Optical properties of semiconductor quantum dots in magnetic fields

Optical properties of semiconductor quantum dots in magnetic fields are reviewed. A theory is described based on a multi-band effective-mass approximation with a nonparabolic conduction electron dispersion, the direct Coulomb interaction, and the electron-hole exchange interaction taken into account. The transition from the quantum-confined Zeeman effect for a weak magnetic field to the quantum-confined Paschen-Back effect to a strong magnetic field is discussed in comparison with atomic spectra in magnetic fields. Experimental results of the optical properties of isolated CuCl, CdSSe, and Si quantum dots in magnetic fields are also discussed in conjunction with the theoretical results.     

Optical properties of individual manganese-doped quantum dots

The magnetic state of a single magnetic ion (Mn²⁺) embedded in an individual quantum dot is optically probed using micro-spectroscopy. The fine structure of a confined exciton in the exchange field of a single Mn²⁺ ion (S=) is analyzed in detail. The exciton–Mn²⁺ exchange interaction shifts the energy of the exciton depending on the Mn²⁺ spin component and six emission lines are observed at zero magnetic field. The emission spectra of individual quantum dots containing a single magnetic Mn atom differ strongly from dot to dot. The differences are explained by the influence of the system geometry, specifically the in-plane asymmetry of the quantum dot and the position of the Mn atom. Depending on both these parameters, one has different characteristic emission features which either reveal or hide the spin state of the magnetic atom. The observed behavior in both zero field and under magnetic field can be explained quantitatively by the interplay between the exciton–Mn²⁺ exchange interaction (dependent on the Mn position) and the anisotropic part of the electron–hole exchange interaction (related to the asymmetry of the quantum dot).     

Optical properties of InAs quantum dots in a Si matrix

We report on the optical properties of nanoscale InAs quantum dots in a Si matrix. At a growth temperature of 400°C, the deposition of 7 ML InAs leads to the formation of coherent islands with dimensions in the 2–4 nm range with a high sheet density. Samples with such InAs quantum dots show a luminescence band in the 1.3 μm region for temperatures up to 170 K. The PL shows a pronounced blue shift with increasing excitation density and decays with a time constant of 440 ns. The optical properties suggest an indirect type II transition for the InAs/Si quantum dots. The electronic structure of InAs/Si QDs is discussed in view of available band offset information.     

Synthesis of graphene oxide and graphene quantum dots from miscanthus via ultrasound-assisted mechano-chemical cracking method

Whilst graphene materials have become increasingly popular in recent years, the followed synthesis strategies face sustainability, environmental and quality challenges. This study proposes an effective, sustainable and scalable ultrasound-assisted mechano-chemical cracking method to produce graphene oxide (GO). A typical energy crop, miscanthus, was used as a carbon precursor and pyrolysed at 1200 °C before subjecting to edge-carboxylation via ball-milling in a CO₂-induced environment. The resultant functionalised biochar was ultrasonically exfoliated in N-Methyl-2-pyrrolidone (NMP) and water to form GOs. The intermediate and end-products were characterised via X-ray diffraction (XRD), Raman, high-resolution transmission electron microscopy (HR-TEM) and atomic force microscopy (AFM) analyses. Results show that the proposed synthesis route can produce good quality and uniform GOs (8–10% monolayer), with up to 96% of GOs having three layers or lesser when NMP is used. Ultrasonication proved to be effective in propagating the self-repulsion of negatively-charged functional groups. Moreover, small amounts of graphene quantum dots were observed, illustrating the potential of producing various graphene materials via a single-step method. Whilst this study has only investigated utilising miscanthus, the current findings are promising and could expand the potential of producing good quality graphene materials from renewable sources via green synthesis routes.     

One-pot synthesis of fluorescent nitrogen-doped graphene quantum dots for portable detection of iron ion

Nitrogen-doped graphene quantum dots (N-GQD) were synthesized by direct thermal decomposition of ammonium citrate tribasic. With the increment of torrefaction temperature, the average size of N-GQD was increased from 2.56 to 3.73 nm. Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy analysis (XPS) proved the successful doping of nitrogen atoms. Besides, the N-GQDs showed blue fluorescence which was quenched by Fe³⁺ ions, and the fluorescence intensity of N-GQDs decayed exponentially. Accordingly, the same quenching effect was observed on a test paper prepared by soaking paper in N-GQDs dispersion. The quenching mechanism was due to electron transfer between Fe³⁺ and functional groups on the surface of N-GQDs which could be confirmed by XPS and diameter growth. Therefore, through this simple method, N-GQDs with high blue fluorescence and high production yield (64%) can be prepared, which provided a new strategy for monitoring and collecting Fe³⁺ in environmental water.     

Influence of stoichiometry on the luminescent properties of InAs quantum dots grown on a heterostructure

We report photoluminescence (PL) spectra of InP/In_xGa_1-xAs/InAs/InP dot-in-a-well structures grown by MOVPE, with different compositions of the ternary layer. Measurements with atomic force microscopy showed that the largest quantum dot (QD) height is obtained when the InAs QDs are grown on the In_xGa_1-xAs layer with a mismatch of 1000 ppm, and the height decreases as the mismatch departs from this value. PL spectra of the QDs showed an asymmetric band, which involves transitions between dot energy levels and can be deconvoluted into two peaks. The highest energy PL peak of this band was observed for the sample with the QDs grown on top of the lattice-matched In_xGa_1-xAs layer and it shifted to lower energies for strained samples as the degree of mismatch increased. Theoretical calculations of the energy levels of the entire structure were used to interpret the obtained PL spectra and determine the possible detection tunability range.     

Synthesis and characterization of graphene quantum dots and their size reduction using swift heavy ion beam

Graphene quantum dots (GQDs) are nanosized fragments of graphene displaying quantum confinement effect. They have shown to be prepared from various methods which include ion beam etching of graphene. However, recently the modification of the GQDs has garnered tremendous attention owing to its suitability for various applications. Here, we have studied the effect of swift ion beam irradiation on the properties of GQDs. The ion beam treatment on the GQDs exhibited the change in observed photoluminescence of GQDs as they exhibited a blue luminescence on excitation with longwave UV (≈365?nm) due to the reduction in size and removal of the ethoxy (–C–O–C–) groups present on the quantum dots. This was confirmed by transmission electron microscopy, particle size analysis, and Fourier transform infrared spectroscopy.     

Strongly confined semiconductor quantum dots: Pair excitations and optical properties

This paper reviews a microscopic model of basic electron-hole pair excitation processes in strongly confined semiconductor quantum dots (QD) and their influence on the optical QD properties. The effects of valence band mixing, Coulomb interaction, and surface polarization are taken into account. The exciton and biexciton wave functions and energies are obtained using a numerical diagonalization method. The computed optical spectra, such as absorption, gain, pump-probe, and two-photon absorption, agree well with experiments.     

EMI shielding effectiveness of graphene decorated with graphene quantum dots and silver nanoparticles reinforced PVDF nanocomposites

Graphene decorated with graphene quantum dots (G-D-GQDs) have been successfully synthesized using solvothermal cutting of graphene oxide. The incorporation of G-D-GQDs in polyvinyledene fluoride (PVDF) matrix shows the total EMI shielding effectiveness (SE_T) of 31 dB at 8 GHz. The main mechanism of high EMI shielding effectiveness is reflection and absorption of EM radiation. The high absorption of EM radiation is due to tunneling of electrons from GQDs. Further, decoration of G-D-GQDs with conducting Ag nanoparticles (G-D-GQDsAg) enhances the SE_T value to 43 dB at 8 GHz of PVDF/G-D-GQDsAg nanocomposite, due to increase in electrical conductivity of PVDF/G-D-GQDsAg nanocomposite and enhanced dispersion of G-D-GQDsAg in PVDF matrix. The incorporation of G-D-GQDs and G-D-GQDsAg in PVDF matrix also increases the thermal stability and crystallinity of PVDF. The increase in thermal stability and crystallinity are more for PVDF/G-D-GQDsAg nanocomposite as compare to PVDF/G-D-GQDs nanocomposite, due to better dispersion of G-D-GQDsAg in PVDF matrix. Thus, PVDF/G-D-GQDsAg nanocomposite having high SE_T value can shield 99.9% of electromagnetic radiation in X-band range, which make it suitable for EMI shielding application for consumer electronic equipment’s.     

Optical modelling of quantum dots

The analogy between quantum mechanics and electromagnetism is used to design an optical waveguide with the same transmission and traversal time as a quantum dot. Two different quantum dot geometries are considered for two typical applications: ultrafast devices and computing.     

One-pot synthesis of highly fluorescent amino-functionalized graphene quantum dots for effective detection of copper ions

In this work, a green and simple one-pot route was developed for the synthesis of highly fluorescent amino-functionalized graphene quantum dots (a-GQDs) via hydrothermal process without any further modification or surface passivation. We synthesized the a-GQDs using glucose as the carbon source and ammonium as a functionalizing agent without the use of a strong acid, oxidant, or other toxic chemical reagent. The as-obtained a-GQDs have a uniform size of 3–4 nm, high contents of amino groups, and show a bright green emission with high quantum yield of 32.8%. Furthermore, the a-GQDs show effective fluorescence quenching for Cu²⁺ ions which can serve as effective fluorescent probe for the detection of Cu²⁺. The fluorescent probe using the obtained a-GQDs exhibits high sensitivity and selectivity toward Cu²⁺ with the limit of detection as low as 5.6 nM. The mechanism of the Cu²⁺ induced fluorescence quenching of a-GQDs can be attributed to the electron transfer by the formation of metal complex between Cu²⁺ and the amino groups on the surface of a-GQDs. These results suggest great potential for the simple and green synthesis of functionalized GQDs and a practical sensing platform for Cu²⁺ detection in environmental and biological applications.     

Substitutional impurity in the graphene quantum dots

The process of formation of the localized defect states due to substitutional impurity in sp²-bonded graphene quantum dot is considered using a simple tight-binding-type calculation. We took into account the interaction of the quantum dot atoms surrounding the substitutional impurity from the second row of elements. To saturate the external dangling sp² orbitals of the carbon additionally 18 hydrogen atoms were introduced. The chemical formula of the quantum dot is H₁₈C₅₁X, where X is the symbol of substitutional atom. The position of the localized levels is determined relative to the host-atoms (C) ε_p energies. We focused on the effect of substitutional doping by the B, N and O on the eigenstate energies and on the total energy change of the graphene dots including for O the effect of lattice distorsion. We conclude that B, N, and O can form stable substitutional defects in graphene quantum dot.     

Pressure effect on optical properties of modified Gaussian quantum dots

In the present work, we intend to study the pressure effect on optical properties of spherical quantum dots by using the modified Gaussian potential. In this regard, the linear, nonlinear and total intersubband absorption coefficients and refractive index changes are investigated for different hydrostatic pressures. According to the results obtained from the present work, it is deduced that: (i) the linear, nonlinear and total refractive index changes decrease and shift towards higher energies when the pressure increases and (ii) the linear, nonlinear and total absorption coefficients increase and shift towards higher energies by increasing the pressure.     

石墨烯量子点的磁性及激发态性质

利用密度泛函理论在B3LYP/6-31G(d)基组水平上研究了具有zigzag边界的石墨烯量子点,结果表明不同大小的石墨烯量子点的基态都是具有磁性的自旋三重态.其磁性一方面来源于zigzag边界上占有凸出位置的碳原子,另一方面来源于带有孤对电子的碳原子.从整体上看,除6b结构外,其他结构的能隙随着苯环数量的增加逐渐减小,而附加电荷却使体系能隙明显减小.用含时密度泛函理论(TD-DFT)对能隙为3.83 eV的由六个苯环排列成的三角形结构进行了激发态的计算,发现第十七激发态强度最大,能量为3.93 eV,对 关键词： 石墨烯量子点 磁性 能隙 激发态     

Quantum confinement in graphene quantum dots

By performing density functional theory calculations, we studied the quantum confinement in charged graphene quantum dots (GQDs), which is found to be clearly edge and shape dependent. It is found that the excess charges have a large distribution at the edges of the GQD. The resulting energy spectrum shift is very nonuniform and hence the Coulomb diamonds in the charge stability diagram vary irregularly, in good agreement with the observed nonperiodic Coulomb blockade oscillation. We also illustrate that the level statistics of the GQDs can be described by a Gaussian distribution, as predicted for chaotic Dirac billiards.

     

Sonocatalytic degradation of methylene blue by a novel graphene quantum dots anchored CdSe nanocatalyst

Cadmium selenide/graphene quantum dots (CdSe/GQDs) nanocatalyst with small band gap energy and a large specific surface area was produced via a facile three-step sonochemical-hydrothermal process. The features of the as-prepared CdSe, GQDs and CdSe/GQDs samples were characterized by photoluminescence spectroscopy (PL), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), X-ray diffraction (XRD), Fourier transformed infrared (FT-IR), diffuse-reflectance spectrophotometer (DRS), and Brunauer–Emmett–Teller (BET) analysis. The sonocatalytic activity of the synthesized CdSe/GQDs was effectively accelerated compared with that of pure CdSe nanoparticles in degradation of methylene blue (MB). The influence of the CdSe/GQDs dosage (0.25–1.25 g/L), initial MB concentration (20–30 mg/L), initial solution pH (3–12), and ultrasonic output power (200–600 W/L) were examined on the sonocatalytic treatment of MB aqueous solutions. The degradation efficiency (DE%) of 99% attained at 1 g/L of CdSe/GQDs, 20 mg/L of MB, pH of 9, and an output power of 200 W/L at 90 min of ultrasonic irradiation. Furthermore, DE% increased with addition of K₂S₂O₈ and H₂O₂ as the enhancers via producing more free radicals. However, addition of sulfate, carbonate, and chloride as radical sweeper decreased DE%. Furthermore, well-reusability of the CdSe/GQDs sonocatalyst was demonstrated for 5 successive runs and some of the sonocatalytic generated intermediates were indicated by GC–MS analysis.