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We describe the use of cadmium telluride quantum dots (CdTe QDs) as antennas for the photosensitization of nitric oxide release from a ruthenium nitrosyl complex with visible light excitation. The CdTe QDs were capped with mercaptopropionic acid to make them water-soluble, and the ruthenium nitrosyl complex was cis-[Ru(NO)(4-ampy)(bpy)2](3+) (Ru-NO; bpy is 2,2'-bipyridine, and 4-ampy is 4-aminopyridine). Solutions of these two components demonstrated concentration-dependent quenching of the QD photoluminescence (PL) as well as photoinduced release of NO from Ru-NO when irradiated by 530 nm light. A NO release enhancement of ∼8 times resulting from this association was observed under longer wavelength excitation in visible light range. The dynamics of the quenching determined by both PL and transient absorption measurements were probed by ultrafast flash photolysis. A charge transfer mechanism is proposed to explain the quenching of the QD excited states as well as the photosensitized release of NO from Ru-NO.

A theoretical–experimental approach is proposed to convert the photoluminescence spectra of colloidal perovskite quantum dot ensembles into accurate estimates for their intrinsic particle size distribution functions. Two main problems were addressed and properly correlated: the size dependence of the first excitonic transition in a single cube-shaped quantum dot and the inhomogeneous broadening of the fluorescence line shape due to the size nonuniformity of the chemically prepared quantum dot suspension in addition to the single-dot homogeneous broadening. By applying the reported methodology to CsPbBr3 quantum dot samples belonging to the strong and intermediate confinement regimes, the calculated size distributions exhibited close agreement with those obtained from transmission electron microscopy, with precise estimates for the average particle size and standard deviation. Specifically for strongly confined ultrasmall CsPbBr3 quantum dots, the presented spectroscopic model for size distribution computation is based on a new analytical expression for the size-dependent bandgap, which was developed within the framework of the finite-depth square-well effective mass approximation accounting for band nonparabolicity effects. Such a quantum mechanical approach correctly predicts the expected transition to the intermediate confinement regime in sufficiently large quantum dots, which are traditionally described by the well-known bandgap equation in the infinite potential barrier limit with a spatially correlated electron–hole wavefunction and nonparabolic carrier effective masses. The proposed calculation scheme originates from general theoretical considerations so that it can be readily adapted to semiconductor quantum dots of many other systems, from all inorganic metal halides to hybrid perovskite materials, regardless of the adopted chemical synthesis route. [ABSTRACT FROM AUTHOR]

Quantum dots (QDs) have attracted much attention and exhibit many attractive properties, including high absorption coefficient, adjustable bandgap, high brightness, long-term stability, and size-dependent emission. It is known that to obtain high-quality luminescent properties (i.e. emission color, color purity, quantum yield, and stability), the synthesis parameters must be precisely controlled. In this work, we have constructed a database with CdTe aqueous synthesis parameters and spectroscopic results and applied machine learning algorithms to better understand the influence of the main synthesis parameters of CdTe QDs on their final emission properties. A strong dependence of the final emission wavelength with the reaction time and surface ligands and precursors concentrations was demonstrated. These parameters adjusted synchronously were shown to be very useful for provide ideal synthesis conditions for the preparation of CdTe QDs with desirable emission wavelengths. Moreover, applying the algorithms correctly allows for obtaining information and insights into the growth kinetics of QDs under different synthetic conditions. [ABSTRACT FROM AUTHOR]

Energy demand, global warming, environmental impacts, sustainability, and energy sources are some of the concerns faced by humanity. Quantum‐dot‐sensitized solar cells (QDSSC) are an alternative solution to addressing some of these issues, in addition to reducing the costs of producing electrical energy. However, QDSSCs present stability problems and low efficiency, less than 16%. In light of this challenge, this review aims to present the main strategies adopted to reduce energy losses that occur in each component of the solar cell, with a focus on one key component: the counter electrode (CE). The CE plays a crucial role in collecting electrons and regenerating the electrolyte, thus impacting the lifespan and efficiency of QDSSCs. As such, this review discusses the main advancements in CEs based on key materials such as metal sulfides, carbonaceous materials, and composites. The efforts related to the synthesis and application of different counter electrodes for QDSSCs are explored. [ABSTRACT FROM AUTHOR]

Incorporation of quantum dots (QDs) into porous matrices has triggered the development of novel optical devices. In this work, TiO2 sensitized by CdTe incorporated into bacterial nanocellulose (BNC) membranes were tested as photoelectrodes in a photoelectrochemical cell directed to the water splitting for hydrogen generation. The flexible membranes were produced by immersing BNC membranes in an aqueous solution of CdTe capped with glutathione (CdTe-GSH) and further deposited over a thin layer of TiO2. Incorporation of CdTe-GSH into BNC membranes was confirmed by infrared spectroscopy. Fluorescence spectroscopy revealed that the luminescence intensity increased with the immersion time in the CdTe-GSH solution. Field-emission gun scanning electron microscopy (FEG-SEM) images revealed that the CdTe/QDs (5 nm) were homogeneously dispersed on the cellulose nanofibers. BNC/CdTe-GSH membranes was tested as photoelectrodes. Photoelectrochemical cells exhibited a significant photocurrent in wavelengths ranging from 400 to 800 nm, which indicates their potential for applications as flexible electrodes, sensors and photovoltaic systems. [ABSTRACT FROM AUTHOR]

We report here on the direct observation of distinct two-photon transition channels in glutathione-capped (GSH) CdTe quantum dots (QDs) in a very strong confinement regime. CdTe-GSH QDs with different average diameters (2.5, 3.0, and 3.3 nm) were synthesized through the one-pot method and their two-photon absorption (2PA) spectrum determined by a femtosecond wavelength-tunable Z-scan. Our results show that the two lower-energy one-photon-allowed excitonic transitions, 1S3/2(h) → 1S(e) and 2S3/2(h) → 1S(e), are also accessed via 2PA. These results were ascribed to the relaxation of the parity selection rules due to the noncentrosymmetric structure of the CdTe QDs (zinc-blended structure), whose magnitude are determined by surface defects and structural irregularities present in CdTe-GSH QDs, in the strong confinement regime. [ABSTRACT FROM AUTHOR]

We conducted a comparative synthesis of water-soluble CdTe/CdS colloidal nanocrystalline semiconductors of the core/shell type. We prepared the CdS shell using two different methods: a one-pot approach and successive ionic layer adsorption and reaction (SILAR); in both cases, we used 3-mercaptopropionic acid (MPA) as the surface ligand. In the one-pot approach, thiourea was added over the freshly formed CdTe dispersion, and served as the sulfur source. We achieved thicker CdS layers by altering the Cd:S stoichiometric ratio (1:1, 1:2, 1:4, and 1:8). The Cd:S ratios 1:1 and 1:2 furnished the best optical properties; these ratios also made the formation of surface defects less likely. For CdTe/CdS obtained using SILAR, we coated the surface of three differently sized CdTe cores (2.17, 3.10, and 3.45 nm) with one to five CdS layers using successive injections of the Cd2+ and S2– ions. The results showed that the core size influenced the optical properties of the materials. The deposition of three to five layers over the surface of smaller CdTe colloidal nanocrystals generated strain effects on the core/shell structure. [ABSTRACT FROM AUTHOR]

A novel and simple method is described for preparing colloidal Cu-doped ZnSe(S) quantum dots (QDs) in aqueous media by introducing copper ions using the same method as to prepare colloidal ZnSe(S). More specifically, the Cu-doped ZnSe(S) are prepared through the nucleation-doping method in the presence of 3-mercaptopropionic acid as stabilizers using zinc perchlorate, copper sulphate, and NaHSe as precursors. Confirmation of the preparation of Cu-doped ZnSe(S) nanocrystals (NCs) is done with absorption and emission spectroscopies (UV-vis and PL) as the QDs show intensive green emissions. The reduction of ions Cu2+ to Cu+ is confirmed by using electron paramagnetic resonance (EPR), in which Cu+ ions are silent. The size determination is performed by using transmission electron microscopy (TEM) and dynamic light scattering (DLS), resulting in Cu-doped ZnSe(S) particles with a mean diameter of 4.6 ± 3.5 nm. The excellent stability observed for the nanoparticles overcomes the intrinsic instability of traditional aqueous Cu-doped ZnSe(S) NCs. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of CdS nanoparticles prepared in poly(vinyl alcohol) (PVA) in situ, to produce a series of CdS/PVA nanocomposite films, is described in this paper. The role of 2-mercaptoethanol as the surface ligand for the nanoparticles has been investigated. Different molar concentrations of the cadmium precursor have also been evaluated, aiming at the preparation of stable aqueous colloidal systems and polymeric films. UV-visible (UV-Vis) and photoluminescence spectroscopies together with scanning electron microscopy and transmission electron microscopy have been used for characterization of the growth kinetics and the relative stability of CdS nanocrystals in the polymeric matrix. The results clearly indicate the formation of hexagonal CdS nanoparticles embedded in the PVA matrix. PVA was not effective in stabilizing colloidal CdS nanoparticles against aggregation. However, it leads to a displacement of the first optical transition of CdS due to compressive deformation effect. The combination of PVA with 2-mercaptoethanol as surface ligands had a strong effect on the optical properties of the resulting embedded CdS nanoparticles. [ABSTRACT FROM AUTHOR]

A facile hydrothermal method to synthesize water-soluble copper indium sulfide (CIS) nanocrystals (NCs) at 150 °C is presented. The obtained samples exhibited three distinct photoluminescence peaks in the red, green and blue spectral regions, corresponding to three size fractions, which could be separated by means of size-selective precipitation. While the red and green emitting fractions consist of 4.5 and 2.5 nm CIS NCs, the blue fraction was identified as in situ formed carbon nanodots showing excitation wavelength dependent emission. When used as light absorbers in quantum dot sensitized solar cells, the individual green and red fractions yielded power conversion efficiencies of 2.9% and 2.6%, respectively. With the unfractionated samples, the efficiency values approaching 5% were obtained. This improvement was mainly due to a significantly enhanced photocurrent arising from complementary panchromatic absorption. [ABSTRACT FROM AUTHOR]

Abstract We have interpreted the two-photon absorption spectrum of water-soluble copper indium sulfide (CIS) QDs with stoichiometry 0.18 (Cu), 0.42 (In), and 2 (S) and an average diameter of approximately 2.6 nm. For that, we employed the wavelength-tunable femtosecond Z-scan technique and the parabolic effective-mass approximation model, in which the excitonic transition energies were phenomenologically corrected due to the stoichiometry of the nanocrystal. This model considers a conduction band and three valence sub-bands allowing excitonic transitions via centrosymmetric (Δl = ±1 , where l is the angular momentum of the absorbing state) and non-centrosymmetric (Δl = 0) channels. In such case, this became relevant because the CIS QDs with chalcopyrite crystalline structure is a non-centrosymmetric semiconductor. Thus, our experimental results pointed out two 2 PA allowed bands located at 715 nm (2hv = 3.47 eV) and 625 nm (2hv = 3.97 eV) with cross sections of (6.3 ± 1.0) x 102 GM and (4.5 ± 0.7) x 102 GM, respectively. According to the theoretical model, these 2 PA bands can be ascribed to the 1P 1/2 (h 3) → 1S 3/2 (e) (lower energy band) and 1P 1/2 (h heavy) → 1S 3/2 (e) (90%) / (10%) 1P 1/2 (h split-off) → 1P 3/2 (e) (higher energy band) excitonic transitions. A good agreement (magnitude and spectral position) between the experimental and theoretical data were obtained. However, our experimental data suggest that the higher-energy 2 PA band may have other contributions due to the mixing between the heavy- and the light-hole bands, which the effective mass model does not take into consideration. Highlights • The two-photon absorption spectrum of CIS quantum dots was characterized through the femtosecond Z-scan technique. • The nonlinear optical spectrum was modeled through the parabolic effective-mass approximation model. • The excitonic transition energies were phenomenologically corrected due to the stoichiometry of the nanocrystal. • A good agreement (magnitude and spectral position) between the experimental and theoretical data were obtained. [ABSTRACT FROM AUTHOR]