Metastable Polymorphic Phases in Monolayer TaTe2.

Polymorphic phases and collective phenomena-such as charge density waves (CDWs)-in transition metal dichalcogenides (TMDs) dictate the physical and electronic properties of the material. Most TMDs naturally occur in a single given phase, but the fine-tuning of growth conditions via methods such as molecular beam epitaxy (MBE) allows to unlock otherwise inaccessible polymorphic structures. Exploring and understanding the morphological and electronic properties of new phases of TMDs is an essential step to enable their exploitation in technological applications. Here, scanning tunneling microscopy (STM) is used to map MBE-grown monolayer (ML) TaTe2 . This work reports the first observation of the 1H polymorphic phase, coexisting with the 1T, and demonstrates that their relative coverage can be controlled by adjusting synthesis parameters. Several superperiodic structures, compatible with CDWs, are observed to coexist on the 1T phase. Finally, this work provides theoretical insight on the delicate balance between Te…Te and Ta-Ta interactions that dictates the stability of the different phases. The findings demonstrate that TaTe2 is an ideal platform to investigate competing interactions, and indicate that accurate tuning of growth conditions is key to accessing metastable states in TMDs.

Overcoming Boltzmann's Tyranny in a Transistor via the Topological Quantum Field Effect.

The subthreshold swing is the critical parameter determining the operation of a transistor in low-power applications such as switches. It determines the fraction of dissipation due to the gate capacitance used for turning the device on and off, and in a conventional transistor it is limited by Boltzmann's tyranny to kBT ln(10)/q. Here, we demonstrate that the subthreshold swing of a topological transistor in which conduction is enabled by a topological phase transition via electric field switching, can be sizably reduced in a noninteracting system by modulating the Rashba spin-orbit interaction. By developing a theoretical framework for quantum spin Hall materials with honeycomb lattices, we show that the Rashba interaction can reduce the subthreshold swing by more than 25% compared to Boltzmann's limit in currently available materials but without any fundamental lower bound, a discovery that can guide future material design and steer the engineering of topological quantum devices.

Metal-Organic Frameworks/Conducting Polymer Hydrogel Integrated Three-Dimensional Free-Standing Monoliths as Ultrahigh Loading Li-S Battery Electrodes.

The lithium-sulfur (Li-S) system is a promising material for the next-generation of high energy density batteries with application extending from electrical vehicles to portable devices and aeronautics. Despite progress, the energy density of current Li-S technologies is still below that of conventional intercalation-type cathode materials due to limited stability and utilization efficiency at high sulfur loading. Here, we present a conducting polymer hydrogel integrated highly performing free-standing three-dimensional (3D) monolithic electrode architecture for Li-S batteries with superior electrochemical stability and energy density. The electrode layout consists of a highly conductive three-dimensional network of N,P codoped carbon with well-dispersed metal-organic framework nanodomains of ZIF-67 and HKUST-1. The hierarchical monolithic 3D carbon networks provide an excellent environment for charge and electrolyte transport as well as mechanical and chemical stability. The electrically integrated MOF nanodomains significantly enhance the sulfur loading and retention capabilities by inhibiting the release of lithium polysulfide specificities as well as improving the charge transfer efficiency at the electrolyte interface. Our optimal 3D carbon-HKUST-1 electrode architecture achieves a very high areal capacity of >16 mAh cm-2 and volumetric capacity (CV) of 1230.8 mAh cm-3 with capacity retention of 82% at 0.2C for over 300 cycles, providing an attractive candidate material for future high-energy density Li-S batteries.

Imaging the Breakdown and Restoration of Topological Protection in Magnetic Topological Insulator MnBi2Te4.

Quantum anomalous Hall (QAH) insulators transport charge without resistance along topologically protected chiral 1D edge states. Yet, in magnetic topological insulators to date, topological protection is far from robust, with zero-magnetic field QAH effect only realized at temperatures an order of magnitude below the Néel temperature TN, though small magnetic fields can stabilize QAH effect. Understanding why topological protection breaks down is therefore essential to realizing QAH effect at higher temperatures. Here a scanning tunneling microscope is used to directly map the size of exchange gap (Eg,ex) and its spatial fluctuation in the QAH insulator 5-layer MnBi2Te4. Long-range fluctuations of Eg,ex are observed, with values ranging between 0 (gapless) and 70 meV, appearing to be uncorrelated to individual surface point defects. The breakdown of topological protection is directly imaged, showing that the gapless edge state, the hallmark signature of a QAH insulator, hybridizes with extended gapless regions in the bulk. Finally, it is unambiguously demonstrated that the gapless regions originate from magnetic disorder, by demonstrating that a small magnetic field restores Eg,ex in these regions, explaining the recovery of topological protection in magnetic fields. The results indicate that overcoming magnetic disorder is the key to exploiting the unique properties of QAH insulators.

Defects, band bending and ionization rings in MoS2.

Chalcogen vacancies in transition metal dichalcogenides are widely acknowledged as both donor dopants and as a source of disorder. The electronic structure of sulphur vacancies in MoS2however is still controversial, with discrepancies in the literature pertaining to the origin of the in-gap features observed via scanning tunneling spectroscopy (STS) on single sulphur vacancies. Here we use a combination of scanning tunnelling microscopy and STS to study embedded sulphur vacancies in bulk MoS2crystals. We observe spectroscopic features dispersing in real space and in energy, which we interpret as tip position- and bias-dependent ionization of the sulphur vacancy donor due to tip induced band bending. The observations indicate that care must be taken in interpreting defect spectra as reflecting in-gap density of states, and may explain discrepancies in the literature.

Formation of a Stable Surface Oxide in MnBi2Te4 Thin Films.

Understanding the air stability of MnBi2Te4 thin films is crucial for the development and long-term operation of electronic devices based on magnetic topological insulators. In the present work, we study MnBi2Te4 thin films upon exposure to the atmosphere using a combination of synchrotron-based photoelectron spectroscopy, room-temperature electrical transport, and atomic force microscopy to determine the oxidation process. After 2 days of air exposure, a 2 nm thick oxide passivates the surface, corresponding to the oxidation of only the top two surface layers, with the underlying layers preserved. This protective oxide layer results in samples that still exhibit metallic conduction even after several days of air exposure. Furthermore, the work function decreases from 4.4 eV for pristine MnBi2Te4 to 4.0 eV after the formation of the oxide, along with only a small shift in the core levels, indicating minimal doping as a result of air exposure. With the oxide confined to the top surface layers, and the underlying layers preserved, it may be possible to explore new avenues in how to handle, prepare, and passivate future MnBi2Te4 devices.

Progress in Epitaxial Thin-Film Na3 Bi as a Topological Electronic Material.

Trisodium bismuthide (Na3 Bi) is the first experimentally verified topological Dirac semimetal, and is a 3D analogue of graphene hosting relativistic Dirac fermions. Its unconventional momentum-energy relationship is interesting from a fundamental perspective, yielding exciting physical properties such as chiral charge carriers, the chiral anomaly, and weak anti-localization. It also shows promise for realizing topological electronic devices such as topological transistors. Herein, an overview of the substantial progress achieved in the last few years on Na3 Bi is presented, with a focus on technologically relevant large-area thin films synthesized via molecular beam epitaxy. Key theoretical aspects underpinning the unique electronic properties of Na3 Bi are introduced. Next, the growth process on different substrates is reviewed. Spectroscopic and microscopic features are illustrated, and an analysis of semiclassical and quantum transport phenomena in different doping regimes is provided. The emergent properties arising from confinement in two dimensions, including thickness-dependent and electric-field-driven topological phase transitions, are addressed, with an outlook toward current challenges and expected future progress.

Crossover from 2D Ferromagnetic Insulator to Wide Band Gap Quantum Anomalous Hall Insulator in Ultrathin MnBi2Te4.

Intrinsic magnetic topological insulators offer low disorder and large magnetic band gaps for robust magnetic topological phases operating at higher temperatures. By controlling the layer thickness, emergent phenomena such as the quantum anomalous Hall (QAH) effect and axion insulator phases have been realized. These observations occur at temperatures significantly lower than the Néel temperature of bulk MnBi2Te4, and measurement of the magnetic energy gap at the Dirac point in ultrathin MnBi2Te4 has yet to be achieved. Critical to achieving the promise of this system is a direct measurement of the layer-dependent energy gap and verification of a temperature-dependent topological phase transition from a large band gap QAH insulator to a gapless TI paramagnetic phase. Here we utilize temperature-dependent angle-resolved photoemission spectroscopy to study epitaxial ultrathin MnBi2Te4. We directly observe a layer-dependent crossover from a 2D ferromagnetic insulator with a band gap greater than 780 meV in one septuple layer (1 SL) to a QAH insulator with a large energy gap (>70 meV) at 8 K in 3 and 5 SL MnBi2Te4. The QAH gap is confirmed to be magnetic in origin, as it becomes gapless with increasing temperature above 8 K.

Engineering of SnO2-Graphene Oxide Nanoheterojunctions for Selective Room-Temperature Chemical Sensing and Optoelectronic Devices.

The development of high-performing sensing materials, able to detect ppb-trace concentrations of volatile organic compounds (VOCs) at low temperatures, is required for the development of next-generation miniaturized wireless sensors. Here, we present the engineering of selective room-temperature (RT) chemical sensors, comprising highly porous tin dioxide (SnO2)-graphene oxide (GO) nanoheterojunction layouts. The optoelectronic and chemical properties of these highly porous (>90%) p-n heterojunctions were systematically investigated in terms of composition and morphologies. Optimized SnO2-GO layouts demonstrate significant potential as both visible-blind photodetectors and selective RT chemical sensors. Notably, a low GO content results in an excellent UV light responsivity (400 A W-1), with short rise and decay times, and RT high chemical sensitivity with selective detection of VOCs such as ethanol down to 100 ppb. In contrast, a high concentration of GO drastically decreases the RT response to ethanol and results in good selectivity to ethylbenzene. The feasibility of tuning the chemical selectivity of sensor response by engineering the relative amount of GO and SnO2 is a promising feature that may guide the future development of miniaturized solid-state gas sensors. Furthermore, the excellent optoelectronic properties of these SnO2-GO nanoheterojunctions may find applications in various other areas such as optoelectronic devices and (photo)electrocatalysis.

One-Step Synthesis of Porous Transparent Conductive Oxides by Hierarchical Self-Assembly of Aluminum-Doped ZnO Nanoparticles.

Transparent conductive oxides (TCOs) are highly desirable for numerous applications ranging from photovoltaics to light-emitting diodes and photoelectrochemical devices. Despite progress, it remains challenging to fabricate porous TCOs (pTCOs) that may provide, for instance, a hierarchical nanostructured morphology for the separation of photoexcited hole/electron couples. Here, we present a facile process for the fabrication of porous architectures of aluminum-doped zinc oxide (AZO), a low-cost and earth-abundant transparent conductive oxide. Three-dimensional nanostructured films of AZO with tunable porosities from 10 to 98% were rapidly self-assembled from flame-made nanoparticle aerosols. Successful Al doping was confirmed by X-ray photoemission spectroscopy, high-resolution transmission electron microscopy, elemental mapping, X-ray diffraction, and Fourier transform infrared spectroscopy. An optimal Al-doping level of 1% was found to induce the highest material conductivity, while a higher amount led to partial segregation and formation of aluminum oxide domains. A controllable semiconducting to conducting behavior with a resistivity change of more than 4 orders of magnitudes from about 3 × 102 to 9.4 × 106 Ω cm was observed by increasing the AZO film porosity from 10 to 98%. While the denser AZO morphologies may find immediate application as transparent electrodes, we demonstrate that the ultraporous semiconducting layers have potential as a light-driven gas sensor, showing a high response of 1.92-1 ppm of ethanol at room temperature. We believe that these tunable porous transparent conductive oxides and their scalable fabrication method may provide a highly performing material for future optoelectronic devices.

Room-temperature photodetectors and VOC sensors based on graphene oxide-ZnO nano-heterojunctions.

The rapid development of smart wearable electronics is driving the engineering of novel miniaturized sensing materials that can rapidly respond to very small changes in the concentration of biomarkers at room temperature. Carbon-based nanomaterials offer numerous attractive properties such as low resistivity, good mechanical robustness and integration potential, but lack a strong detection and transduction mechanism for the measurement of chemical molecules or photons. Here, we present a three-dimensional nanostructured architecture comprising optimally integrated graphene oxide (GO)-ZnO heterojunctions for the room temperature sensing of volatile biomarkers. We show that this layout also provides excellent response to UV light showcasing its applicability as a visible-blind photodetector. Notably, the optimal integration of well-dispersed GO nanodomains in a 3D ZnO network significantly enhances the room-temperature chemical sensitivity and light responsivity, while higher GO contents drastically worsen the material performance. This is attributed to the different roles of GO at low and high contents. Small amounts of GO lead to the formation of electron depleted nano-heterojunctions with excellent electron-hole separation efficiency. In contrast, large amounts of GO form a percolating electrical network that inhibits the light and chemical-sensing properties of the ZnO nanoparticles. Our optimal GO-ZnO demonstrates 33 A W-1 responsivity to UV light as well as the room temperature detection of volatile organic compounds down to 100 ppb. We believe that these findings provide guidelines for the future engineering of hybrid carbon-metal oxide devices for applications extending from optoelectronics to chemical sensing and electrocatalysis.

On-surface synthesis of polyethylenedioxythiophene.

On-surface synthesis of conjugated polymers is made challenging by the need to promote the desired reaction while preventing or minimizing unwanted ancillary reactions that compromise the product integrity. We perform a comprehensive study of the reactions of 2,5-dichloro-3,4-ethylenedioxythiophene on coinage metal surfaces, and demonstrate that only on Ag(111) can we obtain a planar polymer product, polyethylenedioxythiophene (PEDOT).

Two-Dimensional Hallmark of Highly Interconnected Three-Dimensional Nanoporous Graphene.

Scaling graphene from a two-dimensional (2D) ideal structure to a three-dimensional (3D) millimeter-sized architecture without compromising its remarkable electrical, optical, and thermal properties is currently a great challenge to overcome the limitations of integrating single graphene flakes into 3D devices. Herewith, highly connected and continuous nanoporous graphene (NPG) samples, with electronic and vibrational properties very similar to those of suspended graphene layers, are presented. We pinpoint the hallmarks of 2D ideal graphene scaled in these 3D porous architectures by combining the state-of-the-art spectromicroscopy and imaging techniques. The connected and bicontinuous topology, without frayed borders and edges and with low density of crystalline defects, has been unveiled via helium ion, Raman, and transmission electron microscopies down to the atomic scale. Most importantly, nanoscanning photoemission unravels a 3D NPG structure with preserved 2D electronic density of states (Dirac cone like) throughout the porous sample. Furthermore, the high spatial resolution brings to light the interrelationship between the topology and the morphology in the wrinkled and highly bent regions, where distorted sp2 C bonds, associated with sp3-like hybridization state, induce small energy gaps. This highly connected graphene structure with a 3D skeleton overcomes the limitations of small-sized individual graphene sheets and opens a new route for a plethora of applications of the 2D graphene properties in 3D devices.