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At least 271 records · Page 15

Enhancing mobility and interface state engineering via UV-ozone treatment in BEOL-compatible ultrathin TiO 2 transistors

It has emerged as a potential candidate to improve the performance of monolithic-three-dimensional (M3D) integration of fused logic and memories through low-temperature in situ synthesis of high-performance metal–oxide–semiconductor (MOS) transistors. Here, we report the demonstration of the BEOL-compatible low thermal budget (350 °C) fabrication process of ultrathin-TiO2 transistors by the combination of RTA and UV-ozone treatment (RTA-UVOz). UV–ozone (UVOz) treatment of TiO2 anatase films significantly enhances stability, boosting ION current and field effect mobility (μ FE ) by two times of magnitude in TiO2 TFTs. UV ozone treatment helps to eliminate pre-existing oxygen vacancies and carbon contamination on TiO2 channels even at low temperature (100 °C), resulting in high-quality channel/dielectric interfaces with low interface states (D it ). During UVOz treatment, oxygen species (O x ) passivate the oxygen vacancies ($V$$^{2+}_{o}$), and hence low concentration of $V$$^{2+}_{o}$ would be left for ionization/de-ionization under PBS/NBS, leading to improved bias stress stability. Furthermore, the TiO 2 TFTs with thin ZrO 2 gate dielectric exhibited excellent performance including a lower subthreshold swing (SS) of 98 mV/dec with high drive I ON current ∼ 4.5 μA/μm, a high I ON /I OFF > 10 9 , and mobility μFE of 7 cm 2 /V-s under a battery powered voltage of 1 V. UV–ozone treatment enables high-performance, CMOS-compatible TiO 2 transistors with a low thermal budget, ideal for next-generation flexible, energy-efficient electronics.

BEOL↗

Multifunctional textured graphene-based coatings on elastomeric gloves for chemical protection

Nanotechnology offers a variety of new tools for the design of next-generation personal protective equipment (PPE). One example is the use of two-dimensional materials as coatings that enhance the performance and ergonomics of elastomeric gloves designed to protect users from hazardous chemicals. Desirable features in such coatings may include molecular barrier function, liquid droplet repellency, stretchability for compatibility with the elastomer, breathability, and an ultrathin profile that preserves the user's manual dexterity and tactile sensation. The present work explores the potential of engineered graphene-based films with out-of-plane texturing as a novel platform to meet these multifold requirements. Graphene-based films in different formulations were fabricated from water-borne inks by vacuum filtration and solution casting methods on glove-derived nitrile rubber substrates. The various coatings were then subjected to tests of molecular permeation by model volatile organic compounds, droplet contact angle, breathability, and mechanical stability during stretching and solvent immersion. The films dramatically improve the barrier properties of glove-derived nitrile. The out-of-plane graphene texturing imparts stretchability through microscale folding/unfolding, while also enhancing droplet repellency in some cases through a lotus-like roughening effect. The combined results suggest that engineered textured graphene-based films are a promising platform for creating multifunctional coatings for a next generation of chemically protective gloves and other elastomer-based PPE.

36 MATERIALS SCIENCE↗

Stabilized hole-selective layer for high-performance inverted p-i-n perovskite solar cells

P-i-n geometry perovskite solar cells (PSCs) offer simplified fabrication, greater amenability to charge extraction layers, and low-temperature processing over n-i-p counterparts. Self-assembled monolayers (SAMs) can enhance the performance of p-i-n PSCs but ultrathin SAMs can be thermally unstable. Here we report a thermally robust hole-selective layer comprised of nickel oxide (NiO x ) nanoparticle film with a surface-anchored (4-(3,11-dimethoxy-7H-dibenzo[c,g]carbazol-7-yl)butyl)phosphonic acid (MeO-4PADBC) SAM that can improve and stabilize the NiO x /perovskite interface. The energetic alignment and favorable contact and binding between NiO x /MeO-4PADBC and perovskite reduced the voltage deficit of PSCs with various perovskite compositions and led to strong interface toughening effects under thermal stress. The resulting 1.53–electron-volt devices achieved 25.6% certified power conversion efficiency and maintained >90% of their initial efficiency after continuously operating at 65 degrees Celsius for 1200 hours under 1-sun illumination.

14 SOLAR ENERGY↗

Controlling antiferromagnetic domains in patterned La0.7Sr0.3FeO3 thin films

Transition metal oxide thin films and heterostructures are promising platforms to achieve full control of the antiferromagnetic (AFM) domain structure in patterned features as needed for AFM spintronic devices. In this work, soft x-ray photoemission electron microscopy was utilized to image AFM domains in micromagnets patterned into La0.7Sr0.3FeO3 (LSFO) thin films and La0.7Sr0.3MnO3 (LSMO)/LSFO superlattices. A delicate balance exists between magnetocrystalline anisotropy, shape anisotropy, and exchange interactions such that the AFM domain structure can be controlled using parameters such as LSFO and LSMO layer thickness, micromagnet shape, and temperature. In LSFO thin films, shape anisotropy gains importance only in micromagnets where at least one extended edge is aligned parallel to an AFM easy axis. In contrast, in the limit of ultrathin LSFO layers in the LSMO/LSFO superlattice, shape anisotropy effects dominate such that the AFM spin axes at micromagnet edges can be aligned along any in-plane crystallographic direction.

Lee, Michael S. (ORCID:0000000177852189)↗

Electronic Structure and Stacking Arrangement of Tungsten Disulfide at the Gold Contact

There is an intensive effort to control the nature of attractive interactions between ultrathin semiconductors and metals and to understand its impact on the electronic properties at the junction. In this work, we present a photoelectron spectroscopy study on the interface between WS 2 films and gold, with a focus on the occupied electronic states near the Brillouin zone center (i.e., the Γ point). To delineate the spectra of WS 2 supported on crystalline Au from the suspended WS 2 , we employ a microscopy approach and a tailored sample structure, in which the WS 2 /Au junction forms a semi-epitaxial relationship and is adjacent to suspended WS 2 regions. The photoelectron spectra, as a function of WS 2 thickness, display the expected splitting of the highest occupied states at the Γ point. In multilayer WS 2 , we discovered variations in the electronic states that spatially align with the crystalline grains of underlying Au. Corroborated by density functional theory calculations, we attribute the electronic structure variations to stacking variations within the WS 2 films. We propose that strong interactions exerted by Au grains cause slippage of the interfacing WS 2 layer with respect to the rest of the WS 2 film. Our findings illustrate that the electronic properties of transition metal dichalcogenides, and more generally 2D layered materials, are physically altered by the interactions with the interfacing materials, in addition to the electron screening and defects that have been widely considered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Epitaxy, exfoliation, and strain-induced magnetism in rippled Heusler membranes

Single-crystalline membranes of functional materials enable the tuning of properties via extreme strain states; however, conventional routes for producing membranes require the use of sacrificial layers and chemical etchants, which can both damage the membrane and limit the ability to make them ultrathin. Here we demonstrate the epitaxial growth of the cubic Heusler compound GdPtSb on graphene-terminated Al 2 O 3 substrates. Despite the presence of the graphene interlayer, the Heusler films have epitaxial registry to the underlying sapphire, as revealed by x-ray diffraction, reflection high energy electron diffraction, and transmission electron microscopy. The weak Van der Waals interactions of graphene enable mechanical exfoliation to yield free-standing GdPtSb membranes, which form ripples when transferred to a flexible polymer handle. Whereas unstrained GdPtSb is antiferromagnetic, measurements on rippled membranes show a spontaneous magnetic moment at room temperature, with a saturation magnetization of 5.2 bohr magneton per Gd. First-principles calculations show that the coupling to homogeneous strain is too small to induce ferromagnetism, suggesting a dominant role for strain gradients. Our membranes provide a novel platform for tuning the magnetic properties of intermetallic compounds via strain (piezomagnetism and magnetostriction) and strain gradients (flexomagnetism).

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Electronically Coupled 2D Polymer/MoS 2 Heterostructures

Emergent quantum phenomena in electronically coupled two-dimensional heterostructures are central to next-generation optical, electronic, and quantum information applications. Tailoring electronic band gaps in coupled heterostructures would permit control of such phenomena and is the subject of significant research interest. Two-dimensional polymers (2DPs) offer a compelling route to tailored band structures through the selection of molecular constituents. However, despite the promise of synthetic flexibility and electronic design, fabrication of 2DPs that form electronically coupled 2D heterostructures remains an outstanding challenge. Here, we report the rational design and optimized synthesis of electronically coupled semiconducting 2DP/2D transition metal dichalcogenide van der Waals heterostructures, demonstrate direct exfoliation of the highly crystalline and oriented 2DP films down to a few nanometers, and present the first thickness-dependent study of 2DP/MoS 2 heterostructures. In this work, control over the 2DP layers reveals enhancement of the 2DP photoluminescence by two orders of magnitude in ultrathin sheets and an unexpected thickness-dependent modulation of the ultrafast excited state dynamics in the 2DP/MoS 2 heterostructure. These results provide fundamental insight into the electronic structure of 2DPs and present a route to tune emergent quantum phenomena in 2DP hybrid van der Waals heterostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of thickness and surface composition on the stability of polarization in ferroelectric Hf x Zr 1 - x O 2 thin films

Using density functional theory, we find that tailoring the surface composition provides a route to stabilize the polar phases of the promising ferroelectric material, Hf x Zr 1-x O 2 . First, we show that for pure Hf O 2 , controlling the positively polarized surface to be relatively oxygen rich adequately screens the ferroelectric surface charges and stabilizes the polar orthorhombic phase. We then demonstrate that the ferroelectric polarization, as measured by the structural polar displacements, increases with decreasing thickness, leading to the emergence of a polar rhombohedral-like phase at the ultrathin limit (1.5 unit cells). Our findings extend to the cases of Hf 0.5 Zr 0.5 O 2 and Zr O 2 , both of which have surface energy landscapes similar to that of Hf O 2 . In conclusion, these findings are consistent with and offer insights into the observed absence of a ferroelectric thickness limit in Hf x Zr 1-x O 2 -based thin films.

36 MATERIALS SCIENCE↗

Field-free spin-orbit torque switching assisted by in-plane unconventional spin torque in ultrathin [Pt/Co] N

Electrical manipulation of magnetization without an external magnetic field is critical for the development of advanced non-volatile magnetic-memory technology that can achieve high memory density and low energy consumption. Several recent studies have revealed efficient out-of-plane spin-orbit torques (SOTs) in a variety of materials for field-free type-z SOT switching. Here, we report on the corresponding type-x configuration, showing significant in-plane unconventional spin polarizations from sputtered ultrathin [Pt/Co] N , which are either highly textured on single crystalline MgO substrates or randomly textured on SiO 2 coated Si substrates. The unconventional spin currents generated in the low-dimensional Co films result from the strong orbital magnetic moment, which has been observed by X-ray magnetic circular dichroism (XMCD) measurement. The x-polarized spin torque efficiency reaches up to −0.083 and favors complete field-free switching of CoFeB magnetized along the in-plane charge current direction. Micromagnetic simulations additionally demonstrate its lower switching current than type-y switching, especially in narrow current pulses. Our work provides additional pathways for electrical manipulation of spintronic devices in the pursuit of high-speed, high-density, and low-energy non-volatile memory.

42 ENGINEERING↗

All‐Printed Ultrahigh‐Responsivity MoS 2 Nanosheet Photodetectors Enabled by Megasonic Exfoliation

Abstract Printed 2D materials, derived from solution‐processed inks, offer scalable and cost‐effective routes to mechanically flexible optoelectronics. With micrometer‐scale control and broad processing latitude, aerosol‐jet printing (AJP) is of particular interest for all‐printed circuits and systems. Here, AJP is utilized to achieve ultrahigh‐responsivity photodetectors consisting of well‐aligned, percolating networks of semiconducting MoS 2 nanosheets and graphene electrodes on flexible polyimide substrates. Ultrathin (≈1.2 nm thick) and high‐aspect‐ratio (≈1 μm lateral size) MoS 2 nanosheets are obtained by electrochemical intercalation followed by megasonic atomization during AJP, which not only aerosolizes the inks but also further exfoliates the nanosheets. The incorporation of the high‐boiling‐point solvent terpineol into the MoS 2 ink is critical for achieving a highly aligned and flat thin‐film morphology following AJP as confirmed by grazing‐incidence wide‐angle X‐ray scattering and atomic force microscopy. Following AJP, curing is achieved with photonic annealing, which yields quasi‐ohmic contacts and photoactive channels with responsivities exceeding 10 3 A W −1 that outperform previously reported all‐printed visible‐light photodetectors by over three orders of magnitude. Megasonic exfoliation coupled with properly designed AJP ink formulations enables the superlative optoelectronic properties of ultrathin MoS 2 nanosheets to be preserved and exploited for the scalable additive manufacturing of mechanically flexible optoelectronics.

2D materials↗

Nucleation and Growth of PbBrF Crystals at the Liquid Mercury–Electrolyte Interface Studied by Operando X-ray Scattering

In this work, detailed in operando studies of electrochemically induced PbBrF deposition at the liquid mercury/liquid electrolyte interface are presented. The nucleation and growth were monitored using time-resolved X-ray diffraction and reflectivity combined with electrochemical measurements, revealing a complex potential-dependent behavior. PbBrF deposition commences at potentials above –0.7 V with the rapid formation of an ultrathin adlayer of one unit cell thickness, on top of which (001)-oriented three-dimensional crystallites are formed. Two potential regimes are identified. At low overpotentials, slow growth of a low surface density film of large crystals is observed. At high overpotentials, crossover to a potential-independent morphology occurs, consisting of a compact PbBrF deposit with a saturation thickness of 25 nm, which forms within a few minutes. This potential behavior can be rationalized by the increasing supersaturation near the interface, caused by the potential-dependent Pb2+ deamalgamation, which changes from a slow reaction-controlled process to a fast transport-controlled process in this range of overpotentials. In addition, growth on the liquid substrate is found to involve complex micromechanical effects, such as crystal reorientation and film breakup during dissolution.

36 MATERIALS SCIENCE↗

Ultrathin Magnesium-Based Coating as an Efficient Oxygen Barrier for Superconducting Circuit Materials

Scaling up superconducting quantum circuits based on transmon qubits necessitates substantial enhancements in qubit coherence time. Over recent years, tantalum (Ta) has emerged as a promising candidate for transmon qubits, surpassing conventional counterparts in terms of coherence time. However, amorphous surface Ta oxide layer may introduce dielectric loss, ultimately placing a limit on the coherence time. In this study, a novel approach for suppressing the formation of tantalum oxide using an ultrathin magnesium (Mg) capping layer is presented. Synchrotron-based X-ray photoelectron spectroscopy studies demonstrate that oxide is confined to an extremely thin region directly beneath the Mg/Ta interface. Additionally, it is demonstrated that the superconducting properties of thin Ta films are improved following the Mg capping, exhibiting sharper and higher-temperature transitions to superconductive and magnetically ordered states. Moreover, an atomic-scale mechanistic understanding of the role of the capping layer in protecting Ta from oxidation is established based on computational modeling. Further, this work provides valuable insights into the formation mechanism and functionality of surface tantalum oxide, as well as a new materials design principle with the potential to reduce dielectric loss in superconducting quantum materials. Ultimately, the findings pave the way for the realization of large-scale, high-performance quantum computing systems.

36 MATERIALS SCIENCE↗

Synthesis and Observation of Emergent Phenomena in Epitaxial Heusler Compound Heterostructures

The proposal was on the synthesis and observation of emergent phenomena in epitaxial Heusler compound heterostructures. The large range of properties and number of Heusler compounds opens up a wide number of potential compounds that will exhibit emergent phenomena. The similarity, large range of relatively inexpensive, large area, high crystal quality, III-V bulk substrates, lattice parameters and the ability to tune the lattice parameters through ternary or quaternary III-V compound semiconductor epitaxial growth, makes III-V semiconductors an ideal choice for substrates for epitaxial growth of Heusler compounds. A number of half Heusler compounds have been predicted to exhibit band inversion, making them topological and are therefore expected to exhibit spin-momentum locked topological surface states with linear dispersion. Others are predicted to be semimetals with Weyl points and others semiconducting and magnetic. During the course of this grant, emphasis has been on investigating Heusler compounds with emergent phenomena and demonstrating the ability to tune their properties through alloying and strain. We have grown toplogical semimetal (PtLuSb, PtMnBi), Weyl (Co 2 MnAl, Co 2 TiGe), half metal (PtMnSb, Co 2 MnSi, Co 2 MnAl x Si 1-x , Co2FeAl), and semiconducting (CoTiSb, NiTiSn) and tuned their properties through alloying and epitaxial strain. We also investigated the closely related materials of rare-earth monopnictide, some of which have also been predicted to be topological. During the attempts to grow the PtMnBi, it was discovered that Bi, another predicted topological material when ultrathin, could be grown epitaxially on InSb, results for which are also reported here. The main focus for this effort has been on using variable photon energy and spin-dependent angle resolved photoemission (ARPES) to determine bulk band structure and surface states of pristine epitaxial films grown on III-V semiconductor and MgO substrates and correlate results with theory and transport measurements. Theory has been critical to interpretation of experimental results and has been essential in guiding experiments. The research benefited from several strong collaborations between the PIs and the beamline scientists at the Advanced Light Source at Lawrence Berkeley Laboratory, the Stanford Linear Accelerator Center (SLAC) at Stanford and at the Max Lab at Lund University in Sweden. The strong experiment - theory collaboration between the PI’s groups, the Palmstrøm group at UCSB and the Janotti group at the University of Delaware, has been critical for interpreting the experimental ARPES and magnetotransport measurements results and making predictions to guide experiments. Weekly interactive Zoom meetings made this work well. A collaboration between the Palmstrøm group and Dr. Alexei Fedorov at the Advanced Light Source (ALS) resulted in significant modifications to his end chamber to accommodate the vacuum suitcase that was designed and constructed in the Palmstrøm group at UCSB. In collaboration with beamline scientists, Drs. Makoto Hashimoto and Donghui Lu at SLAC, Palmstrøm made modifications to the vacuum suitcase and developed special sample holders that allowed samples to be grown in the Palmstrøm MBE systems at UCSB and transported in the UHV vacuum suitcase to SLAC for ARPES measurements. The development of the vacuum suitcase was essential for this grant as it has allowed variable photon energies to be used to identify surface versus bulk states on samples that could not be capped and decapped using As- or Sb-capping layers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

From Filamentary Failure to Durable Halide Perovskite Memristors

Halide perovskites have emerged as promising materials for memristive devices. While their pronounced electrochemical reactivity and fast ionic mobility enable numerous advantages including low-voltage operation and fast switching, the same features also render perovskite-based memristors vulnerable to metallic shunts and poor endurance, limiting their practical applications. Here, we elucidate both the resistive switching and failure mechanisms in perovskite memristors with a fluorine-doped tin oxide (FTO)/methylammonium lead triiodide (MAPbI3)/Ag structure and demonstrate a strategy to substantially enhance device durability. As opposed to commonly invoked filamentary mechanisms, electrical, structural, and spectroscopic analyses reveal that resistive switching arises from interfacial barrier modulation by reversible Ag redox reactions that drive electrochemical doping/dedoping within the perovskite. Device failure, however, originates from metallic Ag0 filamentation that ultimately forms permanent conductive pathways. Introducing an ultrathin Al2O3 interlayer at the inert-electrode interface improves device endurance by more than 30-fold, exceeding 15,000 switching cycles, without compromising other performance metrics. Interfacial characterization indicates that the Al2O3 layer modifies wettability of Ag deposits, promoting planar island growth rather than through-film filamentation. These findings establish a clear link between interfacial electrochemistry, metal precipitation behavior, and memristor reliability, highlighting inert-electrode interfacial engineering as an effective pathway toward durable perovskite-based memristors.

14 SOLAR ENERGY↗

Effects of ultrathin oxides in conducting MIS structures on GaAs

Schottky barrier-type GaAs baseline devices (semiconductor surface etched and then immediately metalized) and GaAs conducting metal oxide-semiconductor devices are fabricated and characterized. The baseline surfaces (no purposeful oxide) are prepared by a basic or an acidic etch, while the surface for the MIS devices are prepared by oxidizing after the etch step. The metallizations used are thin-film Au, Ag, Pd, and Al. It is shown that the introduction of purposeful oxide into these Schottky barrier-type structures examined on n-type GaAs modifies the barrier formation, and that thin interfacial layers can modify barrier formation through trapping and perhaps chemical reactions. For Au- and Pd-devices, enhanced photovoltaic performance of the MIS configuration is due to increased barrier height.

Childs, R. B.↗

Dual interfacial H-bonding-enhanced deep-blue hybrid copper–iodide LEDs

Solution-processed light-emitting diodes based on non-toxic copper–iodide hybrids are a compelling solution for efficient and stable deep-blue lighting, owing to their tunability, high photoluminescence efficiency and environmental sustainability. Here we present a hybrid copper–iodide that shows near-unity photoluminescence quantum yield (99.6%) with an emission wavelength of 449 nm and colour coordinates (0.147, 0.087), alongside its emission mechanism and charge transport characteristics. Here, we use the thin film of this hybrid as the sole active emissive layer to fabricate deep-blue light-emitting diodes and subsequently enhance the device performance through a dual interfacial hydrogen-bond passivation strategy. This synergetic surface modification approach, integrating a hydrogen-bond-acceptor self-assembled monolayer with an ultrathin polymethyl methacrylate capping layer, effectively passivates both heterojunctions of the copper–iodide hybrid emissive layer and optimizes charge injections. We achieve a maximum external quantum efficiency of 12.57%, a maximum luminance of 3,970.30 cd m −2 with colour coordinates (0.147, 0.091) and an excellent operational stability (half-lifetime) of 204 hours under ambient conditions. We further showcase a large-area device of 4 cm 2 that maintains high efficiency. Our findings reveal the potential of copper–iodide-based hybrid materials for applications in solid-state lighting and display technologies, offering a versatile strategy for enhancing device performances.

14 SOLAR ENERGY↗

Covalent Functionalization of Silicon with Plasma-Grown “Fuzzy” Graphene: Robust Aqueous Photoelectrodes for CO 2 Reduction by Molecular Catalysts

Carbon electrodes are ideal for electrochemistry with molecular catalysts, exhibiting facile charge transfer and good stability. Yet for solar-driven catalysis with semiconductor light absorbers, stable semiconductor/carbon interfaces can be difficult to achieve, and carbon’s high optical extinction means it can only be used in ultrathin layers. Here, we demonstrate a plasma-enhanced chemical vapor deposition process that achieves well-controlled deposition of out-of-plane “fuzzy” graphene (FG) on thermally oxidized Si substrates. The resulting Si|FG interfaces possess a silicon oxycarbide (SiOC) interfacial layer, implying covalent bonding between Si and the FG film that is consistent with the mechanical robustness observed from the films. The FG layer is uniform and tunable in thickness and optical transparency by deposition time. Using p-type Si|FG substrates, noncovalent immobilization of cobalt phthalocyanine (CoPc) molecular catalysts was employed for the photoelectrochemical reduction of CO 2 in aqueous solution. The Si|FG|CoPc photocathodes exhibited good catalytic activity, yielding a current density of ∼1 mA/cm 2 , Faradaic efficiency for CO of ∼70% (balance H 2 ), and stable photocurrent for at least 30 h at −1.5 V vs Ag/AgCl under 1-sun illumination. Furthermore, the results suggest that plasma-deposited FG is a robust carbon electrode for molecular catalysts and suitable for further development of aqueous-stable Si photocathodes for CO 2 reduction.

CO2 reduction↗