Molten‐Salt‐Assisted Self‐Assembly (MASA)‐Synthesis of Mesoporous Metal Titanate‐Titania,Metal Sulfide‐Titania,and Metal Selenide‐Titania Thin Films

New synthetic strategies are needed for the assembly of porous metal titanates and metal chalcogenite‐titania thin films for various energy applications. Here, a new synthetic approach is introduced in which two solvents and two surfactants are used. Both surfactants are necessary to accommodate the desired amount of salt species in the hydrophilic domains of the mesophase. The process is called a molten‐salt‐assisted self‐assembly (MASA) because the salt species are in the molten phase and act as a solvent to assemble the ingredients into a mesostructure and they react with titania to form mesoporous metal titanates during the annealing step. The mesoporous metal titanate (meso‐Zn₂TiO₄ and meso‐CdTiO₃) thin films are reacted under H₂S or H₂Se gas at room temperature to yield high quality transparent mesoporous metal chalcogenides. The H₂Se reaction produces rutile and brookite titania phases together with nanocrystalline metal selenides and H₂S reaction of meso‐CdTiO₃ yields nanocrystalline anatase and CdS in the spatially confined pore walls. Two different metal salts (zinc nitrate hexahydrate and cadmium nitrate tetrahydrate) are tested to demonstrate the generality of the new assembly process. The meso‐TiO₂‐CdSe film shows photoactivity under sunlight.     

3D Hexagonal (R‐3m) Mesostructured Nanocrystalline Titania Thin Films: Synthesis and Characterization

A straightforward and reproducible synthesis of crack‐free large‐area thin films of 3D hexagonal (R‐3m) mesostructured nanocrystalline titania (meso‐nc‐TiO₂) using a Pluronic triblock copolymer (P123)/1‐butanol templating system is described. The characterization of the films is achieved using a combination of electron microscopy (high‐resolution scanning electron microscopy and scanning transmission electron microscopy), grazing‐incidence small‐angle X‐ray scattering, in situ high‐temperature X‐ray diffraction, and variable‐angle spectroscopic ellipsometry. The mesostructure of the obtained films is found to be based upon a 3D periodic array of large elliptically shaped cages with diameters around 20 nm interconnected by windows of about 5 nm in size. The mesopores of the film calcined at 300 °C are very highly ordered, and the titania framework of the film has a crystallinity of 40 % being composed of 5.8 nm sized anatase crystallites. The film displays high thermal stability in that the collapse of the pore architecture is incomplete even at 600 °C. The accessible surface area of 3D hexagonal meso‐nc‐TiO₂ estimated by the absorption of methylene blue is nearly twice as large as that of 2D hexagonal meso‐nc‐TiO₂ at the same annealing temperature.     

Highly Conductive Optical Quality Solution‐Processed Films of 2D Titanium Carbide

MXenes comprise a new class of solution‐dispersable, 2D nanomaterials formed from transition metal carbides and nitrides such as Ti₃C₂. Here, it is shown that 2D Ti₃C₂ can be assembled from aqueous solutions into optical quality, nanometer thin films that, at 6500 S cm^?1, surpass the conductivity of other solution‐processed 2D materials, while simultaneously transmitting >97% of visible light per‐nanometer thickness. It is shown that this high conductivity is due to a metal‐like free‐electron density as well as a high degree of coplanar alignment of individual nanosheets achieved through spincasting. Consequently, the spincast films exhibit conductivity over a macroscopic scale that is comparable to the intrinsic conductivity of the constituent 2D sheets. Additionally, optical characterization over the ultraviolet‐to‐near‐infrared range reveals the onset of free‐electron plasma oscillations above 1130 nm. Ti₃C₂ is therefore a potential building block for plasmonic applications at near‐infrared wavelengths and constitutes the first example of a new class of solution‐processed, carbide‐based 2D optoelectronic materials.     

Assembly of Layered Rare‐Earth Hydroxide Nanosheets and SiO2 Nanoparticles to Fabricate Multifunctional Transparent Films Capable of Combinatorial Color Generation

Colloidal solutions of layered rare‐earth hydroxide nanosheets provide a simple route to deposit ultra thin luminescence films. The antireflection and antifogging properties were integrated into transparent luminescent films by the layer‐by‐layer assembly of Eu³⁺, Tb³⁺, Dy³⁺ doped‐hydroxocation nanosheets and negatively‐charged SiO₂ nanoparticles. Resulting multifunctional films exhibited efficient red, green, and blue emissions with controllable intensity. Highly improved transmittance enabled us to display combinatorial color luminescence, which can be achieved by multiply overlapping individual films with different combinations, without significant loss of transparency. Triple overlap of red/green/blue films generated an excellent white‐light under 254 nm UV irradiation.     

High‐Performance,Air‐Stable,Top‐Gate,p‐Channel WSe2 Field‐Effect Transistor with Fluoropolymer Buffer Layer

High‐performance, air‐stable, p‐channel WSe₂ top‐gate field‐effect transistors (FETs) using a bilayer gate dielectric composed of high‐ and low‐k dielectrics are reported. Using only a high‐k Al₂O₃ as the top‐gate dielectric generally degrades the electrical properties of p‐channel WSe₂, therefore, a thin fluoropolymer (Cytop) as a buffer layer to protect the 2D channel from high‐k oxide forming is deposited. As a result, a top‐gate‐patterned 2D WSe₂ FET is realized. The top‐gate p‐channel WSe₂ FET demonstrates a high hole mobility of 100 cm²_­ V^?1 s^?1 and a I_ON/I_OFF ratio > 10⁷ at low gate voltages (V_GS ca. ?4 V) and a drain voltage (V_DS) of ?1 V on a glass substrate. Furthermore, the top‐gate FET shows a very good stability in ambient air with a relative humidity of 45% for 7 days after device fabrication. Our approach of creating a high‐k oxide/low‐k organic bilayer dielectric is advantageous over single‐layer high‐k dielectrics for top‐gate p‐channel WSe₂ FETs, which will lead the way toward future electronic nanodevices and their integration.     

High‐Performance Flexible Thermoelectric Devices Based on All‐Inorganic Hybrid Films for Harvesting Low‐Grade Heat

The fabrication of a flexible thermoelectric (TE) device that contains flexible, all‐inorganic hybrid thin films (p‐type single‐wall carbon nanotubes (SWCNTs)/Sb₂Te₃ and n‐type reduced graphene oxide (RGO)/Bi₂Te₃) is reported. The optimized power factors of the p‐type and n‐type hybrid thin films at ambient temperature are about 55 and 108 µW m^?1 K^?2, respectively. The high performance of these films that are fabricated through the combination of vacuum filtration and annealing can be attributed to their planar orientation and network structure. In addition, a TE device, with 10 couples of legs, shows an output power of 23.6 µW at a temperature gradient of 70 K. A prototype of an integrated photovoltaic‐TE (PV‐TE) device demonstrates the ability to harvest low‐grade “waste” thermal energy from the human body and solar irradiation. The flexible TE and PV‐TE device have great potential in wearable energy harvesting and management.     

Phthalocyanine‐Based 2D Conjugated Metal‐Organic Framework Nanosheets for High‐Performance Micro‐Supercapacitors

2D conjugated metal‐organic frameworks (2D c‐MOFs) are emerging as a novel class of conductive redox‐active materials for electrochemical energy storage. However, developing 2D c‐MOFs as flexible thin‐film electrodes have been largely limited, due to the lack of capability of solution‐processing and integration into nanodevices arising from the rigid powder samples by solvothermal synthesis. Here, the synthesis of phthalocyanine‐based 2D c‐MOF (Ni₂[CuPc(NH)₈]) nanosheets through ball milling mechanical exfoliation method are reported. The nanosheets feature with average lateral size of ≈160 nm and mean thickness of ≈7 nm (≈10 layers), and exhibit high crystallinity and chemical stability as well as a p‐type semiconducting behavior with mobility of ≈1.5 cm² V^?1 s^?1 at room temperature. Benefiting from the ultrathin feature, the nanosheets allow high utilization of active sites and facile solution‐processability. Thus, micro‐supercapacitor (MSC) devices are fabricated mixing Ni₂[CuPc(NH)₈] nanosheets with exfoliated graphene, which display outstanding cycling stability and a high areal capacitance up to 18.9 mF cm^?2; the performance surpasses most of the reported conducting polymers‐based and 2D materials‐based MSCs.     

Metal–Organic Framework (MOF) Derived Electrodes with Robust and Fast Lithium Storage for Li‐Ion Hybrid Capacitors

Hybrid metal–organic frameworks (MOFs) demonstrate great promise as ideal electrode materials for energy‐related applications. Herein, a well‐organized interleaved composite of graphene‐like nanosheets embedded with MnO₂ nanoparticles (MnO₂@C‐NS) using a manganese‐based MOF and employed as a promising anode material for Li‐ion hybrid capacitor (LIHC) is engineered. This unique hybrid architecture shows intriguing electrochemical properties including high reversible specific capacity 1054 mAh g^?1 (close to the theoretical capacity of MnO₂, 1232 mAh g^?1) at 0.1 A g^?1 with remarkable rate capability and cyclic stability (90% over 1000 cycles). Such a remarkable performance may be assigned to the hierarchical porous ultrathin carbon nanosheets and tightly attached MnO₂ nanoparticles, which provide structural stability and low contact resistance during repetitive lithiation/delithiation processes. Moreover, a novel LIHC is assembled using a MnO₂@C‐NS anode and MOF derived ultrathin nanoporous carbon nanosheets (derived from other potassium‐based MOFs) cathode materials. The LIHC full‐cell delivers an ultrahigh specific energy of 166 Wh kg^?1 at 550 W kg^?1 and maintained to 49.2 Wh kg^?1 even at high specific power of 3.5 kW kg^?1 as well as long cycling stability (91% over 5000 cycles). This work opens new opportunities for designing advanced MOF derived electrodes for next‐generation energy storage devices.     

Sodium‐Mediated Epitaxial Growth of 2D Ultrathin Sb2Se3 Flakes for Broadband Photodetection

As an important member of group VA–VIA semiconductors, 2D Sb₂Se₃ has drawn widespread attention thanks to its outstanding optoelectronic properties as compared to the bulk material. However, due to the intrinsic chain‐like crystal structure, the controllable synthesis of ultrathin 2D planar Sb₂Se₃ nanostructures still remains a huge challenge. Herein, for the first time, the crystal structure limitation is overcome and the successful structural evolution of 2D ultrathin Sb₂Se₃ flakes (as thin as 1.3 nm), by introducing a sodium‐mediated chemical vapor deposition (CVD) growth method, is realized. The formation of 2D planar geometry is mainly attributed to the preferential growth of (010) plane with the lowest formation energy. The thickness‐dependent band structure of 2D Sb₂Se₃ flakes shows a wide absorption band from UV to NIR region (300–1000 nm), suggesting its potential application in broadband photodetection. Strikingly, the Sb₂Se₃ flakes–based photodetector demonstrates excellent performance such as broadband response varying from UV to NIR region, high responsivity of 4320 mA W^?1, fast response time (τ_rise ≈ 13.16 ms and τ_decay ≈ 9.61 ms), and strong anisotropic ratio of 2.5@ 532 nm, implying promising potential application in optoelectronics.     

Competing Crystal Growth in Ge–Sb Phase‐Change Films

Analysis of crystal growth in thin films of phase‐change materials can provide deeper insights in the extraordinary phase transformation kinetics of these materials excellently suited for data storage applications. In the present work crystal growth in Ge_xSb_100‐x thin films with x = 6, 7, 8, 9, and 10 is studied in detail, demonstrating that the crystallization temperature increases from ～80 °C for Ge₆Sb₉₄ to ～200 °C for Ge₁₀Sb₉₀ and simultaneously the activation energy for crystal growth also significantly increases from 1.7 eV to 5.5 eV. The most interesting new finding is that in the thin films containing 8, 9, and 10 at% Ge two competing growth modes occur which can have several orders of magnitude difference in growth rate at a single external temperature: an initial mode with isotropic slow growth producing circular crystals with smooth surfaces and growth fronts and a fast growth mode producing crystals with triangular shape having rough surfaces and growth fronts indicative of dendritic‐like growth. The slow‐growth mode becomes increasingly dominant for crystallization at low temperatures when the Ge concentration is increased from 8 to 10 at% Ge. For a certain Ge concentration, the slow growth mode becomes increasingly dominant at lower temperatures and the fast growth mode at higher temperatures. Latent heat produced during crystallization is considered a principal factor explaining the observations. The fast growth mode is associated with (eutectic) decomposition generating more latent heat and instable growth fronts and the slow growth mode is associated with thermodynamically less stable homogeneously alloyed crystals generating less latent heat, but stable growth fronts.     

Electrolyte‐Gated n‐Type Transistors Produced from Aqueous Inks of WS2 Nanosheets

Solution‐processed, low cost thin films of layered semiconductors such as transition metal dichalcogenides (TMDs) are potential candidates for future printed electronics. Here, n‐type electrolyte‐gated transistors (EGTs) based on porous WS₂ nanosheet networks as the semiconductor are demonstrated. The WS₂ nanosheets are liquid phase exfoliated to form aqueous/surfactant stabilized inks, and deposited at low temperatures (T < 120 °C) in ambient atmosphere by airbrushing. No solvent exchange, further additives, or complicated processing steps are required. While the EGTs are primarily n‐type (electron accumulation), some hole transport is also observable. The EGTs show current modulations > 10⁴ with low hysteresis, channel width‐normalized on‐conductances of up to 0.27 µS µm^?1 and estimated electron mobilities around 0.01 cm² V^?1 s^?1. In addition, the WS₂ nanosheet networks exhibit relatively high volumetric capacitance values of 30 F cm^?3. Charge transport within the network depends significantly on the applied lateral electric field and is thermally activated, which supports the notion that hopping between nanosheets is a major limiting factor for these networks and their future application.     

Achieving of Flexible,Free‐Standing,Ultracompact Delaminated Titanium Carbide Films for High Volumetric Performance and Heat‐Resistant Symmetric Supercapacitors

The volumetric performance of supercapacitors (SCs), besides the gravimetric performance, is attracting an increasing attention due to the fast development of electric vehicles and smart devices. Here, a unique design of symmetric supercapacitor material is reported with a tight face‐to‐face architecture by applying a high pressure to the delaminated Ti₃C₂ (d‐Ti₃C₂) films. The high pressure makes the d‐Ti₃C₂ films achieve an increased density, high electron conductivity, good wettability, and abundant interconnected mesopore channels to promote ion transport efficiently, that is, more cations can intercalate/deintercalate in the charging–discharging process. As a result, with the increase of the applying pressure, the d‐Ti₃C₂ film pressured at 40 MPa in 1 m Li₂SO₄ exhibits an ultrahigh capacitance of over 633 F cm^?3, outstanding energy density, and cyclic stability. Especially, the corresponding SC in 1 m 1‐ethyl‐3‐methylimidazolium tetrafluoroborate/acetonitrile organic electrolyte shows a high volumetric energy density of 41 Wh L^?1, which is the highest value reported for the SCs based on MXene materials in organic electrolytes. The outstanding volumetric electrochemical performance and thermal stability of the SCs based on the ultracompact d‐Ti₃C₂ film demonstrate their promising potential as forceful power sources for small electronic devices.     

MoS2/Si Heterojunction with Vertically Standing Layered Structure for Ultrafast,High‐Detectivity,Self‐Driven Visible–Near Infrared Photodetectors

As an interesting layered material, molybdenum disulfide (MoS₂) has been extensively studied in recent years due to its exciting properties. However, the applications of MoS₂ in optoelectronic devices are impeded by the lack of high‐quality p–n junction, low light absorption for mono‐/multilayers, and the difficulty for large‐scale monolayer growth. Here, it is demonstrated that MoS₂ films with vertically standing layered structure can be deposited on silicon substrate with a scalable sputtering method, forming the heterojunction‐type photodetectors. Molecular layers of the MoS₂ films are perpendicular to the substrate, offering high‐speed paths for the separation and transportation of photo‐generated carriers. Owing to the strong light absorption of the relatively thick MoS₂ film and the unique vertically standing layered structure, MoS₂/Si heterojunction photodetectors with unprecedented performance are actualized. The self‐driven MoS₂/Si heterojunction photodetector is sensitive to a broadband wavelength from visible light to near‐infrared light, showing an extremely high detectivity up to ≈10¹³ Jones (Jones = cm Hz^1/2 W^?1), and an ultrafast response speed of ≈3 μs. The performance is significantly better than the photodetectors based on mono‐/multilayer MoS₂ nanosheets. Additionally, the MoS₂/Si photodetectors exhibit excellent stability in air for a month. This work unveils the great potential of MoS₂/Si heterojunction for optoelectronic applications.     

A Stable Conversion and Alloying Anode for Potassium‐Ion Batteries: A Combined Strategy of Encapsulation and Confinement

Potassium‐ion batteries based on conversion/alloying reactions have high potential applications in new‐generation large‐scale energy storage. However, their applications are hindered by inherent large‐volume variations and sluggish kinetics of the conversion/alloying‐type electrode materials during the repeated insertion and extraction of bulky K⁺ ions. Although some efforts have been focused on this issue, the reported potassium‐ion batteries still suffer from poor cycling lifespans. Here, a superior stable antimony selenide (Sb₂Se₃) anode is reported for high‐performance potassium‐ion batteries through a combined strategy of conductive encapsulation and 2D confinement. The Sb₂Se₃ nanorods are uniformly coated with a conductive N‐doped carbon layer and then confined between graphene nanosheets. The synergistic effects between conductive coating and confinement effectively buffer the large volumetric variation of the conversion/alloying anodes, which can maintain structural stability for superior cyclability. The as‐prepared anodes exhibit a high reversible specific capacity of ≈590 mA h g^?1 and outstanding cycling stability over 350 cycles. In situ and ex situ characterizations reveal a high structural integration of the large‐volume‐change Sb₂Se₃ anodes during a reversible K storage mechanism of two‐step conversion and multistep alloying processes. This work can open up a new possibility for the design of stable conversion/alloying‐based anodes for high‐performance potassium‐ion batteries.     

Enhanced Performance Consistency in Nanoparticle/TIPS Pentacene‐Based Organic Thin Film Transistors

In this study, inorganic silica nanoparticles are used to manipulate the morphology of 6,13‐bis(triisopropylsilylethynyl)‐pentacene (TIPS pentacene) thin films and the performance of solution‐processed organic thin‐film transistors (OTFTs). This approach is taken to control crystal anisotropy, which is the origin of poor consistency in TIPS pentacene based OTFT devices. Thin film active layers are produced by drop‐casting mixtures of SiO₂ nanoparticles and TIPS pentacene. The resultant drop‐cast films yield improved morphological uniformity at ～10% SiO₂ loading, which also leads to a 3‐fold increase in average mobility and nearly 4 times reduction in the ratio of measured mobility standard deviation (μ_Stdev) to average mobility (μ_Avg). Grazing‐incidence X‐ray diffraction, scanning and transmission electron microscopy as well as polarized optical microscopy are used to investigate the nanoparticle‐mediated TIPS pentacene crystallization. The experimental results suggest that the SiO₂ nanoparticles mostly aggregate at TIPS pentacene grain boundaries, and 10% nanoparticle concentration effectively reduces the undesirable crystal misorientation without considerably compromising TIPS pentacene crystallinity.     

van der Waals Epitaxial Growth of Atomically Thin 2D Metals on Dangling‐Bond‐Free WSe2 and WS2

2D metals have attracted considerable recent attention for their special physical properties, such as charge density waves, magnetism, and superconductivity. However, despite some recent efforts, the synthesis of ultrathin 2D metals nanosheets down to monolayer thickness remains a significant challenge. Herein, by using atomically flat 2D WSe₂ or WS₂ as the growth substrate, the synthesis of atomically thin 2D metallic MTe₂ (M = V, Nb, Ta) single crystals with the thickness down to the monolayer regime and the creation of atomically thin MTe₂/WSe₂ (WS₂) vertical heterojunctions is reported. Comparison with the growth on the SiO₂/Si substrate under the same conditions reveals that the utilization of the dangling‐bond‐free WSe₂ or WS₂ as the van der Waals epitaxy substrates is crucial for the successful realization of atomically thin MTe₂ (M = V, Nb, Ta) nanosheets. It is further shown that the epitaxial grown 2D metals can function as van der Waals contacts for 2D semiconductors with little interface damage and improved electronic performance. This study defines a robust van der Waals epitaxy pathway to ultrathin 2D metals, which is essential for fundamental studies and potential technological applications of this new class of materials at the 2D limit.     

In Situ Growth of [hk1]‐Oriented Sb2S3 for Solution‐Processed Planar Heterojunction Solar Cell with 6.4% Efficiency

Binary compound antimony sulfide (Sb₂S₃) with its nontoxic and earth‐abundant constituents, is a promising light‐harvesting material for stable and high efficiency thin film photovoltaics. The intrinsic quasi‐1D (Q1D) crystal structure of Sb₂S₃ is known to transfer photogenerated carriers rapidly along the [hk1] orientation. However, producing Sb₂S₃ devices with precise control of [hk1] orientation is challenging and unfavorable crystal orientations of Sb₂S₃ result in severe interface and bulk recombination losses. Herein, in situ vertical growth of Sb₂S₃ on top of ultrathin TiO₂/CdS as the electron transport layer (ETL) by a solution method is demonstrated. The planar heterojunction solar cell using [hk1]‐oriented Sb₂S₃ achieves a power conversion efficiency of 6.4%, performing at almost 20% higher than devices based on a [hk0]‐oriented absorber. This work opens up new prospects for pursuing high‐performance Sb₂S₃ thin film solar cells by tailoring the crystal orientation.     

Single Pulse Laser‐Induced Phase Transitions of PLD‐Deposited Ge2Sb2Te5 Films

Phase transformations between amorphous and crystallized states are induced by irradiation with a single nanosecond laser pulse in Ge₂Sb₂Te₅ films grown by pulsed laser deposition. By adjusting the laser fluence, the two different phases are obtained and can be distinguished by their different optical reflectivity. The effect of laser fluence on the crystalline nature of the films is studied in detail. Large structural differences between the laser‐irradiated and thermally annealed films are revealed, due to the high heating rate and short duration of the laser pulse. X‐ray reflectivity measurements show a density increase of 3.58% upon laser‐induced crystallization.     

Structure and Morphology of PDI8‐CN2 for n‐Type Thin‐Film Transistors

A multiscale investigation of N,N′‐bis(n‐octyl)‐x:y, dicyanoperylene‐3,4:9,10‐bis(dicarboximide), PDI8‐CN2, shows the same molecular arrangement in the bulk and in thin films sublimated on SiO₂/Si wafers. Non‐conventional powder diffraction methods and theoretical calculations concur to provide a coherent picture of the crystalline structure. X‐ray diffraction (XRD) and atomic force microscopy (AFM) analyses of films of different thickness deposited at different substrate temperatures indicate the existence of two temperature‐dependent deposition regimes: a low‐temperature (room temperature) regime and a high‐temperature (80–120 °C) one, each characterized by different growth mechanisms. These mechanisms eventually result in different morphological and structural features of the films, which appear to be highly correlated with the trend of the electrical parameters that are measured in PDI8‐CN2‐based field‐effect transistors.     

Hierarchical Ordered Dual‐Mesoporous Polypyrrole/Graphene Nanosheets as Bi‐Functional Active Materials for High‐Performance Planar Integrated System of Micro‐Supercapacitor and Gas Sensor

Planar integrated systems of micro‐supercapacitors (MSCs) and sensors are of profound importance for 3C electronics, but usually appear poor in compatibility due to the complex connections of device units with multiple mono‐functional materials. Herein, 2D hierarchical ordered dual‐mesoporous polypyrrole/graphene (DM‐PG) nanosheets are developed as bi‐functional active materials for a novel prototype planar integrated system of MSC and NH₃ sensor. Owing to effective coupling of conductive graphene and high‐sensitive pseudocapacitive polypyrrole, well‐defined dual‐mesopores of ≈7 and ≈18 nm, hierarchical mesoporous network, and large surface area of 112 m² g^?1, the resultant DM‐PG nanosheets exhibit extraordinary sensing response to NH₃ as low as 200 ppb, exceptional selectivity toward NH₃ that is much higher than other volatile organic compounds, and outstanding capacitance of 376 F g^?1 at 1 mV s^?1 for supercapacitors, simultaneously surpassing single‐mesoporous and non‐mesoporous counterparts. Importantly, the bi‐functional DM‐PG‐based MSC‐sensor integrated system represents rapid and stable response exposed to 10–40 ppm of NH₃ after only charging for 100 s, remarkable sensitivity of NH₃ detection that is close to DM‐PG‐based MSC‐free sensor, impressive flexibility with ≈82% of initial response value even at 180°, and enhanced overall compatibility, thereby holding great promise for ultrathin, miniaturized, body‐attachable, and portable detection of NH₃.