Polarization‐Sensitive Ultraviolet Photodetection of Anisotropic 2D GeS2

Polarization‐sensitive photodetection in the UV region is highly indispensable in many military and civilian applications. UV‐polarized photodetection usually relies on the use of wide bandgap semiconductors with 1D nanostructures requiring complicated nanofabrication processes. Although the emerging anisotropic 2D semiconductors shed light on the detection of polarization with a simple device architecture, bandgaps of such reported 2D semiconductors are too small to be applied for visible–blind UV‐polarized photodetection. Here, germanium disulfide (GeS₂), the widest bandgap (>3 eV) in the family of in‐plane anisotropic 2D semiconductors explored to date, is introduced as an ideal candidate for UV‐polarized photodetection. The structural, vibrational, and optical anisotropies of GeS₂ are systematically investigated from theory to experiment. GeS₂‐based photodetectors show a strong polarization‐dependent photoresponse in the UV region. GeS₂ with a wide bandgap and high in‐plane anisotropy not only enriches the family of anisotropic 2D semiconductors but also expands the polarized photodetection from the current visible and near‐infrared to the brand‐new UV region.     

Highly Stretchable Bilayer Lattice Structures That Elongate via In‐Plane Deformation

Many emerging technologies such as wearable batteries and electronics require stretchable functional structures made from intrinsically less deformable materials. The stretch capability of most demonstrated stretchable structures often relies on either initially out‐of‐plane configurations or the out‐of‐plane deflection of planar patterns. Such nonplanar features may dramatically increase the surface roughness, cause poor adhesion and adverse effects on subsequent multilayer processing, thereby posing a great challenge for flexible devices that require smooth surfaces (e.g., transparent electrodes in which flat‐surface‐enabled high optical transmittance is preferred). Inspired by the lamellar layouts of collagenous tissues, this work demonstrates a planar bilayer lattice structure, which can elongate substantially via only in‐plane motion and thus maintain a smooth surfaces. The constructed bilayer lattice exhibits a large stretchability up to 360%, far beyond the inherent deformability of the brittle constituent material and comparable to that of state‐of‐the‐art stretchable structures for flexible electronics. A stretchable conductor employing the bilayer lattice designs can remain electrically conductive at a strain of 300%, demonstrating the functionality and potential applications of the bilayer lattice structure. This design opens a new avenue for the development of stretchable structures that demand smooth surfaces.     

In‐Plane Self‐Turning and Twin Dynamics Renders Large Stretchability to Mono‐Like Zigzag Silicon Nanowire Springs

Crystalline Si nanowire (SiNW) springs, produced via a low temperature (<350 °C) thin film technology, are ideal building blocks for stretchable electronics. Herein, a novel cyclic crystallographic‐index‐lowering self‐turning and twin dynamics is reported, during a tin‐catalyzed in‐plane growth of SiNWs, which results in a periodic zigzag SiNW without any external parametric intervention. More interestingly, a unique twin‐reflected interlaced crystal‐domain structure has been identified for the first time, while in situ and real‐time scanning electron microscopy observations reveal a new twin‐triggering growth mechanism that is the key to reset a complete zigzag growth cycle. Direct “stress–strain” testing of the SiNW springs demonstrates a large stretchability of 12% under tensile loading, indicating a whole new strategy and capability to engineer mono‐like SiNW channels for high performance stretchable electronics.     

Virtually Bare Nanocrystal Surfaces: Significantly Enhanced Electrical Transport in CuInSe2 and CuIn1−xGaxSe2 Thin Films upon Ligand Exchange with Thermally Degradable 1‐Ethyl‐5‐Thiotetrazole

A facile and safe ligand exchange method for readily synthesized CuInSe₂ (CIS) and CuIn_1‐xGa_xSe₂ (CIGS) nanocrystals (NCs) from oleylamine to 1‐ethyl‐5‐thiotetrazole, preserving the colloidal stability of the chalcopyrite structure, is presented. 1‐Ethyl‐5‐thiotetrazole as thermally degradable ligand is adapted for the first time for trigonal pyramidal CIS (18 nm), elongated CIS (9 nm) and CIGS NCs (6 nm). Exchanged NC solutions are processed onto gold electrodes yielding ordered thin films. These films are thermally annealed at 260 °C to completely remove 1‐ethyl‐5‐thiotetrazol leaving individual closely assembled NCs with virtually bare surfaces. The current–voltage characteristics of the NC solids are measured prior to ligand thermolysis in the dark and under illumination and after ligand thermolysis in the same manner. The conductivity of trigonal pyramidal CIS increases by four orders of magnitude (1.4 × 10^?9 S cm^?1 (dark) to 1.4 × 10^?5 S cm^?1 (illuminated)) for ligand‐free NC films. Elongated CIS NC films show a three orders of magnitude conductivity increase and CIGS NC films exhibit improved conductivity by two orders of magnitude. Conductivity enhancement thereby depends on the NC size accentuating the role of trap‐states and internal grain boundaries in ligand‐free NC solids for electrical transport. This approach for the first time offers the possibility to address chalcopyrite materials’ electrical properties in a virtually ligand‐free state.     

Effects of Interfacial Dielectric Layers on the Electrical Performance of Top‐Gate In‐Ga‐Zn‐Oxide Thin‐Film Transistors

We investigate the effects of interfacial dielectric layers (IDLs) on the electrical properties of top‐gate In‐Ga‐Zn‐oxide (IGZO) thin film transistors (TFTs) fabricated at low temperatures below 200°C, using a target composition of In:Ga:Zn = 2:1:2 (atomic ratio). Using four types of TFT structures combined with such dielectric materials as Si₃N₄ and Al₂O₃, the electrical properties are analyzed. After post‐annealing at 200°C for 1 hour in an O₂ ambient, the sub‐threshold swing is improved in all TFT types, which indicates a reduction of the interfacial trap sites. During negative‐bias stress tests on TFTs with a Si3N4 IDL, the degradation sources are closely related to unstable bond states, such as Si‐based broken bonds and hydrogen‐based bonds. From constant‐current stress tests of Id = 3 µA, an IGZO‐TFT with heat‐treated Si₃N₄ IDL shows a good stability performance, which is attributed to the compensation effect of the original charge‐injection and electron‐trapping behavior.     

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.     

Doping Dependent In‐Plane and Cross‐Plane Thermoelectric Performance of Thin n‐Type Polymer P(NDI2OD‐T2) Films

Thermoelectric generators pose a promising approach in renewable energies as they can convert waste heat into electricity. In order to build high efficiency devices, suitable thermoelectric materials, both n‐ and p‐type, are needed. Here, the n‐type high‐mobility polymer poly[N,N′‐bis(2‐octyldodecyl)naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene) (P(NDI2OD‐T2)) is focused upon. Via solution doping with 4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzoimidazol‐2‐yl)‐N,N‐diphenylaniline (N‐DPBI), a maximum power factor of (1.84 ± 0.13) µW K^?2 m^?1 is achieved in an in‐plane geometry for 5 wt% dopant concentration. Additionally, UV–vis spectroscopy and grazing‐incidence wide‐angle X‐ray scattering are applied to elucidate the mechanisms of the doping process and to explain the discrepancy in thermoelectric performance depending on the charge carriers being either transported in‐plane or cross‐plane. Morphological changes are found such that the crystallites, built‐up by extended polymer chains interacting via lamellar and π–π stacking, re‐arrange from face‐ to edge‐on orientation upon doping. At high doping concentrations, dopant molecules disturb the crystallinity of the polymer, hindering charge transport and leading to a decreased power factor at high dopant concentrations. These observations explain why an intermediate doping concentration of N‐DPBI leads to an optimized thermoelectric performance of P(NDI2OD‐T2) in an in‐plane geometry as compared to the cross‐plane case.     

CoFe2O4 and CoFe2O4‐SiO2 Nanoparticle Thin Films with Perpendicular Magnetic Anisotropy for Magnetic and Magneto‐Optical Applications

This paper presents an efficient colloidal approach to process CoFe₂O₄ and SiO₂ nanoparticles into thin films for magnetic and magneto‐optical applications. Thin films of varying CoFe₂O₄‐to‐SiO₂ ratios (from 0 to 90 wt%) are obtained by sequential spin coating‐calcination cycles from the corresponding nanoparticle dispersions. Scanning electron microscopy analysis reveals a crack free and nanoparticulate structure of the sintered films with thicknesses of 480–1200 nm. Results from the optical characterization indicate a direct band gap ranging from 2.6 to 3.9 eV depending on the SiO₂ content. Similarly, the refractive indices and absorption coefficients are tunable upon SiO₂ incorporation. In‐plane measurements of the magnetic properties of the CoFe₂O₄ films reveal a superparamagnetic behavior with both Co²⁺ and Fe³⁺ contributing to the magnetism. Polar Kerr measurements show the presence of a spontaneous magnetization in the CoFe₂O₄ and CoFe₂O₄‐SiO₂ (with SiO₂ < 50 wt%) films, pointing to magnetic anisotropy perpendicular to the substrate. The origin of this effect is attributed to the constrained sintering conditions of the nano­particulate film and the negative magnetostriction of CoFe₂O₄.     

Atomic Insight into Thermolysis‐Driven Growth of 2D MoS2

Understanding and controlling the transformations of transition metal dichalcogenides (TMDs) from amorphous precursors into two‐dimensional (2D) materials is important for guiding synthesis, directing fabrication, and tailoring functional properties. Here, the combined effects of thermal energy and electron beam irradiation are explored on the structural evolution of 2D MoS₂ flakes through the thermal decomposition of a (NH₄)₂MoS₄ precursor inside an ultrahigh vacuum (10^?9 Torr) scanning transmission electron microscope (STEM). The influence of reaction temperature, growth substrate, and the initial precursor morphology on the resulting 2D MoS₂ flake morphology, edge structures, and point defects are explored. Although thermal decomposition occurs extremely fast at elevated temperatures and is difficult to capture using current STEM techniques, electron beam irradiation can induce local transformations at lower temperatures, enabling direct observation and interpretation of critical growth steps including oriented attachment and transition from single‐ to multilayer structures at atomic resolution. An increase in the number of layers of the MoS₂ flakes from island growth is investigated using electron beam irradiation. These findings provide insight into the growth mechanisms and factors that control the synthesis of few‐layer MoS₂ flakes through thermolysis and toward the prospect of atomically precise control and growth of 2D TMDs.     

Cu2O Nanocrystal‐Templated Growth of Cu2S Nanocages with Encapsulated Au Nanoparticles and In‐Situ Transmission X‐ray Microscopy Study

Cubic and octahedral Cu₂O nanocrystals and Au–Cu₂O core–shell heterostructures are used as sacrificial templates for the growth of Cu₂S nanocages and Au–Cu₂S core–cage structures. A rapid sulfidation process involving a surface reaction of Cu₂O nanocrystals with Na₂S, followed by etching of the Cu₂O cores with HCl solution for ≈5 sec, results in the fabrication of Cu₂S cages with a wall thickness of 10–20 nm. Transmission electron microscopy characterization reveals the formation of crystalline walls and the presence of ultrasmall pores with sizes of 1 nm or less. Formation of Cu₂O–Cu₂S core–shell structures and their conversion into Cu₂S cages is verified by UV–vis absorption spectroscopy. X‐ray photoelectron spectra further confirm the composition of the cages as Cu₂S. The entire hollowing process via the Kirkendall effect is recorded using in‐situ transmission X‐ray microscopy. After shell formation, continuous ionic diffusion removes the interior Cu₂O. Intermediate structures with remaining central Cu₂O portions and bridging arms to the surrounding cages are observed. The nanocages are also shown to allow molecular transport: anthracene and pyrene penetration into the cages leads to enhanced fluorescence quenching immediately upon adsorption onto the surfaces of the encapsulated gold nanocrystals.     

Anisotropy in Shape and Ligand‐Conjugation of Hybrid Nanoparticulates Manipulates the Mode of Bio–Nano Interaction and Its Outcome

In an attempt to manipulate the biological features of nanomaterials via both anisotropic shape and ligand modification, four types of nanoparticulates with good morphological stability are designed and engineered, including hybrid nanospheres, nanodiscs, and nanodiscs with edge modification or plane modification of octa‐arginine (R8) sequence. It is found that the R8 modification anisotropy can trigger huge differences in the endocytosis, intracellular trafficking, and even tissue penetration of nanoparticulates. From plane modification to edge modification of R8, the maximum increase in cell uptake is up to 17‐fold, which is much more significant than shape anisotropy alone. On the other hand, six types of different cell lines are investigated to simulate biological microenvironment. It is demonstrated that the maximum difference in cell uptake among six cell lines is 12‐fold. Three main driving forces are found to contribute to such bio–nano interactions. Based on the findings of this study, it seems possible to manipulate the biointeraction mode of nanomaterials and its output by regulating their anisotropy in both shape and ligand modification.     

Self‐Assembled In‐Plane Growth of Mg2SiO4 Nanowires on Si Substrates Catalyzed by Au Nanoparticles

In‐plane growth of Mg₂SiO₄ nanowires on Si substrates is achieved by using a vapor transport method with Au nanoparticles as catalyst. The self‐assembly of the as‐grown nanowires shows dependence on the substrate orientation, i.e., they are along one, two, and three particular directions on Si (110), (100), and (111) substrates, respectively. Detailed electron microscopy studies suggest that the Si substrates participate in the formation of Mg₂SiO₄, and the epitaxial growth of the nanowires is confined along the Si <110> directions. This synthesis route is quite reliable, and the dimensions of the Mg₂SiO₄ nanowires can be well controlled by the experiment parameters. Furthermore, using these nanowires, a lithography‐free method is demonstrated to fabricate nanowalls on Si substrates by controlled chemical etching. The Au nanoparticle catalyzed in‐plane epitaxial growth of the Mg₂SiO₄ nanowires hinges on the intimate interactions between substrates, nanoparticles, and nanowires, and our study may help to advance the developments of novel nanomaterials and functional nanodevices.     

2D Versus 3D Crystalline Order in Thin Films of Regioregular Poly(3‐hexylthiophene) Oriented by Mechanical Rubbing and Epitaxy

Highly oriented films of regioregular poly(3‐hexylthiophene) (P3HT) are prepared by two methods: mechanical rubbing and directional epitaxial crystallization. The structure, nanomorphology, and optical and charge‐transport properties of the oriented films are investigated by electron diffraction, high resolution transmission electron microscopy (HR‐TEM), absorption spectroscopy, and transistor field‐effect measurements. In rubbed films, P3HT chains align parallel to the rubbing direction and the crystalline domains orientation changes from preferential edge‐on to flat‐on orientation. The maximum in‐plane orientation probed by absorption spectroscopy is a function of the polymer molecular weight M_w; the lower the M_w, the higher the in‐plane orientation induced by rubbing. The anisotropy of field‐effect mobility measured parallel and perpendicular to the rubbing shows the same trend as the absorption. The M_w‐dependence of the orientation is explained in terms of chain folding and entanglement that prevent the reorientation and reorganization of the π‐stacked chains, especially when M_w ≥ 50 kDa. For comparison, P3HT films are oriented by directional epitaxial crystallization using a zone‐melting technique. Electron diffraction and HR‐TEM show that epitaxial and rubbed films differ in terms of intralamellar order within layers of π‐stacked chains. Comparison of UV‐vis absorption spectra for the different samples suggests that the vibronic structure is sensitive to intralamellar disorder.     

1D SnO2 with Wire‐in‐Tube Architectures for Highly Selective Electrochemical Reduction of CO2 to C1 Products

Electrochemical reduction of CO₂ (ERC) into useful products, such as formic acid and carbon monoxide, is a fascinating approach for CO₂ fixation as well as energy storage. Sn‐based materials are attractive catalysts for highly selective ERC into C₁ products (including HCOOH and CO), but still suffer from high overpotential, low current density, and poor stability. Here, One‐dimensional (1D) SnO₂ with wire‐in‐tube (WIT) structure is synthesized and shows superior selectivity for C₁ products. Using the WIT SnO₂ as the ERC catalyst, very high Faradaic efficiency of C₁ products (>90%) can be achieved at a wide potential range from ?0.89 to ?1.29 V versus RHE, thus substantially suppressing the hydrogen evolution reaction. The electrocatalyst also exhibits excellent long‐term stability. The improved catalytic activity of the WIT SnO₂ over the commercial SnO₂ nanoparticle indicates that higher surface area and large number of grain boundaries can effectively enhance the ERC activity. Synthesized via a facile and low‐cost electrospinning technology, the reduced WIT SnO₂ can serve as a promising electrocatalyst for efficient CO₂ to C₁ products conversion.     

Long‐Term Electrical and Mechanical Function Monitoring of a Human‐on‐a‐Chip System

The goal of human‐on‐a‐chip systems is to capture multiorgan complexity and predict the human response to compounds within physiologically relevant platforms. The generation and characterization of such systems is currently a focal point of research given the long‐standing inadequacies of conventional techniques for predicting human outcome. Functional systems can measure and quantify key cellular mechanisms that correlate with the physiological status of a tissue, and can be used to evaluate therapeutic challenges utilizing many of the same endpoints used in animal experiments or clinical trials. Culturing multiple organ compartments in a platform creates a more physiologic environment (organ–organ communication). Here is reported a human 4‐organ system composed of heart, liver, skeletal muscle, and nervous system modules that maintains cellular viability and function over 28 days in serum‐free conditions using a pumpless system. The integration of noninvasive electrical evaluation of neurons and cardiac cells and mechanical determination of cardiac and skeletal muscle contraction allows the monitoring of cellular function, especially for chronic toxicity studies in vitro. The 28‐day period is the minimum timeframe for animal studies to evaluate repeat dose toxicity. This technology can be a relevant alternative to animal testing by monitoring multiorgan function upon long‐term chemical exposure.     

Precise Control of Lamellar Thickness in Highly Oriented Regioregular Poly(3‐Hexylthiophene) Thin Films Prepared by High‐Temperature Rubbing: Correlations with Optical Properties and Charge Transport

Precise control of orientation and crystallinity is achieved in regioregular poly(3‐hexylthiophene) (P3HT) thin films by using high‐temperature rubbing, a fast and effective alignment method. Rubbing P3HT films at temperatures T_R ≥ 144 °C generates highly oriented crystalline films with a periodic lamellar morphology with a dichroic ratio reaching 25. The crystallinity and the average crystal size along the chain axis direction, l_c, are determined by high‐resolution transmission electron microscopy and differential scanning calorimetry. The inverse of the lamellar period l scales with the supercooling and can accordingly be controlled by the rubbing temperature T_R. Uniquely, the observed exciton coupling in P3HT crystals is correlated to the length of the average planarized chain segments l_c in the crystals. The high alignment and crystallinity observed for T_R > 200 °C cannot translate to high hole mobilities parallel to the rubbing because of the adverse effect of amorphous zones interrupting charge transport between crystalline lamellae. Although tie chains bridge successive P3HT crystals through amorphous zones, their twisted conformation restrains interlamellar charge transport. The evolution of charge transport anisotropy is correlated to the evolution of the dominant contact plane from mainly face‐on (T_R ≤ 100 °C) to edge‐on (T_R ≥ 170 °C).     

Nonvolatile Electrical Control and Heterointerface‐Induced Half‐Metallicity of 2D Ferromagnets

Electrical control of atom‐thick van der Waals (vdW) ferromagnets is a key toward future magnetoelectric nanodevices; however, state‐of‐the‐art control approaches are volatile. In this work, introducing ferroelectric switching as an aided layer is demonstrated to be an effective approach toward achieving nonvolatile electrical control of 2D ferromagnets. For example, when a ferromagnetic monolayer CrI₃ and ferroelectric MXene Sc₂CO₂ come together into multiferroic heterostructures, CrI₃ is controlled by polarized states P↑ and P↓ of Sc₂CO₂. P↑ Sc₂CO₂ does not change the semiconducting nature of CrI₃, but surprisingly P↓ Sc₂CO₂ makes CrI₃ half‐metallic. Nonvolatility of the electrical switching between two oppositely ferroelectric polarized states, therefore, indirectly enables nonvolatile electrical control of CrI₃ between ferromagnetic semiconductor and half‐metal. The heterointerface‐induced half‐metallicity in CrI₃ is intrinsic without resorting to any chemical functionalization or external physical modification, which is rather beneficial to the practical application. This work paves the way for nonvolatile electrical control of 2D vdW ferromagnets and applications of CrI₃ in half‐metal‐based nanospintronics.     

Combinatorial Study of Temperature‐Dependent Nanostructure and Electrical Conduction of Polymer Semiconductors: Even Bimodal Orientation Can Enhance 3D Charge Transport

Temperature‐dependent (80–350 K) charge transport in polymer semiconductor thin films is studied in parallel with in situ X‐ray structural characterization at equivalent temperatures. The study is conducted on a pair of isoindigo‐based polymers containing the same π‐conjugated backbone with different side chains: one with siloxane‐terminated side chains (PII2T‐Si) and the other with branched alkyl‐terminated side chains (PII2T‐Ref). The different chemical moiety in the side chain results in a completely different film morphology. PII2T‐Si films show domains of both edge‐on and face‐on orientations (bimodal orientation) while PII2T‐Ref films show domains of edge‐on orientation (unimodal orientation). Electrical transport properties of this pair of polymers are also distinctive, especially at high temperatures (>230 K). Smaller activation energy (E _A) and larger pre‐exponential factor (μ ₀) in the mobility‐temperature Arrhenius relation are obtained for PII2T‐Si films when compared to those for PII2T‐Ref films. The results indicate that the more effective transport pathway is formed for PII2T‐Si films than for the other, despite the bimodally oriented film structure. The closer π–π packing distance, the longer coherence length of the molecular ordering, and the smaller disorder of the transport energy states for PII2T‐Si films altogether support the conduction to occur more effectively through a system with both edge‐on and face on orientations of the conjugated molecules. Reminding the 3D nature of conduction in polymer semiconductor, our results suggest that the engineering rules for advanced polymer semiconductors should not simply focus on obtaining films with conjugated backbone in edge‐on orientation only. Instead, the engineering should also encounter the contribution of the inevitable off‐directional transport process to attain effective transport from polymer thin films.     

Synthesis of Atomically Thin 1T‐TaSe2 with a Strongly Enhanced Charge‐Density‐Wave Order

Bulk 1T‐TaSe₂ as a charge‐density‐wave (CDW) conductor is of special interest for CDW‐based nanodevice applications because of its high CDW transition temperature. Reduced dimensionality of the strongly correlated material is expected to result in significantly different collective properties. However, the growth of atomically thin 1T‐TaSe₂ crystals remains elusive, thus hampering studies of dimensionality effects on the CDW of the material. Herein, chemical vapor deposition (CVD) of atomically thin TaSe₂ crystals is reported with controlled 1T phase. Scanning transmission electron microscopy suggests the high crystallinity and the formation of CDW superlattice in the ultrathin 1T‐TaSe₂ crystals. The commensurate–incommensurate CDW transition temperature of the grown 1T‐TaSe₂ increases with decreasing film thickness and reaches a value of 570 K in a 3 nm thick layer, which is 97 K higher than that of previously reported bulk 1T‐TaSe₂. This work enables the exploration of collective phenomena of 1T‐TaSe₂ in the 2D limit, as well as offers the possibility of utilizing the high‐temperature CDW films in ultrathin phase‐change devices.