Substrate-Free Self-Assembly Approach toward Large-Area Nanomembranes

Free-standing two-dimensional nanostrucutures, such as graphene and semiconductor nanomembranes (NMs) featuring their integration with flexible polymer substrates, address applications in which electronic devices need to be stretchable or conformally positioned to nonplanar surfaces. We report a surfactant-directed surface assembly approach to producing large-area NMs at the water–air interface. The NMs were produced by employing the surfactants as templates as well as incorporating them in the crystal structures. By using excess amount of sodium dodecylsulfate (SDS), a tightly packed monolayer of dodecylsulfate (DS) ion was formed and directed the crystallization of submillimeter-sized zinc hydroxy dodecylsulfate (ZHDS) single-crystalline NMs over the entire water surface. This free-standing NM can be readily transferred to an arbitrary substrate and converted to ZnO <i>via</i> heat treatment. A flexible thin-film transistor was also fabricated using the transferred NMs and demonstrated reasonably good n-type transport properties. This approach circumvented the needs of single-crystalline substrates for making large-area NMs from materials that do not possess a laminate structure. It is a low-cost and large-scale synthesis technique and has great potential in developing NMs and flexible devices from various functional materials that are not feasible by conventional selective etching or delamination approaches

Cellulose Nanofibril/Reduced Graphene Oxide/Carbon Nanotube Hybrid Aerogels for Highly Flexible and All-Solid-State Supercapacitors

A novel type of highly flexible and all-solid-state supercapacitor that uses cellulose nanofibril (CNF)/reduced graphene oxide (RGO)/carbon nanotube (CNT) hybrid aerogels as electrodes and H₂SO₄/poly­(vinyl alcohol) (PVA) gel as the electrolyte was developed and is reported here. These flexible solid-state supercapacitors were fabricated without any binders, current collectors, or electroactive additives. Because of the porous structure of the CNF/RGO/CNT aerogel electrodes and the excellent electrolyte absorption properties of the CNFs present in the aerogel electrodes, the resulting flexible supercapacitors exhibited a high specific capacitance (i.e., 252 F g^–1 at a discharge current density of 0.5 A g^–1) and a remarkable cycle stability (i.e., more than 99.5% of the capacitance was retained after 1000 charge–discharge cycles at a current density of 1 A g^–1). Furthermore, the supercapacitors also showed extremely high areal capacitance, areal power density, and energy density (i.e., 216 mF cm^–2, 9.5 mW cm^–2, and 28.4 μWh cm^–2, respectively). In light of its excellent electrical performance, low cost, ease of large-scale manufacturing, and environmental friendliness, the CNF/RGO/CNT aerogel electrodes may have a promising application in the development of flexible energy-storage devices

Graphene/Phase Change Material Nanocomposites: Light-Driven, Reversible Electrical Resistivity Regulation via Form-Stable Phase Transitions

Innovative photoresponsive materials are needed to address the complexity of optical control systems. Here, we report a new type of photoresponsive nanomaterial composed of graphene and a form-stable phase change material (PCM) that exhibited a 3 orders of magnitude change in electrical resistivity upon light illumination while retaining its overall original solid form at the macroscopic level. This dramatic change in electrical resistivity also occurred reversibly through the on/off control of light illumination. This was attributed to the reversible phase transition (i.e., melting/recrystallization) behavior of the microscopic crystalline domains present in the form-stable PCM. The reversible phase transition observed in the graphene/PCM nanocomposite was induced by a reversible temperature change through the on/off control of light illumination because graphene can effectively absorb light energy and convert it to thermal energy. In addition, this graphene/PCM nanocomposite also possessed excellent mechanical properties. Such photoresponsive materials have many potential applications, including flexible electronics

Flexible Infrared Responsive Multi-Walled Carbon Nanotube/Form-Stable Phase Change Material Nanocomposites

Flexible infrared (IR)-responsive materials, such as polymer nanocomposites, that exhibit high levels of IR responses and short response times are highly desirable for various IR sensing applications. However, the IR-induced photoresponses of carbon nanotube (CNT)/polymer nanocomposites are typically limited to 25%. Herein, we report on a family of unique nanocomposite films consisting of multi-walled carbon nanotubes (MWCNTs) uniformly distributed in a form-stable phase change material (PCM) that exhibited rapid, dramatic, reversible, and cyclic IR-regulated responses in air. The 3 wt % MWCNT/PCM nanocomposite films demonstrated cyclic, IR-regulated on/off electrical conductivity ratios of 11.6 ± 0.6 and 570.0 ± 70.5 times at IR powers of 7.3 and 23.6 mW/mm², respectively. The excellent performances exhibited by the MWCNT/PCM nanocomposite films were largely attributed to the IR-regulated cyclic and reversible form-stable phase transitions occurring in the PCM matrix due to MWCNT’s excellent photoabsorption and thermal conversion capabilities, which subsequently affected the thickness of the interfacial PCM between adjacent conductive MWCNTs and thus the electron tunneling efficiency between the MWCNTs. Our findings suggest that these unique MWCNT/PCM nanocomposites offer promising new options for high-performance and flexible optoelectronic devices, including thermal imaging, IR sensing, and optical communication

Cl-Doped ZnO Nanowires with Metallic Conductivity and Their Application for High-Performance Photoelectrochemical Electrodes

Doping semiconductor nanowires (NWs) for altering their electrical and optical properties is a critical strategy for tailoring the performance of nanodevices. ZnO NWs grown by hydrothermal method are pervasively used in optoelectronic, photovoltaic, and piezoelectric energy-harvesting devices. We synthesized in situ Cl-doped ZnO NWs with metallic conductivity that would fit seamlessly with these devices and improve their performance. Possible Cl doping mechanisms were discussed. UV–visible absorption spectroscopy confirmed the visible light transparency of Cl-doped ZnO NWs. Cl-doped ZnO NW/TiO₂ core/shell-structured photo­electro­chemical (PEC) anode was fabricated to demonstrate the application potential of highly conductive ZnO NWs. Higher photocurrent density and overall PEC efficiency compared with the undoped ZnO NW-based device were achieved. The successful doping and low resistivity of ZnO could unlock the potential of ZnO NWs for applications in low-cost flexible transparent electrodes

Optically Detected Magnetic Resonance for Selective Imaging of Diamond Nanoparticles

While there is great interest in understanding the fate and transport of nanomaterials in the environment and in biological systems, the detection of nanomaterials in complex matrices by fluorescence methods is complicated by photodegradation, blinking, and the presence of natural organic material and other fluorescent background signals that hamper detection of fluorescent nanomaterials of interest. Optically detected magnetic resonance (ODMR) of nitrogen–vacancy (N_V) centers in diamond nanoparticles provides a pathway toward background-free fluorescence measurements, as the application of a resonant microwave field can selectively modulate the intensity from N_V centers in nanodiamonds of various diameters in complex materials systems using on-resonance and off-resonance microwave fields. This work represents the first investigation showing how nanoparticle diameter impacts the N_V center lifetime and thereby directly impacts the accessible contrast and signal-to-noise ratio when using ODMR to achieve background-free imaging of N_V^–nanodiamonds in the presence of interfering fluorophores. These results provide new insights that will guide the choice of optimum nanoparticle size and methodology for background-free imaging and sensing applications, while also providing a model system to explore the fate and transport of nanomaterials in the environment

Band-Bending of Ga-Polar GaN Interfaced with Al₂O₃ through Ultraviolet/Ozone Treatment

Understanding the band bending at the interface of GaN/dielectric under different surface treatment conditions is critically important for device design, device performance, and device reliability. The effects of ultraviolet/ozone (UV/O₃) treatment of the GaN surface on the energy band bending of atomic-layer-deposition (ALD) Al₂O₃ coated Ga-polar GaN were studied. The UV/O₃ treatment and post-ALD anneal can be used to effectively vary the band bending, the valence band offset, conduction band offset, and the interface dipole at the Al₂O₃/GaN interfaces. The UV/O₃ treatment increases the surface energy of the Ga-polar GaN, improves the uniformity of Al₂O₃ deposition, and changes the amount of trapped charges in the ALD layer. The positively charged surface states formed by the UV/O₃ treatment-induced surface factors externally screen the effect of polarization charges in the GaN, in effect, determining the eventual energy band bending at the Al₂O₃/GaN interfaces. An optimal UV/O₃ treatment condition also exists for realizing the “best” interface conditions. The study of UV/O₃ treatment effect on the band alignments at the dielectric/III-nitride interfaces will be valuable for applications of transistors, light-emitting diodes, and photovoltaics

Highly Stretchable Carbon Nanotube Transistors with Ion Gel Gate Dielectrics

Field-effect transistors (FETs) that are stretchable up to 50% without appreciable degradation in performance are demonstrated. The FETs are based on buckled thin films of polyfluorene-wrapped semiconducting single-walled carbon nanotubes (CNTs) as the channel, a flexible ion gel as the dielectric, and buckled metal films as electrodes. The buckling of the CNT film enables the high degree of stretchability while the flexible nature of the ion gel allows it to maintain a high quality interface with the CNTs during stretching. An excellent on/off ratio of >10⁴, a field-effect mobility of 10 cm²·V^–1·s^–1, and a low operating voltage of <2 V are achieved over repeated mechanical cycling, with further strain accommodation possible. Deformable FETs are expected to facilitate new technologies like stretchable displays, conformal devices, and electronic skins

Enhanced Performance of Ge Photodiodes <i>via</i> Monolithic Antireflection Texturing and α‑Ge Self-Passivation by Inverse Metal-Assisted Chemical Etching

Surface antireflection micro and nanostructures, normally formed by conventional reactive ion etching, offer advantages in photovoltaic and optoelectronic applications, including wider spectral wavelength ranges and acceptance angles. One challenge in incorporating these structures into devices is that optimal optical properties do not always translate into electrical performance due to surface damage, which significantly increases surface recombination. Here, we present a simple approach for fabricating antireflection structures, with self-passivated amorphous Ge (α-Ge) surfaces, on single crystalline Ge (c-Ge) surface using the inverse metal-assisted chemical etching technology (I-MacEtch). Vertical Schottky Ge photodiodes fabricated with surface structures involving arrays of pyramids or periodic nano-indentations show clear improvements not only in responsivity, due to enhanced optical absorption, but also in dark current. The dark current reduction is attributed to the Schottky barrier height increase and self-passivation effect of the i-MacEtch induced α-Ge layer formed on top of the c-Ge surface. The results demonstrated in this work show that MacEtch can be a viable technology for advanced light trapping and surface engineering in Ge and other semiconductor based optoelectronic devices

Thin Film Receiver Materials for Deterministic Assembly by Transfer Printing

We present a specially designed materials chemistry that provides ultrathin adhesive layers with persistent tacky surfaces in solid, nonflowable forms for use in transfer printing and related approaches to materials and micro/nanostructure assembly. The material can be photocured after assembly, to yield a robust and highly transparent coating that is also thermally and electrically stable, for applications in electronics, optoelectronics, and other areas of interest