Bottom‐Up Fabrication of Semiconductive Metal–Organic Framework Ultrathin Films

Though generally considered insulating, recent progress on the discovery of conductive porous metal–organic frameworks (MOFs) offers new opportunities for their integration as electroactive components in electronic devices. Compared to classical semiconductors, these metal–organic hybrids combine the crystallinity of inorganic materials with easier chemical functionalization and processability. Still, future development depends on the ability to produce high‐quality films with fine control over their orientation, crystallinity, homogeneity, and thickness. Here self‐assembled monolayer substrate modification and bottom‐up techniques are used to produce preferentially oriented, ultrathin, conductive films of Cu‐CAT‐1. The approach permits to fabricate and study the electrical response of MOF‐based devices incorporating the thinnest MOF film reported thus far (10 nm thick).     

Self‐Assembly of Ferromagnetic Organic–Inorganic Perovskite‐Like Films

Perovskite‐based organic–inorganic hybrids hold great potential as active layers in electronics or optoelectronics or as components of biosensors. However, many of these applications require thin films grown with good control over structure and thickness—a major challenge that needs to be addressed. The work presented here is an effort towards this goal and concerns the layer‐by‐layer deposition at ambient conditions of ferromagnetic organic–inorganic hybrids consisting of alternating CuCl₄‐octahedra and organic layers. The Langmuir‐Blodgett technique used to assemble these structures provides intrinsic control over the molecular organization and film thickness down to the molecular level. Magnetic characterization reveals that the coercive field for these thin films is larger than that for solution‐grown layered bulk crystals. The strategy presented here suggests a promising cost effective route to facilitate the excellently controlled growth of sophisticated materials on a wide variety of substrates that have properties relevant for the high density storage media and spintronic devices.     

Selective Growth of Metal‐Free Metallic and Semiconducting Single‐Wall Carbon Nanotubes

A major obstacle for the use of single‐wall carbon nanotubes (SWCNTs) in electronic devices is their mixture of different types of electrical conductivity that strongly depends on their helical structure. The existence of metal impurities as a residue of a metallic growth catalyst may also lower the performance of SWCNT‐based devices. Here, it is shown that by using silicon oxide (SiO_x) nanoparticles as a catalyst, metal‐free semiconducting and metallic SWCNTs can be selectively synthesized by the chemical vapor deposition of ethanol. It is found that control over the nanoparticle size and the content of oxygen in the SiO_x catalyst plays a key role in the selective growth of SWCNTs. Furthermore, by using the as‐grown semiconducting and metallic SWCNTs as the channel material and source/drain electrodes, respectively, all‐SWCNT thin‐film transistors are fabricated to demonstrate the remarkable potential of these SWCNTs for electronic devices.     

Direct Laser‐Patterned Micro‐Supercapacitors from Paintable MoS2 Films

Micrometer‐sized electrochemical capacitors have recently attracted attention due to their possible applications in micro‐electronic devices. Here, a new approach to large‐scale fabrication of high‐capacitance, two‐dimensional MoS₂ film‐based micro‐supercapacitors is demonstrated via simple and low‐cost spray painting of MoS₂ nanosheets on Si/SiO₂ chip and subsequent laser patterning. The obtained micro‐supercapacitors are well defined by ten interdigitated electrodes (five electrodes per polarity) with 4.5 mm length, 820 μm wide for each electrode, 200 μm spacing between two electrodes and the thickness of electrode is ～0.45 μm. The optimum MoS₂‐based micro‐supercapacitor exhibits excellent electrochemical performance for energy storage with aqueous electrolytes, with a high area capacitance of 8 mF cm^?2 (volumetric capacitance of 178 F cm^?3) and excellent cyclic performance, superior to reported graphene‐based micro‐supercapacitors. This strategy could provide a good opportunity to develop various micro‐/nanosized energy storage devices to satisfy the requirements of portable, flexible, and transparent micro‐electronic devices.     

Growing Oxide Nanowires and Nanowire Networks by Solid State Contact Diffusion into Solution‐Processed Thin Films

New techniques to directly grow metal oxide nanowire networks without the need for initial nanoparticle seed deposition or postsynthesis nanowire casting will bridge the gap between bottom‐up formation and top‐down processing for many electronic, photonic, energy storage, and conversion technologies. Whether etched top‐down, or grown from catalyst nanoparticles bottom‐up, nanowire growth relies on heterogeneous material seeds. Converting surface oxide films, ubiquitous in the microelectronics industry, to nanowires and nanowire networks by the incorporation of extra species through interdiffusion can provide an alternative deposition method. It is shown that solution‐processed thin films of oxides can be converted and recrystallized into nanowires and networks of nanowires by solid‐state interdiffusion of ionic species from a mechanically contacted donor substrate. NaVO₃ nanowire networks on smooth Si/SiO₂ and granular fluorine‐doped tin oxide surfaces can be formed by low‐temperature annealing of a Na diffusion species‐containing donor glass to a solution‐processed V₂O₅ thin film, where recrystallization drives nanowire growth according to the crystal habit of the new oxide phase. This technique illustrates a new method for the direct formation of complex metal oxide nanowires on technologically relevant substrates, from smooth semiconductors, to transparent conducting materials and interdigitated device structures.     

Epitaxial Lift‐Off of Centimeter‐Scaled Spinel Ferrite Oxide Thin Films for Flexible Electronics

Mechanical flexibility of electronic devices has attracted much attention from research due to the great demand in practical applications and rich commercial value. Integration of functional oxide materials in flexible polymer materials has proven an effective way to achieve flexibility of functional electronic devices. However, the chemical and mechanical incompatibilities at the interfaces of dissimilar materials make it still a big challenge to synthesize high‐quality single‐crystalline oxide thin film directly on flexible polymer substrates. This study reports an improved method that is employed to successfully transfer a centimeter‐scaled single‐crystalline LiFe₅O₈ thin film on polyimide substrate. Structural characterizations show that the transferred films have essentially no difference in comparison with the as‐grown films with respect to the microstructure. In particular, the transferred LiFe₅O₈ films exhibit excellent magnetic properties under various mechanical bending statuses and show excellent fatigue properties during the bending cycle tests. These results demonstrate that the improved transfer method provides an effective way to compose single‐crystalline functional oxide thin films onto flexible substrates for applications in flexible and wearable electronics.     

One‐Step Solution Phase Growth of Transition Metal Dichalcogenide Thin Films Directly on Solid Substrates

Ultrathin transition metal dichalcogenides (TMDs) have exotic electronic properties. With success in easy synthesis of high quality TMD thin films, the potential applications will become more viable in electronics, optics, energy storage, and catalysis. Synthesis of TMD thin films has been mostly performed in vacuum or by thermolysis. So far, there is no solution phase synthesis to produce large‐area thin films directly on target substrates. Here, this paper reports a one‐step quick synthesis (within 45–90 s) of TMD thin films (MoS₂, WS₂, MoSe₂, WSe₂, etc.) on solid substrates by using microwave irradiation on a precursor‐containing electrolyte solution. The numbers of the quintuple layers of the TMD thin films are precisely controllable by varying the precursor's concentration in the electrolyte solution. A photodetector made of MoS₂ thin film comprising of small size grains shows near‐IR absorption, supported by the first principle calculation, exhibits a high photoresponsivity (>300 mA W^?1) and a fast response (124 µs). This study paves a robust way for the synthesis of various TMD thin films in solution phases.     

Mixed Ionic and Electronic Conductor for Li‐Metal Anode Protection

Li‐metal is the optimal choice as an anode due to its highest energy density. However, Li‐anodes suffer safety problems from dendritic Li‐growth and continuous corrosion by liquid electrolytes. Here, an effective strategy of using ultrathin and conformal mixed ionic and electronic ceramic conductor (MIEC) is proposed to stabilize Li‐anodes. An ultrathin Li_0.35La_0.52[V]_0.13TiO₃ (LLTO) ceramic film with superior ionic conductivity is first obtained by sintering single‐crystal LLTO nanoparticles, which have controlled surface facets and particle sizes. Then the MIEC property is developed in the LLTO film by introducing toluene as catalyst, which triggers the chemical reactions between LLTO and Li‐metal, leading to high electronic conductivity in the LLTO film. After evaporating toluene, a hybrid LLTO/Li anode with a conformal and stable interface is formed. When applying the hybrid anodes in Li‐metal batteries, the MIEC ceramic film blocks Li‐corrosion from electrolyte and the formation of Li‐dendrites by buffering the Li‐ion concentration gradient and leveling secondary current distribution on Li‐metal surface. At the same time, the Coulombic efficiency of batteries reaches to 98%. This finding will impact the general approach for tailoring the properties of Li‐metal anodes for achieving better Li‐metal battery performance.     

Seed‐Assisted Growth for Low‐Temperature‐Processed All‐Inorganic CsPbIBr2 Solar Cells with Efficiency over 10%

All‐inorganic CsPbIBr₂ perovskite has recently received growing attention due to its balanced band gap and excellent environmental stability. However, the requirement of high‐temperature processing limits its application in flexible devices. Herein, a low‐temperature seed‐assisted growth (SAG) method for high‐quality CsPbIBr₂ perovskite films through reducing the crystallization temperature by introducing methylammonium halides (MAX, X = I, Br, Cl) is demonstrated. The mechanism is attributed to MA cation based perovskite seeds, which act as nuclei lowering the formation energy of CsPbIBr₂ during the annealing treatment. It is found that methylammonium bromide treated perovskite (Pvsk‐Br) film fabricated at low temperature (150 °C) shows micrometer‐sized grains and superior charge dynamic properties, delivering a device with an efficiency of 10.47%. Furthermore, an efficiency of 11.1% is achieved for a device based on high‐temperature (250 °C) processed Pvsk‐Br film via the SAG method, which presents the highest reported efficiency for inorganic CsPbIBr₂ solar cells thus far.     

Self‐Assembled Ordered Three‐Phase Au–BaTiO3–ZnO Vertically Aligned Nanocomposites Achieved by a Templating Method

Complex multiphase nanocomposite designs present enormous opportunities for developing next‐generation integrated photonic and electronic devices. Here, a unique three‐phase nanostructure combining a ferroelectric BaTiO₃, a wide‐bandgap semiconductor of ZnO, and a plasmonic metal of Au toward multifunctionalities is demonstrated. By a novel two‐step templated growth, a highly ordered Au–BaTiO₃–ZnO nanocomposite in a unique “nanoman”‐like form, i.e., self‐assembled ZnO nanopillars and Au nanopillars in a BaTiO₃ matrix, is realized, and is very different from the random three‐phase ones with randomly arranged Au nanoparticles and ZnO nanopillars in the BaTiO₃ matrix. The ordered three‐phase “nanoman”‐like structure provides unique functionalities such as obvious hyperbolic dispersion in the visible and near‐infrared regime enabled by the highly anisotropic nanostructures compared to other random structures. Such a self‐assembled and ordered three‐phase nanocomposite is obtained through a combination of vapor–liquid–solid (VLS) and two‐phase epitaxy growth mechanisms. The study opens up new possibilities in the design, growth, and application of multiphase structures and provides a new approach to engineer the ordering of complex nanocomposite systems with unprecedented control over electron–light–matter interactions at the nanoscale.     

Scalable Manufacturing of Free-Standing,Strong Ti3C2Tx MXene Films with Outstanding Conductivity

Free-standing films that display high strength and high electrical conductivity are critical for flexible electronics, such as electromagnetic interference (EMI) shielding coatings and current collectors for batteries and supercapacitors. 2D Ti₃C₂T_x flakes are ideal candidates for making conductive films due to their high strength and metallic conductivity. It is, however, challenging to transfer those outstanding properties of single MXene flakes to macroscale films as a result of the small flake size and relatively poor flake alignment that occurs during solution-based processing. Here, a scalable method is shown for the fabrication of strong and highly conducting pure MXene films containing highly aligned large MXene flakes. These films demonstrate record tensile strength up to ≈570 MPa for a 940 nm thick film and electrical conductivity of ≈15 100 S cm⁻¹ for a 214 nm thick film, which are both the highest values compared to previously reported pure Ti₃C₂T_x films. These films also exhibit outstanding EMI shielding performance (≈50 dB for a 940 nm thick film) that exceeds other synthetic materials with comparable thickness. MXene films with aligned flakes provide an effective route for producing large-area, high-strength, and high-electrical-conductivity MXene-based films for future electronic applications.     

Epitaxial Growth of Oriented Metalloporphyrin Network Thin Film for Improved Selectivity of Volatile Organic Compounds

This study reports an oriented and homogenous cobalt‐metalloporphyrin network (PIZA‐1) thin film prepared by liquid phase epitaxial (LPE) method. The thickness of the obtained thin films can be well controlled, and their photocurrent properties can also be tuned by LPE cycles or the introduction of conductive guest molecules (tetracyanoquinodimethane and C₆₀) into the PIZA‐1 pores. The study of quartz crystal microbalance adsorption confirms that the PIZA‐1 thin film with [110]‐orientation presents much higher selectivity of benzene over toluene and p‐xylene than that of the PIZA‐1 powder with mixed orientations. These results reveal that the selective adsorption of volatile organic compounds highly depends on the growth orientations of porphyrin‐based metal‐organic framework thin films. Furthermore, the work will provide a new perspective for developing important semiconductive sensing materials with improved selectivity of guest compounds.     

Two‐Dimensional Mott Insulators in SrVO3 Ultrathin Films

Strongly correlated oxides that undergo a metal‐insulator transition (MIT) are a subject of great current interest for their potential application to future electronics as switches and sensors. Recent advances in thin film technology have opened up new avenues to tailor MIT for novel devices beyond conventional CMOS scaling. Here, dimensional‐crossover‐driven MITs are demonstrated in high‐quality epitaxial SrVO₃ (SVO) thin films grown by a pulsed electron‐beam deposition technique. Thick SVO films (∼25 nm) exhibit metallic behavior with the electrical resistivity following the T² law corresponding to a Fermi liquid system. A temperature driven MIT is induced in SVO ultrathin films with thicknesses below 6.5 nm. The transition temperature T_MIT is at 50 K for the 6.5 nm film, 120 K for the 5.7 nm film and 205 K for the 3 nm film. The emergence of the observed MIT can be attributed to the dimensional crossover from a three‐dimensional metal to a two‐dimensional Mott insulator, as the resulting reduction in the effective bandwidth W opens a band gap at the Fermi level. The magneto‐transport study of the SVO ultrathin films also confirm the observed MIT is due to the electron‐electron interactions other than disorder‐induced localization.     

High‐Brightness Blue Light‐Emitting Diodes Enabled by a Directly Grown Graphene Buffer Layer

Single‐crystalline GaN‐based light‐emitting diodes (LEDs) with high efficiency and long lifetime are the most promising solid‐state lighting source compared with conventional incandescent and fluorescent lamps. However, the lattice and thermal mismatch between GaN and sapphire substrate always induces high stress and high density of dislocations and thus degrades the performance of LEDs. Here, the growth of high‐quality GaN with low stress and a low density of dislocations on graphene (Gr) buffered sapphire substrate is reported for high‐brightness blue LEDs. Gr films are directly grown on sapphire substrate to avoid the tedious transfer process and GaN is grown by metal–organic chemical vapor deposition (MOCVD). The introduced Gr buffer layer greatly releases biaxial stress and reduces the density of dislocations in GaN film and In_xGa_1?xN/GaN multiple quantum well structures. The as‐fabricated LED devices therefore deliver much higher light output power compared to that on a bare sapphire substrate, which even outperforms the mature process derived counterpart. The GaN growth on Gr buffered sapphire only requires one‐step growth, which largely shortens the MOCVD growth time. This facile strategy may pave a new way for applications of Gr films and bring several disruptive technologies for epitaxial growth of GaN film and its applications in high‐brightness LEDs.     

Metal–Organic Gel‐Derived FexOy/Nitrogen‐Doped Carbon Films for Enhanced Lithium Storage

The development of cost‐effective and flexible electrodes is demanding in the field of energy storage. Herein, flexible Fe_xO_y/nitrogen‐doped carbon films (Fe_xO_y/NC‐MOG) are prepared by facile electrospinning of Fe‐based metal–organic gels (MOGs) followed by high‐temperature carbonization. This approach allows the even mixing of fragile coordination polymers with polyacrylonitrile into flexible films while reserving the structural characteristics of coordination polymers. After thermal treatment, Fe_xO_y/NC‐MOG films possess uniformly distributed Fe_xO_y nanoparticles and larger accessible surface areas than traditional Fe_xO_y‐NC films without MOG. Taking advantage of the unique structure, Fe_xO_y/NC‐MOG exhibits a superior rate performance (449.8 mA h g^?1 at 5000 mA g^–1) and long cycle life (629.3 mA h g^–1 after 500 cycles at 1000 mA g^–1) when used as additive‐free anodes in lithium‐ion batteries.     

Solution Combustion Synthesis: Low‐Temperature Processing for p‐Type Cu:NiO Thin Films for Transparent Electronics

Low‐temperature solution processing opens a new window for the fabrication of oxide semiconductors due to its simple, low cost, and large‐area uniformity. Herein, by using solution combustion synthesis (SCS), p‐type Cu‐doped NiO (Cu:NiO) thin films are fabricated at a temperature lower than 150 °C. The light doping of Cu substitutes the Ni site and disperses the valence band of the NiO matrix, leading to an enhanced p‐type conductivity. Their integration into thin‐film transistors (TFTs) demonstrates typical p‐type semiconducting behavior. The optimized Cu_5%NiO TFT exhibits outstanding electrical performance with a hole mobility of 1.5 cm² V^?1 s^?1, a large on/off current ratio of ≈10⁴, and clear switching characteristics under dynamic measurements. The employment of a high‐k ZrO₂ gate dielectric enables a low operating voltage (≤2 V) of the TFTs, which is critical for portable and battery‐driven devices. The construction of a light‐emitting‐diode driving circuit demonstrates the high current control capability of the resultant TFTs. The achievement of the low‐temperature‐processed Cu:NiO thin films via SCS not only provides a feasible approach for low‐cost flexible p‐type oxide electronics but also represents a significant step toward the development of complementary metal–oxide semiconductor circuits.     

Homogeneous 2D MoTe2 p–n Junctions and CMOS Inverters formed by Atomic‐Layer‐Deposition‐Induced Doping

Recently, α‐MoTe₂, a 2D transition‐metal dichalcogenide (TMD), has shown outstanding properties, aiming at future electronic devices. Such TMD structures without surface dangling bonds make the 2D α‐MoTe₂ a more favorable candidate than conventional 3D Si on the scale of a few nanometers. The bandgap of thin α‐MoTe₂ appears close to that of Si and is quite smaller than those of other typical TMD semiconductors. Even though there have been a few attempts to control the charge‐carrier polarity of MoTe₂, functional devices such as p–n junction or complementary metal–oxide–semiconductor (CMOS) inverters have not been reported. Here, we demonstrate a 2D CMOS inverter and p–n junction diode in a single α‐MoTe₂ nanosheet by a straightforward selective doping technique. In a single α‐MoTe₂ flake, an initially p‐doped channel is selectively converted to an n‐doped region with high electron mobility of 18 cm² V^?1 s^?1 by atomic‐layer‐deposition‐induced H‐doping. The ultrathin CMOS inverter exhibits a high DC voltage gain of 29, an AC gain of 18 at 1 kHz, and a low static power consumption of a few nanowatts. The results show a great potential of α‐MoTe₂ for future electronic devices based on 2D semiconducting materials.     

Biodegradable Protein‐based Films and Their Properties: A Comparative Study

Biodegradable protein‐based films prepared from different protein sources [commercial bovine gelatine (CG), giant catfish skin gelatine (GG), soy protein isolates (SPI), fish myofibrillar protein (FMP) and whey protein concentrate (WPC)] were all investigated for their mechanical, physical, chemical, thermal and barrier properties. The properties of the resulting films were then compared with those of commercial wrap films [polyvinyl chloride (PVC)]. The film forming solution containing 7% (w/v) protein and 50% (w/w) glycerol was used to produce the films through a casting method. Of the protein‐based films, the GG film had the highest tensile strength and elongation, while the WPC film exhibited the lowest film solubility, water vapour permeability, light transmission in UV‐Vis range (200–800 nm) and film transparency. However, the colour of the FMP film and the thickness were closer to that of the PVC film, particularly the L* and b* values. The appearances of the protein‐based films were similar to the PVC film, and they were uniformly transparent. Therefore, biodegradable films produced from different types of protein sources exhibited differences in their properties. These results are consistent with data from FTIR and protein pattern analyses. Based on these findings, different sources of protein‐based films can be used as an alternative for food packaging applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Anion‐Sorbent Composite Separators for High‐Rate Lithium‐Ion Batteries

Novel composite separators containing metal–organic‐framework (MOF) particles and poly(vinyl alcohol) are fabricated by the electrospinning process. The MOF particles containing opened metal sites can spontaneously adsorb anions while allowing effective transport of lithium ions in the electrolyte, leading to dramatically improved lithium‐ion transference number t_Li⁺ (up to 0.79) and lithium‐ion conductivity. Meanwhile, the incorporation of the MOF particles alleviates the decomposition of the electrolyte, enhances the electrode reaction kinetics, and reduces the interface resistance between the electrolyte and the electrodes. Implementation of such composite separators in conventional lithium‐ion batteries leads to significantly improved rate capability and cycling durability, offering a new prospective toward high‐performance lithium‐ion batteries.     

Chemical and Morphological Control of Interfacial Self‐Doping for Efficient Organic Electronics

Solution‐based processing of materials for electrical doping of organic semiconductor interfaces is attractive for boosting the efficiency of organic electronic devices with multilayer structures. To simplify this process, self‐doping perylene diimide (PDI)‐based ionene polymers are synthesized, in which the semiconductor PDI components are embedded together with electrolyte dopants in the polymer backbone. Functionality contained within the PDI monomers suppresses their aggregation, affording self‐doping interlayers with controllable thickness when processed from solution into organic photovoltaic devices (OPVs). Optimal results for interfacial self‐doping lead to increased power conversion efficiencies (PCEs) of the fullerene‐based OPVs, from 2.62% to 10.64%, and of the nonfullerene‐based OPVs, from 3.34% to 10.59%. These PDI–ionene interlayers enable chemical and morphological control of interfacial doping and conductivity, demonstrating that the conductive channels are crucial for charge transport in doped organic semiconductor films. Using these novel interlayers with efficient doping and high conductivity, both fullerene‐ and nonfullerene‐based OPVs are achieved with PCEs exceeding 9% over interlayer thicknesses ranging from ≈3 to 40 nm.