Selective Isolation of Mono- to Quadlayered 2D Materials via Sonication-Assisted Micromechanical Exfoliation.

Mechanical exfoliation methods of two-dimensional materials have been an essential process for advanced devices and fundamental sciences. However, the exfoliation method usually generates various thick flakes, and a bunch of thick bulk flakes usually covers an entire substrate. Here, we developed a method to selectively isolate mono- to quadlayers of transition metal dichalcogenides (TMDCs) by sonication in organic solvents. The analysis reveals the importance of low interface energies between solvents and TMDCs, leading to the effective removal of bulk flakes under sonication. Importantly, a monolayer adjacent to bulk flakes shows cleavage at the interface, and the monolayer can be selectively isolated on the substrate. This approach can extend to preparing a monolayer device with crowded 17 electrode fingers surrounding the monolayer and for the measurement of electrostatic device performance.

Enhancement of InN Luminescence by Introduction of Graphene Interlayer.

Indium nitride (InN) luminescence is substantially enhanced by the introduction of a multilayer graphene interlayer, mitigating the lattice mismatch between the InN epilayer and the Gallium nitride (GaN) template on a sapphire substrate via weak van der Waals interaction between graphene and nitride layers. The InN epilayers are deposited by radio-frequency plasma-assisted molecular beam epitaxy (MBE), and are characterized by spatially-resolved photoluminescence spectroscopy using confocal microscopy. A small blue shift of the emission band from the band gap evidences a low density of equilibrium carriers, and a high quality of InN on multilayer graphene. A deposition temperature of ~375 °C is determined as optimal. The granularity, which is observed for the InN epilayers deposited on multilayer graphene, is shown to be eliminated, and the emission intensity is further enhanced by the introduction of an aluminum nitride (AlN) buffer layer between graphene and InN.

Evidence for line width and carrier screening effects on excitonic valley relaxation in 2D semiconductors.

Monolayers of transition metal dichalcogenides (TMDC) have recently emerged as excellent platforms for exploiting new physics and applications relying on electronic valley degrees of freedom in two-dimensional (2D) systems. Here, we demonstrate that Coulomb screening by 2D carriers plays a critical role in excitonic valley pseudospin relaxation processes in naturally carrier-doped WSe2 monolayers (1L-WSe2). The exciton valley relaxation times were examined using polarization- and time-resolved photoluminescence spectroscopy at temperatures ranging from 10 to 160 K. We show that the temperature-dependent exciton valley relaxation times in 1L-WSe2 under various exciton and carrier densities can be understood using a unified framework of intervalley exciton scattering via momentum-dependent long-range electron-hole exchange interactions screened by 2D carriers that depend on the carrier density and the exciton linewidth. Moreover, the developed framework was successfully applied to engineer the valley polarization of excitons in 1L-WSe2. These findings may facilitate the development of TMDC-based opto-valleytronic devices.

Thermal dissociation of inter-layer excitons in MoS2/MoSe2 hetero-bilayers.

We describe photoluminescence (PL), PL excitation, and time-resolved PL spectroscopy of hetero-bilayers comprising monolayers (1L) of MoS2 and MoSe2 at cryogenic temperatures. A PL peak showing a decay time of 2.5 ns was observed below 100 K, which can be attributed to an inter-layer exciton emission in the 1L-MoS2/1L-MoSe2 hetero-bilayers. An inter-layer exciton binding energy of ∼90 meV is determined from its thermal dissociation behavior; the band offset of each layer obtained from this value is consistent with previously reported first-principles calculations. Moreover, generation of inter-layer charged excitons (trions) is implied from the gate modulation of the inter-layer exciton PL spectra.

Correction: Thermal dissociation of inter-layer excitons in MoS2/MoSe2 hetero-bilayers.

Correction for 'Thermal dissociation of inter-layer excitons in MoS2/MoSe2 hetero-bilayers' by Shinichiro Mouri et al., Nanoscale, 2017, DOI: 10.1039/c7nr01598d.

Evidence for Fast Interlayer Energy Transfer in MoSe2/WS2 Heterostructures.

Strongly bound excitons confined in two-dimensional (2D) semiconductors are dipoles with a perfect in-plane orientation. In a vertical stack of semiconducting 2D crystals, such in-plane excitonic dipoles are expected to efficiently couple across van der Waals gap due to strong interlayer Coulomb interaction and exchange their energy. However, previous studies on heterobilayers of group 6 transition metal dichalcogenides (TMDs) found that the exciton decay dynamics is dominated by interlayer charge transfer (CT) processes. Here, we report an experimental observation of fast interlayer energy transfer (ET) in MoSe2/WS2 heterostructures using photoluminescence excitation (PLE) spectroscopy. The temperature dependence of the transfer rates suggests that the ET is Förster-type involving excitons in the WS2 layer resonantly exciting higher-order excitons in the MoSe2 layer. The estimated ET time of the order of 1 ps is among the fastest compared to those reported for other nanostructure hybrid systems such as carbon nanotube bundles. Efficient ET in these systems offers prospects for optical amplification and energy harvesting through intelligent layer engineering.

Highly stable perovskite solar cells with an all-carbon hole transport layer.

Nano-carbon materials (carbon nanotubes, graphene, and graphene oxide) have potential application for photovoltaics because of their excellent optical and electronic properties. Here, we demonstrate that a single-walled carbon nanotubes/graphene oxide buffer layer greatly improves the photovoltaic performance of organo-lead iodide perovskite solar cells. The carbon nanotubes/graphene oxide buffer layer works as an efficient hole transport/electron blocking layer. The photovoltaic conversion efficiency of 13.3% was achieved in the organo-lead iodide perovskite solar cell due to the complementary properties of carbon nanotubes and graphene oxide. Furthermore, the great improvement of photovoltaic performance stability in the perovskite solar cells using carbon nanotubes/graphene oxide/polymethyl methacrylate was demonstrated in comparison with that using a typical organic hole transport layer of 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene.

Efficient near-infrared up-conversion photoluminescence in carbon nanotubes.

Photoluminescence phenomena normally obey Stokes' law of luminescence according to which the emitted photon energy is typically lower than its excitation counterparts. Here we show that carbon nanotubes break this rule under one-photon excitation conditions. We found that the carbon nanotubes exhibit efficient near-infrared photoluminescence upon photoexcitation even at an energy lying >100-200 meV below that of the emission at room temperature. This apparently anomalous phenomenon is attributed to efficient one-phonon-assisted up-conversion processes resulting from unique excited-state dynamics emerging in an individual carbon nanotube with accidentally or intentionally embedded localized states. These findings may open new doors for energy harvesting, optoelectronics and deep-tissue photoluminescence imaging in the near-infrared optical range.

Enhanced photovoltaic performances of graphene/Si solar cells by insertion of a MoS2 thin film.

Transition-metal dichalcogenides exhibit great potential as active materials in optoelectronic devices because of their characteristic band structure. Here, we demonstrated that the photovoltaic performances of graphene/Si Schottky junction solar cells were significantly improved by inserting a chemical vapor deposition (CVD)-grown, large MoS2 thin-film layer. This layer functions as an effective electron-blocking/hole-transporting layer. We also demonstrated that the photovoltaic properties are enhanced with the increasing number of graphene layers and the decreasing thickness of the MoS2 layer. A high photovoltaic conversion efficiency of 11.1% was achieved with the optimized trilayer-graphene/MoS2/n-Si solar cell.

Considerably improved photovoltaic performance of carbon nanotube-based solar cells using metal oxide layers.

Carbon nanotube-based solar cells have been extensively studied from the perspective of potential application. Here we demonstrated a significant improvement of the carbon nanotube solar cells by the use of metal oxide layers for efficient carrier transport. The metal oxides also serve as an antireflection layer and an efficient carrier dopant, leading to a reduction in the loss of the incident solar light and an increase in the photocurrent, respectively. As a consequence, the photovoltaic performance of both p-single-walled carbon nanotube (SWNT)/n-Si and n-SWNT/p-Si heterojunction solar cells using MoOx and ZnO layers is improved, resulting in very high photovoltaic conversion efficiencies of 17.0 and 4.0%, respectively. These findings regarding the use of metal oxides as multifunctional layers suggest that metal oxide layers could improve the performance of various electronic devices based on carbon nanotubes.

Nonlinear photoluminescence spectroscopy of carbon nanotubes with localized exciton states.

We report distinctive nonlinear behavior of photoluminescence (PL) intensities from localized exciton states embedded in single-walled carbon nanotubes (SWNTs) at room temperature. We found that PL from the local states exhibits strong nonlinear behavior with increasing continuous-wave excitation power density, whereas free exciton PL shows only weak sublinear behavior. The strong nonlinear behavior was observed regardless of the origin of the local states and found to be nearly independent of the local state density. These results indicate that the strong PL nonlinearity arises from a universal mechanism to SWNTs with sparse local states. The significant nonlinear PL is attributed to rapid ground-state depletion of the local states caused by an efficient accumulation of photogenerated free excitons into the sparse local states through one-dimensional diffusional migration of excitons along the nanotube axis; this mechanism is verified by Monte Carlo simulations of exciton diffusion dynamics.

Redox properties of a single (7,5)single-walled carbon nanotube determined by an in situ photoluminescence spectroelectrochemical method.

The determination of electronic states of single-walled carbon nanotubes (SWNTs) has been a central issue in science and nanotechnology of carbon nanotubes. We here describe the oxidation and reduction potentials of a single SWNT determined by in situ photoluminescence (PL) spectroelectrochemical measurements. By PL imaging and single SWNT PL spectroscopy, the stepwise quenching behavior of the PL from a single (7,5)SWNT was detected as the outer-applied potentials increased. Based on the analysis of the obtained potential-dependent PL plots using the Nernst equation, the oxidation and reduction potentials of the (7,5) tube are successfully determined as 0.41 V and -0.38 V vs. Ag/AgCl, respectively, which shift from those of the bulk (7,5)SWNTs. We further observed a PL blueshift and narrowing of the line width as the external-applied potential to the single SWNT increases. The present results are important for understanding the electronic properties of a single (n,m)SWNT and its applications.

Excitonic Photoluminescence from Nanodisc States in Graphene Oxides.

The origin of near-infrared (NIR) luminescence from graphene oxide (GO) is investigated by photoluminescence (PL) excitation spectroscopy, time-resolved PL spectroscopy, and density functional theory based many body perturbation theories. The energy of experimentally observed NIR PL peak depends on the excitation energy, and the peak broadens with increasing excitation energy. It is found that the PL decay curves in time-resolved spectroscopy show build-up behavior at lower emission energies due to energy transfer between smaller to larger graphene nanodisc (GND) states embedded in GO. We demonstrate that the NIR PL originates from ensemble emission of GND states with a few nanometers in size. The theoretical calculations reveal the electronic and excitonic properties of individual GND states with various sizes, which accounts for the inhomogeneously broadened NIR PL. We further demonstrate that the electronic properties are highly sensitive to the protonation and deprotonation processes of GND states using both the experimental and theoretical approaches.

Tunable photoluminescence of monolayer MoS2 via chemical doping.

We demonstrate the tunability of the photoluminescence (PL) properties of monolayer (1L)-MoS2 via chemical doping. The PL intensity of 1L-MoS2 was drastically enhanced by the adsorption of p-type dopants with high electron affinity but reduced by the adsorption of n-type dopants. This PL modulation results from switching between exciton PL and trion PL depending on carrier density in 1L-MoS2. Achievement of the extraction and injection of carriers in 1L-MoS2 by this solution-based chemical doping method enables convenient control of optical and electrical properties of atomically thin MoS2.

Empirical prediction of electronic potentials of single-walled carbon nanotubes with a specific chirality (n,m).

The determination of the electronic states of single-walled carbon nanotubes (SWNTs) with a specific chirality has been a central issue in the science of SWNTs. Here we present the empirical equations with fitting parameters for the determination of the reduction and oxidation potentials of SWNTs for a wide range of diameters and chiral angles. In these equations, a distinct chirality family dependence of the reduction potentials is observed, while the oxidation potentials show a simple diameter dependence nearly proportional to the inversed nanotube diameter. Based on observations of the asymmetric chirality dependence between the reduction and oxidation potentials, the Fermi levels of the SWNTs were revealed to have a definite chirality family dependence, which indicates that the work functions of the SWNTs with small diameters deviate from the values for the large diameter SWNTs and graphene. We also performed quantum chemical calculations to compare the experiment to the calculations.

Exploring the Origin of Blue and Ultraviolet Fluorescence in Graphene Oxide.

We studied the fluorescence (FL) properties of highly exfoliated graphene oxide (GO) in aqueous solution using continuous-wave and time-resolved FL spectroscopy. The FL spectra of highly exfoliated GO showed two distinct peaks at ∼440 (blue) and ∼300 nm [ultraviolet (UV)]. The FL of GO in the UV region at ∼300 nm was observed for the first time. The average FL lifetimes of the emission peaks at ∼440 and ∼300 nm are 8-13 and 6-8 ns, respectively. The experimentally observed peak wavelengths of pH-dependent FL, FL excitation spectra, and the FL lifetimes are nearly coincident with those of aromatic compounds bound with oxygen functional groups, which suggests that the FL comes from sp(2) fragments consisting of small numbers of aromatic rings with oxygen functional groups acting as FL centers in the GO.

Observation of negative and positive trions in the electrochemically carrier-doped single-walled carbon nanotubes.

Understanding of electronic and optical features of single-walled carbon nanotubes (SWNTs) has been a central issue in science and nanotechnology of carbon nanotubes. We describe the detection of both the positive trion (positively charged exciton) and negative trion (negatively charged exciton) as a three-particle bound state in the SWNTs at room temperature by an in situ photoluminescence spectroelectrochemistry method for an isolated SWNT film cast on an ITO electrode. The electrochemical hole and electron dopings enable us to detect such trions on the SWNTs. The large energy difference between the singlet bright exciton and the negative and positive trions showing a tube diameter dependence is determined by both the exchange splitting energy and the trion binding energy. In contrast to conventional compound semiconductors, on the SWNTs, the negative trion has almost the same binding energy to the positive trion, which is attributed to nearly identical effective masses of the holes and electrons.

Nanoparticles of iron(II) spin-crossover.

We report the synthesis of spin crossover 69 nm spherical nanoparticles of [Fe(NH2-trz)3](Br)2.3H2O.0.03(surfactant) (NH2trz = 4-amino-1,2,4-triazole, surfactant = Lauropal), prepared by the reverse micelle technique, which exhibit at room temperature a thermal hysteresis characterized by magnetic, diffuse reflectivity and Raman studies.