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At least 1,387 records · Page 77

Novel Electroforming-Free Nanoscaffold Memristor with Very High Uniformity, Tunability, and Density

Dynamical tuning of the concentration of defects in oxides provides a route to controlling new functionalities. [ 1 ] The chemical potential to capture the functionalities driven by mobile ions and defects can be one of the key control parameters (as well as electric field, magnetic field, and stress) for tuning the functionality of complex oxides. [ 1 ] Interesting signatures related to oxygen vacancies have been explicitly observed in widespread physical applications, including solid oxide fuel cells, [ 2 ] catalysts, [ 3 ] optoelectronics, [ 4 ] and electronics. [ 5–14 ]

36 MATERIALS SCIENCE↗

Transition-Metal Substitution Doping in Synthetic Atomically Thin Semiconductors

Semiconductor impurity doping has enabled an entire generation of technology. The emergence of alternative semiconductor material systems, such as transition metal dichalcogenides (TMDCs), requires the development of scalable doping strategies. We report an unprecedented one-pot synthesis for transition-metal substitution in large-area, synthetic monolayer TMDCs. Electron microscopy, optical and electronic transport characterization and ab initio calculations indicate that our doping strategy preserves the attractive qualities of TMDC monolayers, including semiconducting transport and strong direct-gap luminescence. These results are expected to encourage exploration of transition-metal substitution in two-dimensional systems, potentially enabling next-generation optoelectronic technology in the atomically-thin regime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Graphene‐Assisted Antioxidation of Tungsten Disulfide Monolayers: Substrate and Electric‐Field Effect

Transition metal dichalcogenides (TMDs) have emerged as promising materials to complement graphene for advanced optoelectronics. However, irreversible degradation of chemical vapor deposition‐grown monolayer TMDs via oxidation under ambient conditions limits applications of TMD‐based devices. Here, the growth of oxidation‐resistant tungsten disulfide (WS 2 ) monolayers on graphene is demonstrated, and the mechanism of oxidation of WS 2 on SiO 2 , graphene/SiO 2 , and on graphene suspended in air is elucidated. While WS 2 on a SiO 2 substrate begins oxidation within weeks, epitaxially grown WS 2 on suspended graphene does not show any sign of oxidation, attributed to the screening effect of surface electric field caused by the substrate. The control of a local oxidation of WS 2 on a SiO 2 substrate by a local electric field created using an atomic force microscope tip is also demonstrated.

Kang, Kyungnam↗

Nanocomposites from Solution-Synthesized PbTe-BiSbTe Nanoheterostructure with Unity Figure of Merit at Low-Medium Temperatures (500-600 K)

The large-scale implementation of thermoelectric devices is inhibited, in part, by the limited temperature range where each material can operate at its highest efficiency, as evaluated by the dimensionless figure of merit ( zT = S 2 σT/κ ). To date, Bi 2 Te 3 -based materials have been restricted to zT ≥ 1 between 300-500 K, before the onset of bipolar conduction reduces the zT significantly. Herein, we show that a scalable, low-temperature solution process method can be used to synthesize precursor material for Pb-doped Bi x Sb 2-x Te 3 bulk nanocomposites with a zT = 1 over the 500-600 K range, making this material suitable for low-grade waste heat recovery for the first time. Our success in increasing the efficiency of p-type Bi x Sb 2-x Te 3 at higher temperatures can be largely explained by the increase in the optical band gap, according to the Burstein-Moss shift, due to Pb doping, thus delaying the onset of bipolar conduction. Furthermore, the solution synthesis method enabled controlled nanostructuring of the bulk materials, which greatly reduced the thermal conductivity over the investigated temperature range. Lastly, our scalable synthesis processing method may be applicable to not only other thermoelectrics, but also in fields such as photocatalysis, electronics and optoelectronics.

36 MATERIALS SCIENCE↗

Enhanced Performance of a Self-Powered Organic/Inorganic Photodetector by Pyro-Phototronic and Piezo-Phototronic Effects

Self-powered photodetectors (PDs) have long been realized by utilizing photovoltaic effect and their performances can be effectively enhanced by introducing the piezo-phototronic effect. Recently, a novel pyro-phototronic effect is invented as an alternative approach for performance enhancement of self-powered PDs. Here, a self-powered organic/inorganic PD is demonstrated and the influences of externally applied strain on the pyro-phototronic and the photovoltaic effects are thoroughly investigated. Under 325 nm 2.30 mW cm -2 UV illumination and at a -0.45% compressive strain, the PD's photocurrent is dramatically enhanced from ≈14.5 to ≈103 nA by combining the pyro-phototronic and piezo-phototronic effects together, showing a significant improvement of over 600%. Theoretical simulations have been carried out via the finite element method to propose the underlying working mechanism. Moreover, the pyro-phototronic effect can be introduced by applying a -0.45% compressive strain to greatly enhance the PD's response to 442 nm illumination, including photocurrent, rise time, and fall time. This work provides in-depth understandings about the pyro-phototronic and the piezo-phototronic effects on the performances of self-powered PD to light sources with different wavelengths and indicates huge potential of these two effects in optoelectronic devices.

36 MATERIALS SCIENCE↗

300% Enhancement of Carrier Mobility in Uniaxial-Oriented Perovskite Films Formed by Topotactic-Oriented Attachment

Organic-inorganic perovskites with intriguing optical and electrical properties have attracted significant research interests due to their excellent performance in optoelectronic devices. Recent efforts on preparing uniform and large-grain polycrystalline perovskite films have led to enhanced carrier lifetime up to several microseconds. However, the mobility and trap densities of polycrystalline perovskite films are still significantly behind their single-crystal counterparts. Here, a facile topotactic-oriented attachment (TOA) process to grow highly oriented perovskite films, featuring strong uniaxial-crystallographic texture, micrometer-grain morphology, high crystallinity, low trap density (≈4 x 10 14 cm -3 ), and unprecedented 9 GHz charge-carrier mobility (71 cm 2 V -1 s -1 ), is demonstrated. TOA-perovskite-based n-i-p planar solar cells show minimal discrepancies between stabilized efficiency (19.0%) and reverse-scan efficiency (19.7%). In conclusion, the TOA process is also applicable for growing other state-of-the-art perovskite alloys, including triple-cation and mixed-halide perovskites.

14 SOLAR ENERGY↗

Unraveling the Solution‐State Supramolecular Structures of Donor–Acceptor Polymers and their Influence on Solid‐State Morphology and Charge‐Transport Properties

Abstract Polymer self‐assembly in solution prior to film fabrication makes solution‐state structures critical for their solid‐state packing and optoelectronic properties. However, unraveling the solution‐state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution‐state structure and the charge‐transport properties in field‐effect transistors. Here, for the first time, it is revealed that the thin‐film morphology of a conjugated polymer inherits the features of its solution‐state supramolecular structures. A “solution‐state supramolecular structure control” strategy is proposed to increase the electron mobility of a benzodifurandione‐based oligo( p‐ phenylene vinylene) (BDOPV)‐based polymer. It is shown that the solution‐state structures of the BDOPV‐based conjugated polymer can be tuned such that it forms a 1D rod‐like structure in good solvent and a 2D lamellar structure in poor solvent. By tuning the solution‐state structure, films with high crystallinity and good interdomain connectivity are obtained. The electron mobility significantly increases from the original value of 1.8 to 3.2 cm 2 V −1 s −1 . This work demonstrates that “solution‐state supramolecular structure” control is critical for understanding and optimization of the thin‐film morphology and charge‐transport properties of conjugated polymers.

Zheng, Yu‐Qing↗

Piezo-Phototronic Effect on Selective Electron or Hole Transport through Depletion Region of Vis-NIR Broadband Photodiode

Silicon underpins nearly all microelectronics today and will continue to do so for some decades to come. However, for silicon photonics, the indirect band gap of silicon and lack of adjustability severely limit its use in applications such as broadband photodiodes. Here, a high-performance p-Si/n-ZnO broadband photodiode working in a wide wavelength range from visible to near-infrared light with high sensitivity, fast response, and good stability is reported. The absorption of near-infrared wavelength light is significantly enhanced due to the nanostructured/textured top surface. The general performance of the broadband photodiodes can be further improved by the piezo-phototronic effect. The enhancement of responsivity can reach a maximum of 78% to 442 nm illumination, the linearity and saturation limit to 1060 nm light are also significantly increased by applying external strains. The photodiode is illuminated with different wavelength lights to selectively choose the photogenerated charge carriers (either electrons or holes) passing through the depletion region, to investigate the piezo-phototronic effect on electron or hole transport separately for the first time. This is essential for studying the basic principles in order to develop a full understanding about piezotronics and it also enables the development of the better performance of optoelectronics.

36 MATERIALS SCIENCE↗

Triplet Harvesting from Intramolecular Singlet Fission in Polytetracene

Abstract Singlet fission (SF), a promising mechanism of multiple exciton generation, has only recently been engineered as a fast, efficient, intramolecular process (iSF). The challenge now lies in designing and optimizing iSF materials that can be practically applied in high‐performance optoelectronic devices. However, most of the reported iSF systems, such as those based on donor–acceptor polymers or pentacene, have low triplet energies, which limits their applications. Tetracene‐based materials can overcome significant challenges, as the tetracene triplet state is practically useful, ≈1.2 eV. Here, the synthesis and excited state dynamics of a conjugated tetracene homopolymer are studied. This polymer undergoes ultrafast iSF in solution, generating high‐energy triplets on a sub‐picosecond time scale. Magnetic‐field‐dependent photocurrent measurements of polytetracene‐based devices demonstrate the first example of iSF‐generated triplet extraction in devices, exhibiting the potential of iSF materials for use in next‐generation devices.

Pun, Andrew B.↗

Controlling Molecular Doping in Organic Semiconductors

The field of organic electronics thrives on the hope of enabling low-cost, solution-processed electronic devices with mechanical, optoelectronic, and chemical properties not available from inorganic semiconductors. A key to the success of these aspirations is the ability to controllably dope organic semiconductors with high spatial resolution. In this work, recent progress in molecular doping of organic semiconductors is summarized, with an emphasis on solution-processed p-type doped polymeric semiconductors. Highlighted topics include how solution-processing techniques can control the distribution, diffusion, and density of dopants within the organic semiconductor, and, in turn, affect the electronic properties of the material. Research in these areas has recently intensified, thanks to advances in chemical synthesis, improved understanding of charged states in organic materials, and a focus on relating fabrication techniques to morphology. Significant disorder in these systems, along with complex interactions between doping and film morphology, is often responsible for charge trapping and low doping efficiency. However, the strong coupling between doping, solubility, and morphology can be harnessed to control crystallinity, create doping gradients, and pattern polymers. These breakthroughs suggest a role for molecular doping not only in device function but also in fabrication—applications beyond those directly analogous to inorganic doping.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron-Phonon Coupling

Unusual photophysical properties of organic–inorganic hybrid perovskites have not only enabled exceptional performance in optoelectronic devices, but also led to debates on the nature of charge carriers in these materials. This study makes the first observation of intense terahertz (THz) emission from the hybrid perovskite methylammonium lead iodide (CH 3 NH 3 PbI 3 ) following photoexcitation, enabling an ultrafast probe of charge separation, hot–carrier transport, and carrier–lattice coupling under 1–sun–equivalent illumination conditions. Using this approach, the initial charge separation/transport in the hybrid perovskites is shown to be driven by diffusion and not by surface fields or intrinsic ferroelectricity. Diffusivities of the hot and band–edge carriers along the surface normal direction are calculated by analyzing the emitted THz transients, with direct implications for hot–carrier device applications. Furthermore, photogenerated carriers are found to drive coherent terahertz–frequency lattice distortions, associated with reorganizations of the lead–iodide octahedra as well as coupled vibrations of the organic and inorganic sublattices. This strong and coherent carrier–lattice coupling is resolved on femtosecond timescales and found to be important both for resonant and far–above–gap photoexcitation. As a result, this study indicates that ultrafast lattice distortions play a key role in the initial processes associated with charge transport.

36 MATERIALS SCIENCE↗

Exploring Anomalous Polarization Dynamics in Organometallic Halide Perovskites

Organometallic halide perovskites (OMHPs) have attracted broad attention as prospective materials for optoelectronic applications. Among the many anomalous properties of these materials, of special interest are the ferroelectric properties including both classical and relaxor-like components, as a potential origin of slow dynamics, field enhancement, and anomalous mobilities. Here, ferroelectric properties of the three representative OMHPs are explored, including FAPb x Sn 1–x I 3 (x = 0, x = 0.85) and FA 0.85 MA 0.15 PbI 3 using band excitation piezoresponse force microscopy and contact mode Kelvin probe force microscopy, providing insight into long- and short-range dipole and charge dynamics in these materials and probing ferroelectric density of states. Furthermore, second-harmonic generation in thin films of OMHPs is observed, providing a direct information on the noncentrosymmetric polarization in such materials. Overall, the data provide strong evidence for the presence of ferroelectric domains in these systems; however, the domain dynamics is suppressed by fast ion dynamics. These materials hence present the limit of ferroelectric materials with spontaneous polarization dynamically screened by ionic and electronic carriers.

36 MATERIALS SCIENCE↗

High-Z Sensitized Plastic Scintillators: A Review

The need for affordable and reliable radiation detectors has prompted significant investment in new radiation detector materials, due to concerns about national security and nuclear nonproliferation. Plastic scintillators provide an affordable approach to large volume detectors, yet their performance for high-energy gamma radiation is severely limited by the small radiation stopping power inherent to their low atomic number. Although some sensitization attempts with organometallics were made in the 1950s to 1960s, the concomitant decrease in light yield has limited the usefulness of these sensitized detectors. Recently, with new knowledge gained during the rapid development of organic optoelectronics and nanotechnology, there has been a revived interest in the field of heavy element sensitized plastic scintillators. In this paper, the recent efforts on sensitized plastic scintillators are summarized. Basic scintillator physics is first reviewed. The discussion then focuses on two major thrusts in the field: sensitization with: (1) organometallics and (2) oxide and fluoride nanoparticles. The design rationales and major results are examined in detail, with existing limitations and possible future pathways discussed. Lastly, special attention is paid to the underlying energy deposition and transfer processes, as these determine the key performance metrics such as light yield and radioluminescence decay lifetime.

36 MATERIALS SCIENCE↗

Resonance-Enhanced Absorption in Hollow Nanoshell Spheres with Omnidirectional Detection and High Responsivity and Speed

Optical resonance formed inside a nanocavity resonator can trap light within the active region and hence enhance light absorption, effectively boosting device or material performance in applications of solar cells, photodetectors (PDs), and photocatalysts. Complementing conventional circular and spherical structures, a new type of multishelled spherical resonant strategy is presented. Due to the resonance–enhanced absorption by multiple convex shells, ZnO nanoshell PDs show improved optoelectronic performance and omnidirectional detection of light at different incidence angles and polarization. In addition, the response and recovery speeds of these devices are improved (0.8 and 0.7 ms, respectively) up to three orders of magnitude faster than in previous reports because of the existence of junction barriers between the nanoshells. As a result, the general design principles behind these hollow ZnO nanoshells pave a new way to improve the performance of sophisticated nanophotonic devices.

36 MATERIALS SCIENCE↗