+ character with evidence of phase segregation tendencies with the increasing Mn content and increasing Mn3+ formal charge. Phase segregation may occur due to structural incompatibility between cubic and tetragonal crystal structures associated with Mn4+ and Jahn–Teller active Mn3+ octahedra, respectively. Our results help in explaining the reported differences across samples in these promising materials for renewable energy technologies. 

Additively manufactured electronics (AMEs), also known as printed electronics, are becoming increasingly important for the anticipated Internet of Things (IoT). This requires manufacturing technologies that allow the integration of various pure functional materials and devices onto different flexible and rigid surfaces. However, the current ink-based technologies suffer from complex and expensive ink formulation, ink-associated contaminations (additives/solvents), and limited sources of printing materials. Thus, printing contamination-free and multimaterial structures and devices is challenging. Here, a multimaterial additive nanomanufacturing (M-ANM) technique utilizing directed laser deposition at the nano and microscale is demonstrated, allowing the printing of lateral and vertical hybrid structures and devices. This M-ANM technique involves pulsed laser ablation of solid targets placed on a target carousel inside the printer head for in-situ generation of contamination-free nanoparticles, which are then guided via a carrier gas toward the nozzle and onto the surface of the substrate, where they are sintered and printed in real-time by a second laser. The target carousel brings a particular target in engagement with the ablation laser beam in predetermined sequences to print multiple materials, including metals, semiconductors, and insulators, in a single process. Using this M-ANM technique, various multimaterial devices such as silver/zinc oxide (Ag/ZnO) photodetector and hybrid silver/aluminum oxide (Ag/Al2O3) circuits are printed and characterized. The quality and versatility of our M-ANM technique offer a potential manufacturing option for emerging IoT. 

This work demonstrates the advantage of carrying out silicon ion (Si+) implantation at high temperatures for forming controlled heavily doped regions in gallium oxide. Room temperature (RT, 25 °C) and high temperature (HT, 600 °C) Si implants were carried out into MBE grown (010) β-Ga2O3 films to form ∼350 nm deep Si-doped layers with average concentrations up to ∼1.2 × 1020 cm−3. For such high concentrations, the RT sample was too resistive for measurement, but the HT samples had 82.1% Si dopant activation efficiency with a high sheet electron concentration of 3.3 × 1015 cm−2 and an excellent mobility of 92.8 cm2/V·s at room temperature. X-ray diffraction measurements indicate that HT implantation prevents the formation of other Ga2O3 phases and results in reduced structural defects and lattice damage. These results are highly encouraging for achieving ultra-low resistance heavily doped Ga2O3 layers using ion implantation. 

4d transition metal oxides have emerged as promising materials for numerous applications including high mobility electronics. SrNbO3 is one such candidate material, serving as a good donor material in interfacial oxide systems and exhibiting high electron mobility in ultrathin films. However, its synthesis is challenging due to the metastable nature of the d1 Nb4+ cation and the limitations in the delivery of refractory Nb. To date, films have been grown primarily by pulsed laser deposition (PLD), but development of a means to grow and stabilize the material via molecular beam epitaxy (MBE) would enable studies of interfacial phenomena and multilayer structures that may be challenging by PLD. To that end, SrNbO3 thin films were grown using hybrid MBE for the first time using a tris(diethylamido)(tert-butylimido) niobium precursor for Nb and an elemental Sr source on GdScO3 substrates. Varying thicknesses of insulating SrHfO3 capping layers were deposited using a hafnium tert-butoxide precursor for Hf on top of SrNbO3 films to preserve the metastable surface. Grown films were transferred in vacuo for x-ray photoelectron spectroscopy to quantify elemental composition, density of states at the Fermi energy, and Nb oxidation state. Ex situ studies by x-ray absorption near edge spectroscopy and scanning transmission electron microscopy illustrate that the SrHfO3 capping plays an important role in preserving the crystalline quality of the material and the Nb 4d1 metastable charge state under atmospheric conditions.