Emissive ZnO-graphene quantum dots for white-light-emitting diodes

Hybrid nanostructures combining inorganic materials and graphene are being developed for applications such as fuel cells, batteries, photovoltaics and sensors. However, the absence of a bandgap in graphene has restricted the electrical and optical characteristics of these hybrids, particularly their emissive properties. Here, we use a simple solution method to prepare emissive hybrid quantum dots consisting of a ZnO core wrapped in a shell of single-layer graphene. We then use these quantum dots to make a white-light-emitting diode with a brightness of 798?cd?m(-2). The strain introduced by curvature opens an electronic bandgap of 250?meV in the graphene, and two additional blue emission peaks are observed in the luminescent spectrum of the quantum dot. Density functional theory calculations reveal that these additional peaks result from a splitting of the lowest unoccupied orbitals of the graphene into three orbitals with distinct energy levels. White emission is achieved by combining the quantum dots with other emissive materials in a multilayer light-emitting diode.     

Quantum Confinement of Dirac Quasiparticles in Graphene Patterned with Sub-Nanometer Precision

Quantum confinement of graphene Dirac-like electrons in artificially crafted nanometer structures is a long sought goal that would provide a strategy to selectively tune the electronic properties of graphene, including bandgap opening or quantization of energy levels. However, creating confining structures with nanometer precision in shape, size, and location remains an experimental challenge, both for top-down and bottom-up approaches. Moreover, Klein tunneling, offering an escape route to graphene electrons, limits the efficiency of electrostatic confinement. Here, a scanning tunneling microscope (STM) is used to create graphene nanopatterns, with sub-nanometer precision, by the collective manipulation of a large number of H atoms. Individual graphene nanostructures are built at selected locations, with predetermined orientations and shapes, and with dimensions going all the way from 2 nm up to 1 µm. The method permits the patterns to be erased and rebuilt at will, and it can be implemented on different graphene substrates. STM experiments demonstrate that such graphene nanostructures confine very efficiently graphene Dirac quasiparticles, both in 0D and 1D structures. In graphene quantum dots, perfectly defined energy bandgaps up to 0.8 eV are found that scale as the inverse of the dot’s linear dimension, as expected for massless Dirac fermions.     

Positioning and immobilization of individual quantum dots with nanoscale precision

We demonstrate a technique for the precise immobilization of nanoscale objects at accurate positions on two-dimensional surfaces. We have developed a water-based photoresist that causes nanostructures such as colloidal quantum dots to segregate to a thin layer at surfaces. By combining this material with electroosmotic feedback control, we demonstrate the ability to position selected, individual quantum dots at specific locations and to immobilize them with 130 nm precision via localized UV exposure.     

Experimental study and modeling of atomic-scale friction in zigzag and armchair lattice orientations of MoS2

Physical properties of two-dimensional materials, such as graphene, black phosphorus, molybdenum disulfide (MoS₂) and tungsten disulfide, exhibit significant dependence on their lattice orientations, especially for zigzag and armchair lattice orientations. Understanding of the atomic probe motion on surfaces with different orientations helps in the study of anisotropic materials. Unfortunately, there is no comprehensive model that can describe the probe motion mechanism. In this paper, we report a tribological study of MoS₂ in zigzag and armchair orientations. We observed a characteristic power spectrum and friction force values. To explain our results, we developed a modified, two-dimensional, stick-slip Tomlinson model that allows simulation of the probe motion on MoS₂ surfaces by combining the motion in the Mo layer and S layer. Our model fits well with the experimental data and provides a theoretical basis for tribological studies of two-dimensional materials.     

Electronic structure and optical property of semiconductor nanocrystallites

Semiconductor nanostructures show many special physical properties associated with quantum confinement effects, and have many applications in the opto-electronic and microelectronic fields. However, it is difficult to calculate their electronic states by the ordinary plane wave or linear combination of atomic orbital methods. In this paper, we review some of our works in this field, including semiconductor clusters, self-assembled quantum dots, and diluted magnetic semiconductor quantum dots. In semiconductor clusters we introduce energy bands and effective-mass Hamiltonian of wurtzite structure semiconductors, electronic structures and optical properties of spherical clusters, ellipsoidal clusters, and nanowires. In self-assembled quantum dots we introduce electronic structures and transport properties of quantum rings and quantum dots, and resonant tunneling of 3-dimensional quantum dots. In diluted magnetic semiconductor quantum dots we introduce magnetic-optical properties, and magnetic field tuning of the effective g factor in a diluted magnetic semiconductor quantum dot.     

Nanoscale patterning of colloidal quantum dots on transparent and metallic planar surfaces

The patterning of colloidal quantum dots with nanometer resolution is essential for their application in photonics and plasmonics. Several patterning approaches, such as the use of polymer composites, molecular lock-and-key methods, inkjet printing and microcontact printing of quantum dots have been recently developed. Herein, we present a simple method of patterning colloidal quantum dots for photonic nanostructures such as straight lines, rings and dot patterns either on transparent or metallic substrates. Sub-10?nm width of the patterned line could be achieved with a well-defined sidewall profile. Using this method, we demonstrate a surface plasmon launcher from a quantum dot cluster in the visible spectrum.     

石墨烯量子点在生物医学中的研究进展

石墨烯量子点是石墨烯超家族的衍生物,与高维度石墨烯相比,具有良好的生物相容性,较低的细胞毒性及较好的化学修饰性。自发现以来,石墨烯量子点的应用领域被逐渐地拓宽。其中石墨烯量子点的生物应用主要包括生物成像、生物传感器、药物运输、基因载体、抗菌抗病毒及肿瘤的光动力治疗研究等。主要介绍了近几年有关石墨烯量子点生物相容性及其在生物医学研究的进展,并对其发展前景进行了展望。     

Optical anisotropy in self-assembled InAs nanostructures grown on GaAs high index substrate

We present a study of the optical properties of InAs self-assembled nanostructures grown by molecular beam epitaxy on GaAs(11N)A substrates (N?=?3-5). Photoluminescence (PL) measurements revealed good optical properties of InAs quantum dots (QDs) grown on GaAs(115)A compared to those grown on GaAs(113)A and (114)A orientations substrate. An additional peak localized at 1.39 eV has been shown on PL spectra of both GaAs(114)A and (113)A samples. This peak persists even at lower power density. Supporting on the polarized photoluminescence characterization, we have attributed this additional peak to the quantum strings (QSTs) emission. A theoretical study based on the resolution of the three dimensional Schr?dinger equation, using the finite element method, including strain and piezoelectric-field effect was adopted to distinguish the observed photoluminescence emission peaks. The mechanism of QDs and QSTs formation on such a high index GaAs substrates was explained in terms of piezoelectric driven atoms and the equilibrium surfaces at edges.     

Patterning nanoroads and quantum dots on fluorinated graphene

Using ab initio methods we have investigated the fluorination of graphene and find that different stoichiometric phases can be formed without a nucleation barrier, with the complete “2D-Teflon” CF phase being thermodynamically most stable. The fluorinated graphene is an insulator and turns out to be a perfect matrix-host for patterning nanoroads and quantum dots of pristine graphene. The electronic and magnetic properties of the nanoroads can be tuned by varying the edge orientation and width. The energy gaps between the highest occupied and lowest unoccupied molecular orbitals (HOMO-LUMO) of quantum dots are size-dependent and show a confinement typical of Dirac fermions. Furthermore, we study the effect of different basic coverage of F on graphene (with stoichiometries CF and C₄F) on the band gaps, and show the suitability of these materials to host quantum dots of graphene with unique electronic properties.     

Deterministic Assembly of Single Sub-20 nm Functional Nanoparticles Using a Thermally Modified Template with a Scanning Nanoprobe

A deterministic assembly technique for single sub-20 nm functional nanoparticles is developed based on nanostructured templates fabricated by hot scanning nanoprobes. With this technique, single nanoparticles including quantum dots, polystyrene fluorescent nanobeads, and gold nanoparticles are successfully assembled into 2D arrays with high yields. Experimental and theoretical analyses show that the key for the high yields is the hot-probe-based template fabrication technique, which creates geometrical nanotraps and modifies their surface energy simultaneously. In addition to single nanoparticle patterning, further experiments demonstrate that this technique is also capable of building complex nanostructures, such as nanoparticle clusters with well-defined shapes and heterogeneously integrated nanostructures consisting of quantum dots and silver nanowires. It opens the door to many important applications.     

Quantum dot encoding of aptamer-linked nanostructures for one-pot simultaneous detection of multiple analytes

One major challenge in analytical chemistry is multiplex sensing of a number of analytes with each analyte displaying a different signal. To meet such a challenge, quantum dots that emit at 525 and 585 nm are used to encode aptamer-linked nanostructures sensitive to adenosine and cocaine, respectively. In addition to quantum dots, the nanostructures also contain gold nanoparticles that serve as quenchers. Addition of target analytes disassembles the nanostructures and results in increased emission from quantum dots. Simultaneous colorimetric and fluorescent detection and quantification of both molecules in one pot is demonstrated.     

Fabrication of dumbbell-like CdTe/Au nanohybrids

Dumbbell-like CdTe/Au nanohybrids were synthesized by assembly of CdTe quantum dots with the assistance of AuCl₄⁻ in aqueous solution. The products were characterized by TEM and SEM techniques. The images reveal that dumbbell-like nanostructures with uniform size were well formed. The dumbbell-like nanostructures were further characterized by HRTEM and EDX spectrum. The results indicate that the as-prepared dumbbell-like nanostructures were composed of CdTe quantum dots and Au nanoparticles. The effect of HAuCl₄ concentration on the morphology of the products was also investigated, which shows that the morphology of the products evolved from sheaf-like nanostructures to rod-like nanostructures and finally dumbbell-like nanostructures as the HAuCl₄ concentration increased. Based on the above results, a possible mechanism for the formation of dumbbell-like CdTe/Au nanohybrids is proposed.     

One-step,solvothermal synthesis of graphene-CdS and graphene-ZnS quantum dot nanocomposites and their interesting photovoltaic properties

The synthesis of graphene-semiconductor nanocomposites has attracted increasing attention due to their interesting optoelectronic properties. However the synthesis of such nanocomposites, with decorated particles well dispersed on graphene, is still a great challenge. This work reports a facile, one-step, solvothermal method for the synthesis of graphene-CdS and graphene-ZnS quantum dot nanocomposites directly from graphene oxide, with CdS and ZnS very well dispersed on the graphene nanosheets. Photoluminescence measurements showed that the integration of CdS and ZnS with graphene significantly decreases their photoluminescence. Transient photovoltage studies revealed that the graphene-CdS nanocomposite exhibits a very unexpected strong positive photovoltaic response, while separate samples of graphene and CdS quantum dots (QDs) of a similar size do not show any photovoltaic response.     

Study of the chemical and morphological evolution of InSb(001) surface under low energy ion bombardment

InSb(001) surfaces were subjected to 4 keV Ar⁺ bombardment at oblique angles of incidence with ion fluences in the range of 9.0 × 10¹³-6.2 × 10¹⁷ ions/cm². The evolution of bombardment induced surface structures and their chemical composition were studied with Atomic Force Microscopy (AFM) and Kelvin Probe Force Microscopy (KPFM) in UHV, and “ex situ” with Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray spectroscopy (EDX). Various morphological features, such as small dots, wires and for very high ion fluence ripple-like structures were observed. It was found that both the initial surface crystallographic structure and the ion beam direction influence the developing anisotropic nanostructures on the irradiated surface. It was also found that the time evolution of the nanostructured surface in terms of surface roughness σ, follows a power law σ ∼ t^β. The surface nanostructures (dots and wires), at every stage of their development, are found to have different work functions in comparison to the surrounding InSb substrate. The results indicate that the nanostructures developed on the irradiated InSb surfaces consist of indium.     

Improved Charge Extraction Beyond Diffusion Length by Layer‐by‐Layer Multistacking Intercalation of Graphene Layers inside Quantum Dots Films

Charge collection is critical in any photodetector or photovoltaic device. Novel materials such as quantum dots (QDs) have extraordinary light absorption properties, but their poor mobility and short diffusion length limit efficient charge collection using conventional top/bottom contacts. In this work, a novel architecture based on multiple intercalated chemical vapor deposition graphene monolayers distributed in an orderly manner inside a QD film is studied. The intercalated graphene layers ensure that at any point in the absorbing material, photocarriers will be efficiently collected and transported. The devices with intercalated graphene layers have superior quantum efficiency over single‐bottom graphene/QD devices, overcoming the known restriction that the diffusion length imposes on film thickness. QD film with increased thickness shows efficient charge collection over the entire λ ≈ 500–1000 nm spectrum. This architecture could be applied to boost the performance of other low‐cost materials with poor mobility, allowing efficient collection for films thicker than their diffusion length.     

Blinking suppression and intensity recurrences in single CdSe-oligo(phenylene vinylene) nanostructures: experiment and kinetic model

We report time-resolved single molecule fluorescence imaging of individual CdSe quantum dots that are functionalized with oligomeric conjugated organic ligands. The fluorescence intensity trajectories from these composite nanostructures display both a strong degree of blinking suppression and intensity fluctuations with characteristic recurrence times on the order of 10-60?s. In addition, fluorescence decay rate measurements of individual hybrid nanostructures indicate significantly modified non-radiative quantum dot decay rates relative to conventional ZnS-capped CdSe quantum dots. We show that a modified diffusive reaction coordinate model with slow fluctuations in quantum dot electron energies (1S(e), 1P(e)) can reproduce the experimentally observed behaviour.     

Atomic layer deposition of lead sulfide quantum dots on nanowire surfaces

Quantum dots provide unique advantages in the design of novel optoelectronic devices owing to the ability to tune their properties as a function of size. Here we demonstrate a new technique for fabrication of quantum dots during the nucleation stage of atomic layer deposition (ALD) of PbS. Islands with sub-10 nm diameters were observed during the initial ALD cycles by transmission electron microscopy, and in situ observations of the coalescence and sublimation behavior of these islands show the possibility of further modifying the size and density of dots by annealing. The ALD process can be used to cover high-aspect-ratio nanostructures, as demonstrated by the uniform coating of a Si nanowire array with a single layer of PbS quantum dots. Photoluminescence measurements on the quantum dot/nanowire composites show a blue shift when the number of ALD cycles is decreased, suggesting a route to fabricate unique three-dimensional nanostructured devices such as solar cells.     

Calculated optical transitions in a silicon quantum wire modulated by a quantum dot

The photoluminescence lifetimes of Si quantum wires and dots have been previously calculated within a continuum model that takes into account the anisotropy of silicon band structure. Here, we present our calculations on the optical transitions in Si quantum wires modulated by a quantum dot. The geometrical parameters of the buldged wire are appropriate for porous Si and the ground state is localized. The photoluminescence lifetimes are calculated and compared with those of straight wires and dots. The magnitude of the lifetime is sensitive to the structural parameters of the nanostructures. Lifetimes varying from nanoseconds to milliseconds have been obtained. The results of the calculations provide insight to the optical properties of Si nanostructures.     

A facile method for fabrication of large area graphene nanostructures

In this study, we introduce a novel method to produce large area interconnected graphene nanostructures. A single layer CVD (Chemical Vapor Deposition) grown graphene was nanostructured by employing dewetted Ni thin film as an etching mask for the underlying graphene. As a result, a network of graphene nanostructures with irregular shapes and widths down to 10 nm is obtained. The FET (field effect transistor) devices fabricated employing the nanostructured graphene as channel material exhibit increased on/off current ratio compared to pristine graphene indicating a slight band gap opening due to the quantum confinement effect in such narrow graphene nanostructures. This technique can be useful for the large scale fabrication of graphene based electronic devices such as FETs and sensors.