Our preliminary investigation of the absorption and the photoluminescence response of selectively separated graphene quantum dots using centrifugation indicate that the photoluminescence is more sensitive to the size of the quantum dot than the absorption. We observed ∼143nm blueshift from 623nm to 480nm in the visible region of the photoluminescence with increasing successive centrifugation (decreasing size) and not in the corresponding absorption spectra in the visible region. However, for the first time, we observed a blueshift in the absorption spectra in the UV regions that is tentatively attributed to quantum confinement. Further detailed work is underway to confirm the blueshift in the absorption and correlate with deep UV photoluminescence and morphological quantification of the quantum dots size distribution using high resolution transmission electron microscope.

The actual incorporation of dopant species into the ZnS Quantum Dots (QDs) host lattice will induce structural defects evidenced by a red shift in the corresponding exciton. The doping should create new intermediate energetic levels between the valence and conduction bands of the ZnS and affect the electron-hole recombination. These trap states would favour the energy transfer processes involved with the generation of cytotoxic radicals, so-called Reactive Oxygen Species, opening the possibility to apply these nanomaterials in cancer research. Any synthesis approach should consider the direct formation of the QDs in biocompatible medium. Accordingly, the present work addresses the microwave-assisted aqueous synthesis of pure and doped ZnS QDs. As-synthesized quantum dots were fully characterized on a structural, morphological and optical viewpoint. UV-Vis analyzes evidenced the excitonic peaks at approximately 310 nm, 314 nm and 315 nm for ZnS, Cu-ZnS and Mn-ZnS, respectively, Cu/Zn and Mn/Zn molar ratio was 0.05%. This indicates the actual incorporation of the dopant species into the host lattice. In addition, the Photoluminescence spectrum of non-doped ZnS nanoparticles showed a high emission peak that was red shifted when Mn2+ or Cu2+ were added during the synthesis process. The main emission peak of non-doped ZnS, Cu-doped ZnS and Mn-doped ZnS were observed at 438 nm, 487 nm and 521 nm, respectively. Forthcoming work will address the capacity of pure and Cu-, Mn-ZnS quantum dots to generate cytotoxic Reactive Oxygen Species for cancer treatment applications.

Fully inorganic lead halide perovskite nanocrystals (NCs) are of interest for photovoltaic and light emitting devices due to optoelectronic properties. Understanding the surface chemistry of these materials is of importance as surface defects can introduce trap-states which reduce their functionality. Here we use Density Functional Theory (DFT) to model surface defects introduced by Pb2+ on a CsPbBr3 NC atomistic model. Two types of defects are studied: (i) an under-coordinated Pb2+ surface atom and (ii) Pb2+ atomic or molecular adsorbents to the NC surface. From the DFT calculations we compute the density of states (DOS) and absorption spectra of the defect models to the pristine fully-passivated NC model. We observe that for the low surface defect regime explored here that neither (i) or (ii) produce trap-states inside of the bandgap and exhibit bright optical absorption for the lowest energy transition. From the models studied, it was found that the Pb2+ atomic absorbent provides broadening of the conduction band edge, which implies chemisorption of Pb2+ to the NC surface. At higher defect densities it would be expected that Pb2+ atomic absorbents would introduce trap-states and degrade the opto-electronic properties of these materials.

The presence of a direct optical bandgap in the transition metal dichalcogenide (TMD) layers leads to promising applications in optoelectronic devices such as phototransistors and photodetectors. These devices are commonly fabricated using few-layer and monolayer MoS2 sheets obtained using mechanical exfoliation or chemical vapor deposition techniques. The hybrid structure of quantum dots (QDs) and 2D materials has been investigated to provide outstanding properties for various applications. Herein we report the fabrication of a hybrid QDs/MoS2 photodetector consisting of graphene quantum dots (GQDs) and multilayer MoS2 sheets. The hybrid GQDs and MoS2 films are characterized by atomic force microscopy (AFM); additionally, the I-V characteristics are measured by two-point probe station.

Phonons are critical in understanding the electronic, optical and optoelectronic properties of transition metal dichalcogenides (TMDs). The interpretation of lineshapes is important for understanding the effect of specific physical processes on the electronic, optical and optoelectronic properties of TMDs. We employ an analytical approach to investigate the influence of the layered effect, the quantum size effect, the Breit-Wigner-Fano effect, and the inhomogeneous heating effect on the phonon lineshape of TMDs, using WS2 and MoS2 as prototypes. We demonstrate the similarities and differences in how individual processes affect the lineshapes and also the effect of combining processes. Such an approach is useful in guiding the interpretation of the phonon lineshapes of TMDs in particular, and nanostructures in general.

In this study, non-cadmium-based quantum dots were synthesized and used as catalysts for the photochemical reduction of bicarbonate to value-added formic acid. Three types of quantum dots (CuS, CuInS2, and CuInS2/ZnS) were chosen because of they feature environmentally benign properties, possess wide optical absorption, and exhibit excellent photocatalytic activity. All three photocatalysts exhibited excellent efficiency in the photo-reduction of bicarbonate to formic acid, with CuInS2/ZnS showing the highest photon to formate conversion efficiency of 6.07 ± 0.07%. We attribute these exceptional results to their smaller bandgap leading to enhanced visible light absorption and the application of an appropriate hole scavenger that prolongs photo-generated charge carrier separation. To the best of our knowledge, the application of quantum dots in photocatalysis is still quite limited; this report describes the highest apparent quantum efficiency (AQE) to date.

Application of lead-halide perovskite nanostructures for photovoltaic and light emitting applications depends on fashion of the surface termination. The reasonable choice of surface ligands for perovskite nanostructures prevent formation of trap states and contribute to chemical stability, wide opening of the bandgap, and intensity of absorption and photoluminescence of perovskite nanostructures. This work provides atomistic arguments for dual ligand protocol of surface passivation of fully inorganic perovskite quantum dots with fully organic ligands being a mix of cations (ethyl-ammonium) and anions (acetic) in nearly equal proportions. Computed binding energies of either individual ligands or anion-cation pairs demonstrate high stability in comparison to thermal energy and are concluded to be favourable choice in synthesis of colloidal perovskite quantum dots for light emitting applications.

A new quantum dot synthesis method based on metallic-block copolymer precursors was developed. The synthesis produced CdS QDs assembled into chains. This method provides a new model for the study of 1D QD chains to determine its effect on charge transport and optoelectronic coupling. This synthesis method was readily extended to other semiconductor materials including PbS and perovskites producing QDs of various shapes. It evidenced further promise of this synthesis method to assist in the assembly, shape and size control of various nanomaterials

HgTe nanocrystals are extremely interesting materials to obtain a highly tunable absorption spectrum in the infrared range. Here, we discuss the two extreme cases of strongly confined and barely confined HgTe nanocrystals. We discuss the synthesis and optoelectronic properties of HgTe 2D nanoplatelets where the confinement energy can be as large as 1.5 eV. This material presents enhanced (mostly narrower) light emitting properties compared to spherical nanocrystals emitting at the same wavelength. Moreover, absorption spectra, majority carriers and time response can be tuned by carefully choosing the surface chemistry and applying a well-chosen gate bias. HgTe can also be used to explore the effect of vanishing confinement and to obtain quasi bulk properties with tunable absorption in the THz, up to 150 µm.

The design of the surface chemistry of colloidal semiconductor nanocrystals (NCs) presents a powerful synthetic approach that allows to tune the optical and electronic properties of the particles in independent and precisely desired manner, to provide chemical and colloidal stability in diverse media, and, finally, to control their targeted applicability ranging from catalysis, medicine to advanced electronic devices. In this article, we summarize the successful functionalization of colloidal NCs with specifically chosen ligands using a novel ligand-exchange strategy. To transform diverse colloidal NCs into a competitive class of solution-processed semiconductors for electronic applications, we replaced the pristine, insulating ligands with tiny inorganic and hybrid inorganic/organic species. The surface modification with inorganic ions modulates the charge carrier density in NC units and guarantees enhanced interparticle interactions. The subsequent functionalization of the all-inorganic-capped NCs with organic molecules leads to the formation of hybrid inorganic/organic-capped NCs. For example, the introduction of short amine molecules enables to preserve the optical and electronic characteristics of their all-inorganic counterparts, while extending the solubility range and improving the ability to form long-range ordered 2D and 3D superstructures. Moreover, these short amines can be further used as convenient axillary co-ligands facilitating the surface functionalization of all-inorganic NCs with other biocompatible molecules, such as polyethylene glycol (PEG). This opens further perspectives for NCs not only in optoelectronic but also in biological and medical applications.

In this work the one-band effective Hamiltonian governing the electronic states of a quantum dot/ring in a homogenous magnetic field is used to derive a pair/quadruple of nonlinear eigenvalue problems corresponding to different spin orientations and in case of rotational symmetry additionally to quantum number -L•i. We show, that each of those pair/quadruple of nonlinear problems allows for the min-max characterization of its eigenvalues under certain conditions, which are satisfied for our examples and the common InAs/GaAs heterojunction. Exploiting the minmax property we devise efficient iterative projection methods simultaneously handling the pair/quadruple of nonlinear problems and thereby saving up to 40% of the computational time as compared to the nonlinear Arnoldi method applied to each of the problems separately.