Photoinduced Self-Gating of Perovskite Photovoltaic Cells in Ionic Liquid.

We demonstrate that the power conversion efficiency (PCE), photocurrent, and fill factor (FF) of perovskite solar cells (PSC) can be significantly improved by the photoinduced self-gating in ionic liquids (ILs) via n-doping of the carbon nanotube (CNT) top electrode on the fullerene electron transport layer (ETL). CNTs, graphene, and other carbon electrodes have been proven to be stable electrodes for PSC, but efficiency was not high. We have previously shown that the performance of PSCs with CNT electrodes can be improved by IL gating with gate voltage (Vg) applied from an external power source. Here we demonstrate that effective self-gating in ILs is possible by a photoinduced process, without an external source. The open circuit voltage (Voc) generated by the PSC itself can be applied to the CNT/C60 electrode as Vg leading to photogating. This self-gating with Voc is compared to photocharging of CNTs in ILs without any gating for two types of fullerene ETLs: C60 and C70, Two types of ILs, DEME-TFSI and BMIM-BF4, are tested for two types of nanotubes electrodes: single wall (SWCNT), and multiwall (MWCNT). The resulting improvements are analyzed using the effective diode-circuit (DC) and the drift-diffusion (DD) models. Self-gating allows the PCE improvement from 3-5% to 10-11% for PSCs with a thick ETL, while for optimal combination of a thin SWCNT/ETL with added layers for improved stability, the PCE reached 13.2% in DEME-TFSI IL.

Photogating interfacial effects in carbon nanotube-based transistors on a Si/SiO2 substrate toward highly sensitive photodetection.

Single-walled carbon nanotubes (SWCNTs) are considered to be promising material platforms for various photodetectors (including phototransistors) due to their unique optoelectrical properties (e.g., high mobility and a wide variety of bandgap values). Herein, we present highly sensitive phototransistors which utilised sparse networks of SWCNTs on a silicon/silica substrate and operated by means of the photogating effect. The response of SWCNTs to photo-induced electrostatic charges (photogating effect) was highly dependent on the conductivity type of the channel, which was "metallic" or "semiconducting", depending on the SWCNT density. We determined the performance of these transistors depending on the characteristics of the substrate and conductivity type of the SWCNT channel. The optimized configuration of phototransistors with a channel comprising a sparse network of SWCNTs permitted improvement in the specific detectivity and relative response compared with previously reported photodetectors based on graphene and carbon nanotubes. We demonstrated an absolute responsivity of ∼60 A W-1 at an incident light power of ∼2 nW, specific detectivity of 7.8 × 1011 cm·Hz1/2 W-1, and response time of 300 µs. These data revealed the high potential of photogating-based SWCNTs detectors for extremely weak signals with a high signal-to-noise ratio.

Robust method for uniform coating of carbon nanotubes with V2O5 for next-generation transparent electrodes and Li-ion batteries.

Composites comprising vanadium-pentoxide (V2O5) and single-walled carbon nanotubes (SWCNTs) are promising components for emerging applications in optoelectronics, solar cells, chemical and electrochemical sensors, etc. We propose a novel, simple, and facile approach for SWCNT covering with V2O5 by spin coating under ambient conditions. With the hydrolysis-polycondensation of the precursor (vanadyl triisopropoxide) directly on the surface of SWCNTs, the nm-thick layer of oxide is amorphous with a work function of 4.8 eV. The material recrystallizes after thermal treatment at 600 °C, achieving the work function of 5.8 eV. The key advantages of the method are that the obtained coating is uniform with a tunable thickness and does not require vacuuming or heating during processing. We demonstrate the groundbreaking results for two V2O5/SWCNT applications: transparent electrode and cathode for Li-ion batteries. As a transparent electrode, the composite shows stable sheet resistance of 160 Ω sq-1 at a 90% transmittance (550 nm) - the best performance reported for SWCNTs doped by metal oxides. As a cathode material, the obtained specific capacity (330 mA h g-1) is the highest among all the other V2O5/SWCNT cathodes reported so far. This approach opens new horizons for the creation of the next generation of metal oxide composites for various applications, including optoelectronics and electrochemistry.

Dumbbell-Shaped Ho-Doped Fiber Laser Mode-Locked by Polymer-Free Single-Walled Carbon Nanotubes Saturable Absorber.

We propose a simple dumbbell-shaped scheme of a Holmium-doped fiber laser incorporating a minimum number of optical elements. Mode-locking regimes were realized with the help of polymer-free single-walled carbon nanotubes (SWCNTs) synthesized using an aerosol (floating catalyst) CVD method. We show that such a laser scheme is structurally simple and more efficient than a conventional one using a ring cavity and a similar set of optical elements. In addition, we investigated the effect of SWCNT film transmittance, defined by the number of 40 nm SWCNT layers on the laser's performance: operating regimes, stability, and self-starting. We found that three SWCNT layers with an initial transmittance of about 40% allow stable self-starting soliton mode-locking at a wavelength of 2076 nm with a single pulse energy of 0.6 nJ and a signal-to-noise ratio of more than 60 dB to be achieved.

Role of Hydrogen in Ethylene-Based Synthesis of Single-Walled Carbon Nanotubes.

We examined the effect of hydrogen on the growth of single-walled carbon nanotubes in the aerosol (a specific case of the floating catalyst) chemical vapor deposition process using ethylene as a carbon source and ferrocene as a precursor for a Fe-based catalyst. With a comprehensive set of physical methods (UV-vis-NIR and Raman spectroscopies, transmission electron microscopy, scanning electron microscopy, differential mobility analysis, and four-probe sheet resistance measurements), we showed hydrogen to inhibit ethylene pyrolysis extending the window of synthesis parameters. Moreover, the detailed study at different temperatures allowed us to distinguish three different regimes for the hydrogen effect: pyrolysis suppression at low concentrations (I) followed by surface cleaning/activation promotion (II), and surface blockage/nanotube etching (III) at the highest concentrations. We believe that such a detailed study will help to reveal the complex role of hydrogen and contribute toward the synthesis of single-walled carbon nanotubes with detailed characteristics.

Bithiophene as a Sulfur-Based Promotor for the Synthesis of Carbon Nanotubes and Carbon-Carbon Composites.

We assess bithiophene (C8H6S2) as a novel sulfur-based promotor for the growth of single-walled carbon nanotubes (SWCNTs) in the aerosol (floating catalyst) CVD method. Technologically suitable equilibrium vapor pressure and an excess of hydrocarbon residuals formed under its decomposition make bithiophene an attractive promoter for the production of carbon nanotubes in general and specifically for ferrocene-based SWCNT growth. Indeed, we detect a moderate enhancement in the carbon nanotube yield and a decrease in the equivalent sheet resistance of the films at a low bithiophene content, indicating the improvement of the product properties. Moreover, the relatively high concentrations and low temperature stability of bithiophene result in non-catalytical decomposition, leading to the formation of pyrolytic carbon deposits; the deposits appear as few-layer graphene structures. Thus, bithiophene pyrolysis opens a route for the cheap production of hierarchical composite thin films comprising carbon nanotubes and few-layer graphene, which might be of practical use for hierarchical adsorbents, protective membranes, or electrocatalysis.

Atomistic Mechanism of Friction-Force Independence on the Normal Load and Other Friction Laws for Dynamic Structural Superlubricity.

We explore dynamic structural superlubricity for the case of a relatively large contact area, where the friction force is proportional to the area (exceeding ∼100 nm^{2}) experimentally, numerically, and theoretically. We use a setup composed of two molecular smooth incommensurate surfaces: graphene-covered tip and substrate. The experiments and molecular dynamic simulations demonstrate independence of the friction force on the normal load for a wide range of normal loads and relative surface velocities. We propose an atomistic mechanism for this phenomenon, associated with synchronic out-of-plane surface fluctuations of thermal origin, and confirm it by numerical experiments. Based on this mechanism, we develop a theory for this type of superlubricity and show that friction force increases linearly with increasing temperature and relative velocity for velocities larger than a threshold velocity. The molecular dynamic results are in a fair agreement with predictions of the theory.

Novel Push-Pull Benzodithiophene-Containing Polymers as Hole-Transport Materials for Efficient Perovskite Solar Cells.

Donor-acceptor conjugated polymers are considered advanced semiconductor materials for the development of thin-film electronics. One of the most attractive families of polymeric semiconductors in terms of photovoltaic applications are benzodithiophene-based polymers owing to their highly tunable electronic and physicochemical properties, and readily scalable production. In this work, we report the synthesis of three novel push-pull benzodithiophene-based polymers with different side chains and their investigation as hole transport materials (HTM) in perovskite solar cells (PSCs). It is shown that polymer P3 that contains triisopropylsilyl side groups exhibits better film-forming ability that, along with high hole mobilities, results in increased characteristics of PSCs. Encouraging a power conversion efficiency (PCE) of 17.4% was achieved for P3-based PSCs that outperformed the efficiency of devices based on P1, P2, and benchmark PTAA polymer. These findings feature the great potential of benzodithiophene-based conjugated polymers as dopant-free HTMs for the fabrication of efficient perovskite solar cells.

Tuning the Optical Properties and Conductivity of Bundles in Networks of Single-Walled Carbon Nanotubes.

The films of single-walled carbon nanotubes (SWCNTs) are a promising material for flexible transparent electrodes, which performance depends not only on the properties of individual nanotubes but also, foremost, on bundling of individual nanotubes. This work investigates the impact of densification on optical and electronic properties of SWCNT bundles and fabricated films. Our ab initio analysis shows that the optimally densified bundles, consisting of a mixture of quasi-metallic and semiconducting SWCNTs, demonstrate quasi-metallic behavior and can be considered as an effective conducting medium. Our density functional theory calculations indicate the band curving and bandgap narrowing with the reduction of the distance between nanotubes inside bundles. Simulation results are consistent with the observed conductivity improvement and shift of the absorption peaks in SWCNT films densified in isopropyl alcohol. Therefore, not only individual nanotubes but also the bundles should be considered as building blocks for high-performance transparent conductive SWCNT-based films.

Albumin Stabilized Fe@C Core-Shell Nanoparticles as Candidates for Magnetic Hyperthermia Therapy.

Carbon-encapsulated iron nanoparticles (Fe@C) with a mean diameter of 15 nm have been synthesized using evaporation-condensation flow-levitation method by the direct iron-carbon gas-phase reaction at high temperatures. Further, Fe@C were stabilized with bovine serum albumin (BSA) coating, and their electromagnetic properties were evaluated to test their performance in magnetic hyperthermia therapy (MHT) through a specific absorption rate (SAR). Heat generation was observed at different Fe@C concentrations (1, 2.5, and 5 mg/mL) when applied 331 kHz and 60 kA/m of an alternating magnetic field, resulting in SAR values of 437.64, 129.36, and 50.4 W/g for each concentration, respectively. Having such high SAR values at low concentrations, obtained material is ideal for use in MHT.

Design of an Artificial Opal/Photonic Crystal Interface for Alcohol Intoxication Assessment: Capillary Condensation in Pores and Photonic Materials Work Together.

Alcohol intoxication has a dangerous effect on human health and is often associated with a risk of catastrophic injuries and alcohol-related crimes. A demand to address this problem adheres to the design of new sensor systems for the real-time monitoring of exhaled breath. We introduce a new sensor system based on a porous hydrophilic layer of submicron silica particles (SiO2 SMPs) placed on a one-dimensional photonic crystal made of Ta2O5/SiO2 dielectric layers whose operation relies on detecting changes in the position of surface wave resonance during capillary condensation in pores. To make the active layer of SiO2 SMPs, we examine the influence of electrostatic interactions of media, particles, and the surface of the crystal influenced by buoyancy, gravity force, and Stokes drag force in the frame of the dip-coating preparation method. We evaluate the sensing performance toward biomarkers such as acetone, ammonia, ethanol, and isopropanol and test sensor system capabilities for alcohol intoxication assessment. We have found this sensor to respond to all tested analytes in a broad range of concentrations. By processing the sensor signals by principal component analysis, we selectively determined the analytes. We demonstrated the excellent performance of our device for alcohol intoxication assessment in real-time.

Tunable force sensor based on carbon nanotube fiber for fine mechanical and acoustic technologies.

Design of new smart prosthetics or robotic grippers gives a major impetus to low-cost manufacturing and rapid prototyping of force sensing devices. In this paper, we examine piezoresistive force sensors based on carbon nanotube fibers fabricated by a novel wet pulling technique. The developed sensor is characterized by an adjustable force range coupled with high sensitivity to enable the detection of a wide range of forces and displacements limited by the experimental setup only. We have demonstrated the applicability of the developed unit in tactile sensing, displacement sensing, and nanophone vibration monitoring system and evaluated its force sensing characteristics, i.e. displacement/force input and resistance/mechanical response. In the experiments it measures 0-115 N force range within 2.5 mm displacement. Moreover, the sensor demonstrates good linearity, low hysteresis, and stability when tested over 10 000 cycles. The developed sensor suits multiple applications in the field of soft and transparent sensors, nanophones, actuators, and other robotics devices for both regular and extreme environments, e.g. deep underwater and radioactive environment.

In vitro toxicity of carbon nanotubes: a systematic review.

Carbon nanotube (CNT) toxicity-related issues provoke many debates in the scientific community. The controversial and disputable data about toxicity doses, proposed hazard effects, and human health concerns significantly restrict CNT applications in biomedical studies, laboratory practices, and industry, creating a barrier for mankind in the way of understanding how exactly the material behaves in contact with living systems. Raising the toxicity question again, many research groups conclude low toxicity of the material and its potential safeness at some doses for contact with biological systems. To get new momentum for researchers working on the intersection of the biological field and nanomaterials, i.e., CNT materials, we systematically reviewed existing studies with in vitro toxicological data to propose exact doses that yield toxic effects, summarize studied cell types for a more thorough comparison, the impact of incubation time, and applied toxicity tests. Using several criteria and different scientific databases, we identified and analyzed nearly 200 original publications forming a "golden core" of the field to propose safe doses of the material based on a statistical analysis of retrieved data. We also differentiated the impact of various forms of CNTs: on a substrate and in the form of dispersion because in both cases, some studies demonstrated good biocompatibility of CNTs. We revealed that CNTs located on a substrate had negligible impact, i.e., 90% of studies report good viability and cell behavior similar to control, therefore CNTs could be considered as a prospective conductive substrate for cell cultivation. In the case of dispersions, our analysis revealed mean values of dose/incubation time to be 4-5 µg mL-1 h-1, which suggested the material to be a suitable candidate for further studies to get a more in-depth understanding of its properties in biointerfaces and offer CNTs as a promising platform for fundamental studies in targeted drug delivery, chemotherapy, tissue engineering, biosensing fields, etc. We hope that the present systematic review will shed light on the current knowledge about CNT toxicity, indicate "dark" spots and offer possible directions for the subsequent studies based on the demonstrated here tabulated and statistical data of doses, cell models, toxicity tests, viability, etc.

Transparent Conducting Films Based on Carbon Nanotubes: Rational Design toward the Theoretical Limit.

Electrically conductive thin-film materials possessing high transparency are essential components for many optoelectronic devices. The advancement in the transparent conductor applications requires a replacement of indium tin oxide (ITO), one of the key materials in electronics. ITO and other transparent conductive metal oxides have several drawbacks, including poor flexibility, high refractive index and haze, limited chemical stability, and depleted raw material supply. Single-walled carbon nanotubes (SWCNTs) are a promising alternative for transparent conducting films (TCFs) because of their unique and excellent chemical and physical properties. Here, the latest achievements in the optoelectronic performance of TCFs based on SWCNTs are analyzed. Various approaches to evaluate the performance of transparent electrodes are briefly reviewed. A roadmap for further research and development of the transparent conductors using "rational design," which breaks the deadlock for obtaining the TCFs with a performance close to the theoretical limit, is also described.

Multifunctional Elastic Nanocomposites with Extremely Low Concentrations of Single-Walled Carbon Nanotubes.

Stretchable and flexible electronics has attracted broad attention over the last years. Nanocomposites based on elastomers and carbon nanotubes are a promising material for soft electronic applications. Despite the fact that single-walled carbon nanotube (SWCNT) based nanocomposites often demonstrate superior properties, the vast majority of the studies were devoted to those based on multiwalled carbon nanotubes (MWCNTs) mainly because of their higher availability and easier processing procedures. Moreover, high weight concentrations of MWCNTs are often required for high performance of the nanocomposites in electronic applications. Inspired by the recent drop in the SWCNT price, we have focused on fabrication of elastic nanocomposites with very low concentrations of SWCNTs to reduce the cost of nanocomposites further. In this work, we use a fast method of coagulation (antisolvent) precipitation to fabricate elastic composites based on thermoplastic polyurethane (TPU) and SWCNTs with a homogeneous distribution of SWCNTs in bulk TPU. Applicability of the approach is confirmed by extra low percolation threshold of 0.006 wt % and, as a consequence, by the state-of-the-art performance of fabricated elastic nanocomposites at very low SWCNT concentrations for strain sensing (gauge factor of 82 at 0.05 wt %) and EMI shielding (efficiency of 30 dB mm-1 at 0.01 wt %).

Gentle Patterning Approaches toward Compatibility with Bio-Organic Materials and Their Environmental Aspects.

Advances in material science, bioelectronic, and implantable medicine combined with recent requests for eco-friendly materials and technologies inevitably formulate new challenges for nano- and micropatterning techniques. Overall, the importance of creating micro- and nanostructures is motivated by a large manifold of fundamental and applied properties accessible only at the nanoscale. Lithography is a crucial family of fabrication methods to create prototypes and produce devices on an industrial scale. The pure trend in the miniaturization of critical electronic semiconducting components has been recently enhanced by implementing bio-organic systems in electronics. So far, significant efforts have been made to find novel lithographic approaches and develop old ones to reach compatibility with delicate bio-organic systems and minimize the impact on the environment. Herein, such delicate materials and sophisticated patterning techniques are briefly reviewed.

High-Quality Graphene Using Boudouard Reaction.

Following the game-changing high-pressure CO (HiPco) process that established the first facile route toward large-scale production of single-walled carbon nanotubes, CO synthesis of cm-sized graphene crystals of ultra-high purity grown during tens of minutes is proposed. The Boudouard reaction serves for the first time to produce individual monolayer structures on the surface of a metal catalyst, thereby providing a chemical vapor deposition technique free from molecular and atomic hydrogen as well as vacuum conditions. This approach facilitates inhibition of the graphene nucleation from the CO/CO2 mixture and maintains a high growth rate of graphene seeds reaching large-scale monocrystals. Unique features of the Boudouard reaction coupled with CO-driven catalyst engineering ensure not only suppression of the second layer growth but also provide a simple and reliable technique for surface cleaning. Aside from being a novel carbon source, carbon monoxide ensures peculiar modification of catalyst and in general opens avenues for breakthrough graphene-catalyst composite production.

Single-step extraction of small-diameter single-walled carbon nanotubes in the presence of riboflavin.

We propose a novel approach to disperse and extract small-diameter single-walled carbon nanotubes (SWCNTs) using an aqueous solution of riboflavin and Sephacryl gel. The extraction of small-diameter semiconducting SWCNTs was observed, regardless of the initial diameter distribution of the SWCNTs. Dispersion of SWCNTs occurs due to the adsorption of π-conjugated isoalloxazine moieties on the surface of small-diameter nanotubes and interactions between hydroxy groups of ribityl chains with water. During the SWCNT extraction, specific adsorption of riboflavin to SWCNTs leads to the minimization of interactions between the SWCNTs and gel media. Our experimental findings are supported by ab initio calculations demonstrating the impact of the riboflavin wrapping pattern around the SWCNTs on their interaction with the allyl dextran gel.

Red GaPAs/GaP Nanowire-Based Flexible Light-Emitting Diodes.

We demonstrate flexible red light-emitting diodes based on axial GaPAs/GaP heterostructured nanowires embedded in polydimethylsiloxane membranes with transparent electrodes involving single-walled carbon nanotubes. The GaPAs/GaP axial nanowire arrays were grown by molecular beam epitaxy, encapsulated into a polydimethylsiloxane film, and then released from the growth substrate. The fabricated free-standing membrane of light-emitting diodes with contacts of single-walled carbon nanotube films has the main electroluminescence line at 670 nm. Membrane-based light-emitting diodes (LEDs) were compared with GaPAs/GaP NW array LED devices processed directly on Si growth substrate revealing similar electroluminescence properties. Demonstrated membrane-based red LEDs are opening an avenue for flexible full color inorganic devices.

Flexible Perovskite CsPbBr3 Light Emitting Devices Integrated with GaP Nanowire Arrays in Highly Transparent and Durable Functionalized Silicones.

The architecture of transparent contacts is of utmost importance for creation of efficient flexible light-emitting devices (LEDs) and other deformable electronic devices. We successfully combined the newly synthesized transparent and durable silicone rubbers and the semiconductor materials with original fabrication methods to design LEDs and demonstrate their significant flexibility. We developed electrodes based on a composite GaP nanowire-phenylethyl-functionalized silicone rubber membrane, improved with single-walled carbon nanotube films for a hybrid poly(ethylene oxide)-metal-halide perovskite (CsPbBr3) flexible green LED. The proposed approach provides a novel platform for fabrication of flexible hybrid optoelectronic devices.