Homogeneous 2D MoTe2 CMOS Inverters and p–n Junctions Formed by Laser‐Irradiation‐Induced p‐Type Doping

Among all typical transition‐metal dichalcogenides (TMDs), the bandgap of α‐MoTe₂ is smallest and is close to that of conventional 3D Si. The properties of α‐MoTe₂ make it a favorable candidate for future electronic devices. Even though there are a few reports regarding fabrication of complementary metal–oxide‐semiconductor (CMOS) inverters or p–n junction by controlling the charge‐carrier polarity of TMDs, the fabrication process is complicated. Here, a straightforward selective doping technique is demonstrated to fabricate a 2D p–n junction diode and CMOS inverter on a single α‐MoTe₂ nanoflake. The n‐doped channel of a single α‐MoTe₂ nanoflake is selectively converted to a p‐doped region via laser‐irradiation‐induced MoO_x doping. The homogeneous 2D MoTe₂ CMOS inverter has a high DC voltage gain of 28, desirable noise margin (NM_H = 0.52 V_DD, NM_L = 0.40 V_DD), and an AC gain of 4 at 10 kHz. The results show that the doping technique by laser scan can be potentially used for future larger‐scale MoTe₂ CMOS circuits.     

Strong Depletion in Hybrid Perovskite p–n Junctions Induced by Local Electronic Doping

A semiconductor p–n junction typically has a doping‐induced carrier depletion region, where the doping level positively correlates with the built‐in potential and negatively correlates with the depletion layer width. In conventional bulk and atomically thin junctions, this correlation challenges the synergy of the internal field and its spatial extent in carrier generation/transport. Organic–inorganic hybrid perovskites, a class of crystalline ionic semiconductors, are promising alternatives because of their direct badgap, long diffusion length, and large dielectric constant. Here, strong depletion in a lateral p–n junction induced by local electronic doping at the surface of individual CH₃NH₃PbI₃ perovskite nanosheets is reported. Unlike conventional surface doping with a weak van der Waals adsorption, covalent bonding and hydrogen bonding between a MoO₃ dopant and the perovskite are theoretically predicted and experimentally verified. The strong hybridization‐induced electronic coupling leads to an enhanced built‐in electric field. The large electric permittivity arising from the ionic polarizability further contributes to the formation of an unusually broad depletion region up to 10 µm in the junction. Under visible optical excitation without electrical bias, the lateral diode demonstrates unprecedented photovoltaic conversion with an external quantum efficiency of 3.93% and a photodetection responsivity of 1.42 A W^?1.     

2D Molecular Crystal Bilayer p–n Junctions: A General Route toward High‐Performance and Well‐Balanced Ambipolar Organic Field‐Effect Transistors

Ambipolar organic field‐effect transistors (OFETs) are vital for the construction of high‐performance all‐organic digital circuits. The bilayer p–n junction structure, which is composed of separate layers of p‐ and n‐type organic semiconductors, is considered a promising way to realize well‐balanced ambipolar charge transport. However, this approach suffers from severely reduced mobility due to the rough interface between the polycrystalline thin films of p‐ and n‐type organic semiconductors. Herein, 2D molecular crystal (2DMC) bilayer p–n junctions are proposed to construct high‐performance and well‐balanced ambipolar OFETs. The molecular‐scale thickness of the 2DMC ensures high injection efficiency and the atomically flat surface of the 2DMC leads to high‐quality p‐ and n‐layer interfaces. Moreover, by controlling the layer numbers of the p‐ and n‐type 2DMCs, the electron and hole mobilities are tuned and well‐balanced ambipolar transport is accomplished. The hole and electron mobilities reach up to 0.87 and 0.82 cm² V^?1 s^?1, respectively, which are the highest values among organic single‐crystalline double‐channel OFETs measured in ambient air. This work provides a general route to construct high‐performance and well‐balanced ambipolar OFETs based on available unipolar materials.     

Realization of In‐Plane p–n Junctions with Continuous Lattice of a Homogeneous Material

Two‐dimensional (2D) in‐plane p–n junctions with a continuous interface have great potential in next‐generation devices. To date, the general fabrication strategies rely on lateral epitaxial growth of p‐ and n‐type 2D semiconductors. An in‐plane p–n junction is fabricated with homogeneous monolayer Te at the step edge on graphene/6H‐SiC(0001). Scanning tunneling spectroscopy reveals that Te on the terrace of trilayer graphene is p‐type, and it is n‐type on monolayer graphene. Atomic‐resolution images demonstrate the continuous lattice of the junction, and mappings of the electronic states visualize the type‐II band bending across the space‐charge region of 6.2 nm with a build‐in field of 4 × 10⁵ V cm^?1. The reported strategy can be extended to other 2D semiconductors on patternable substrates for designed fabrication of in‐plane junctions.     

3D Hollow α‐MnO2 Framework as an Efficient Electrocatalyst for Lithium–Oxygen Batteries

Lithium–oxygen (Li–O₂) batteries are attracting more attention owing to their superior theoretical energy density compared to conventional Li‐ion battery systems. With regards to the catalytically electrochemical reaction on a cathode, the electrocatalyst plays a key role in determining the performance of Li–O₂ batteries. Herein, a new 3D hollow α‐MnO₂ framework (3D α‐MnO₂) with porous wall assembled by hierarchical α‐MnO₂ nanowires is prepared by a template‐induced hydrothermal reaction and subsequent annealing treatment. Such a distinctive structure provides some essential properties for Li–O₂ batteries including the intrinsic high catalytic activity of α‐MnO₂, more catalytic active sites of hierarchical α‐MnO₂ nanowires on 3D framework, continuous hollow network and rich porosity for the storage of discharge product aggregations, and oxygen diffusion. As a consequence, 3D α‐MnO₂ achieves a high specific capacity of 8583 mA h g^?1 at a current density of 100 mA g^?1, a superior rate capacity of 6311 mA h g^?1 at 300 mA g^?1, and a very good cycling stability of 170 cycles at a current density of 200 mA g^?1 with a fixed capacity of 1000 mA h g^?1. Importantly, the presented design strategy of 3D hollow framework in this work could be extended to other catalytic cathode design for Li–O₂ batteries.     

Hierarchical α‐MnO2 Nanowires@Ni1‐xMnxOy Nanoflakes Core–Shell Nanostructures for Supercapacitors

A facile two‐step solution‐phase method has been developed for the preparation of hierarchical α‐MnO₂ nanowires@Ni_1‐xMn_xO_y nanoflakes core–shell nanostructures. Ultralong α‐MnO₂ nanowires were synthesized by a hydrothermal method in the first step. Subsequently, Ni_1‐xMn_xO_y nanoflakes were grown on α‐MnO₂ nanowires to form core–shell nanostructures using chemical bath deposition followed by thermal annealing. Both solution‐phase methods can be easily scaled up for mass production. We have evaluated their application in supercapacitors. The ultralong one‐dimensional (1D) α‐MnO₂ nanowires in hierarchical core–shell nanostructures offer a stable and efficient backbone for charge transport; while the two‐dimensional (2D) Ni_1‐xMn_xO_y nanoflakes on α‐MnO₂ nanowires provide high accessible surface to ions in the electrolyte. These beneficial features enable the electrode with high capacitance and reliable stability. The capacitance of the core–shell α‐MnO₂@Ni_1‐xMn_xO_y nanostructures (x = 0.75) is as high as 657 F g^?1 at a current density of 250 mA g^?1, and stable charging‐discharging cycling over 1000 times at a current density of 2000 mA g^?1 has been realized.     

2D Porous Carbons prepared from Layered Organic–Inorganic Hybrids and their Use as Oxygen‐Reduction Electrocatalysts

2D porous carbon nanomaterials have attracted tremendous attention in different disciplines especially for electrochemical catalysis. The significant advantage of such 2D materials is that nearly all their surfaces are exposed to the electrolyte and can take part in the electrochemical reaction. Here, a versatile active‐salt‐templating strategy to efficiently synthesize 2D porous carbon nanosheets from layered organic–inorganic hybrids is presented. The resulting heteroatom‐doped carbon nanosheets (NFe/CNs) exhibit exceptional performance for the oxygen‐reduction reaction and in Zn–air battery electrodes. The activity of the best catalyst within a series of NFe/CNs exceeds the performance of conventional carbon‐supported Pt catalysts in terms of onset potential (0.930 vs 0.915 V of Pt/C), half‐wave potential (0.859 vs 0.816 V of Pt/C), long‐time stability, and methanol tolerance. Also, when applied as a cathode catalyst in a zinc–air battery the NFe/CNs presented here outperform commercial Pt/C catalysts.     

Probing the Domain Architecture in 2D α‐Mo2C via Polarized Raman Spectroscopy

MXenes are emerging 2D materials with intriguing properties such as excellent stability and high conductivity. Here, a systematic study on the Raman spectra of 2D α‐Mo₂C (molybdenum carbide), a promising member in MXene family, is conducted. Six experimentally observed Raman modes from ultrathin α‐Mo₂C crystal are first assigned with the assistance of phonon dispersion calculated from density functional theory. Angle‐resolved polarized Raman spectroscopy indicates the anisotropy of α‐Mo₂C in the b–c plane. Raman spectroscopy is further used to study the unique domain structures of 2D α‐Mo₂C crystals grown by chemical vapor deposition. A Raman mapping investigation suggests that most of the α‐Mo₂C flakes contain multiple domains and the c‐axes of neighboring domains tend to form a 60° or 120° angle, due to the weak Mo? C bonds in this interstitial carbide and the low formation energy of the carbon chains along three equivalent directions. This study demonstrates that polarized Raman spectroscopy is a powerful and effective way to characterize the domain structures in α‐Mo₂C, which will facilitate the further exploration of the domain‐structure‐related properties and potential applications of α‐Mo₂C.     

Core–Shell Structure and Interaction Mechanism of γ‐MnO2 Coated Sulfur for Improved Lithium‐Sulfur Batteries

Lithium‐sulfur batteries have attracted worldwide interest due to their high theoretical capacity of 1672 mAh g^?1 and low cost. However, the practical applications are hampered by capacity decay, mainly attributed to the polysulfide shuttle. Here, the authors have fabricated a solid core–shell γ‐MnO₂‐coated sulfur nanocomposite through the redox reaction between KMnO₄ and MnSO₄. The multifunctional MnO₂ shell facilitates electron and Li⁺ transport as well as efficiently prevents polysulfide dissolution via physical confinement and chemical interaction. Moreover, the γ‐MnO₂ crystallographic form also provides one‐dimensional (1D) tunnels for the Li⁺ incorporation to alleviate insoluble Li₂S₂/Li₂S deposition at high discharge rate. More importantly, the MnO₂ phase transformation to Mn₃O₄ occurs during the redox reaction between polysulfides and γ‐MnO₂ is first thoroughly investigated. The S@γ‐MnO₂ composite exhibits a good capacity retention of 82% after 300 cycles (0.5 C) and a fade rate of 0.07% per cycle over 600 cycles (1 C). The degradation mechanism can probably be elucidated that the decomposition of the surface Mn₃O₄ phase is the cause of polysulfide dissolution. The recent work thus sheds new light on the hitherto unknown surface interaction mechanism and the degradation mechanism of Li‐S cells.     

Effect of Ni-modified α-Al2O3 prepared by sol–gel and solvothermal methods on the characteristics and catalytic properties of Pd/α-Al2O3 catalysts

In the present study, Ni-modified α-Al₂O₃ with Ni/Al ratios of 0.3 and 0.5 were prepared by sol–gel and solvothermal method and then were impregnated with 0.3 wt.% Pd. Due to different crystallization mechanism of the two preparation methods used, addition of nickel during preparation of α-Al₂O₃ resulted in various species such as NiAl₂O₄, mixed phases between NiAl₂O₄ and α-Al₂O₃, and mixed phases between NiAl₂O₄ and NiO. As revealed by NH₃-temperature programmed desorption, formation of NiAl₂O₄ drastically reduced acidity of alumina, hence lower amounts of coke deposited during acetylene hydrogenation was found for the Ni-modified α-Al₂O₃ supported catalysts. For any given method, ethylene selectivity was improved in the order of Pd/Ni–Al₂O₃-0.5 > Pd/Ni–Al₂O₃-0.3 > Pd/Ni–Al₂O₃-0  Pd/α–Al₂O₃-commercial. When comparing the samples prepared by different techniques, the sol–gel-made samples showed better performances than the solvothermal-derived ones.