Size selective excitonic transition energies in strongly confined CdSe quantum dots

We report on the synthesis of CdSe nanocrystal quantum dots (QDs) of different radii (R). Size dependent optical properties like increase in the confinement energy with decreasing radius for different excitonic transitions are studied. Different excitonic transitions are calculated from the second derivative of UV-vis absorption spectra of as synthesized CdSe QDs. The transitions are assigned to specific states by calculating the transition energies using effective mass approximation. A close matching of the transition energies with the experiment suggesting that the second derivative of the absorption spectra could provide a direct knowledge of the electronic transition for the direct band gap semiconductor quantum dots.     

Hybrid photovoltaic cells with II–VI quantum dot sensitizers fabricated by layer-by-layer deposition of water-soluble components

We present the fabrication of all solid state heterojunction photovoltaic devices consisting of TiO₂ films sensitized by colloidal CdSe and CdTe quantum dots (QDs) and a hole transport layer of the conjugated polymer poly(9,9-dioctyl-fluorene-co-N-(4-butylenphenyl)diphenylamine). The sensitized films were prepared by alternating the layer-by-layer deposition of TiO₂ nanoparticles, water-soluble semiconductor QDs and polycations. Photovoltaic devices sandwiched between fluorinated tin oxide and gold electrodes showed a high rectification ratio and photovoltages of up to 1.15 V. Effective sensitization was observed for CdSe QDs, while incorporated CdTe QDs apparently had no such effect. These findings are explained by confinement effects in QDs.     

Ultrafast electronic delocalization in CdSe/CdS quantum rod heterostructures

Femtosecond cross-polarized transient grating (CPTG) and polarization anisotropy were used to probe the extent of electronic delocalization in CdSe/CdS quantum rod heterostructures (QRH) with a "dot-in-rod" geometry. The alignment of the bulk valence and conduction band edges of CdSe and CdS suggest a "type I" band configuration, leading to localization of both the electron and hole on the CdSe seed, but size quantization effects make the distinction less clear. Photoexcited electrons in 2.1 and 2.9 nm diameter structures have considerable excess kinetic energy above the CdS conduction band and show clear evidence of electron delocalization into the surrounding shell. However, the dependence of the CPTG decay rate on aspect ratio for 2.9 nm seeded QRHs is minimal, suggesting that the delocalization is mostly isotropic (i.e., not preferentially along the rod length). The rates for the 2.1 and 2.9 nm QRHs fall in line with expected trends based on effective exciton size. The 4.2 nm diameter structures also lack any rod length dependence of the CPTG decay and instead exhibit a biexponential decay that is indicative of coupled pathways for fine structure relaxation, likely due to anisotropic interfacial strain. CPTG is found to serve as a unique tool for determining charge transfer and delocalization in nanoheterostructures, which can rarely be predicted accurately from examination of bulk band offsets.     

Fabrication of quantum dot-sensitized solar cells with multilayer TiO2/PbS(X)/CdS/CdSe/ZnS/SiO2 photoanode and optimization of the PbS nanocrystalline layer

In this work, two multilayer photoanode structures of TiO₂/PbS(X)/CdS/ZnS/SiO₂ and TiO₂/PbS(X)/CdS/CdSe/ZnS/SiO₂ were fabricated and applied in quantum dot-sensitized solar cells (QDSCs). Then, the effect of PbS QDs layer on the photovoltaic performance of corresponding cells was investigated. The sensitization was carried out by PbS and CdS QDs layers deposited on TiO₂ scaffold through successive ionic layer adsorption and reaction (SILAR) method. The CdSe QDs film was also formed by a fast, modified chemical bath deposition (CBD) approach. Two passivating ZnS and SiO₂ layers were finally deposited by SILAR and CBD methods, respectively. It was shown that the reference cell with TiO₂/CdS/ZnS/SiO₂ photoanode demonstrated a power conversion efficiency (PCE) of 3.0%. This efficiency was increased to 4.0% for the QDSC with TiO₂/PbS(2)/CdS/ZnS/SiO₂ photoelectrode. This was due to the co-absorption of incident light by low-bandgap PbS nanocrystalline film and also the CdS QDs layer and well transport of the charge carriers. For the CdSe included QDSCs, the PbS-free reference cell represented a PCE of 4.1%. This efficiency was improved to 5.1% for the optimized cell with TiO₂/PbS(2)/CdS/CdSe/ZnS/SiO₂ photoelectrode. The maximized efficiency was enhanced about 25% and 70% compared to the PbS-free reference cells with and without the CdSe QDs layer.

     

Aqueous synthesis of CdSe and CdSe/CdS quantum dots with controllable introduction of Se and S sources

A new and convenient route is developed to synthesize CdSe and core–shell CdSe/CdS quantum dots (QDs) in aqueous solution. CdSe QDs are prepared by introducing H₂Se gas into the aqueous medium containing Cd²⁺ ions. The synthesized CdSe QDs are further capped with CdS to form core–shell CdSe/CdS QDs by reacting with H₂S gas. The gaseous precursors, H₂Se and H₂S, are generated on-line by reducing SeO₃ ^2? with NaBH₄ and the reaction between Na₂S and H₂SO₄, and introduced sequentially into the solution to form CdSe and CdSe/CdS QDs, respectively. The synthesized water-soluble CdSe and CdSe/CdS QDs possess high quantum yield (3 and 20 %) and narrow full-width-at-half-maximum (43 and 38 nm). The synthesis process is easily reproducible with simple apparatus and low-toxic chemicals. The relatively standard deviation of maxima fluorescence intensity is only 2.1 % (n = 7) for CdSe and 3.6 % (n = 7) for CdSe/CdS QDs. This developed route is simple, environmentally friendly and can be readily extended to the large-scale aqueous synthesis of QDs.     

Hole transport in organic field-effect transistors with active poly(3-hexylthiophene) layer containing CdSe quantum dots

Hybrid field-effect transistors (FETs) based on poly(3-hexylthiophene) (P3HT) containing CdSe quantum dots (QDs) were fabricated. The effect of the concentration of QDs on charge transport in the hybrid material was studied. The influence of the QDs capping ligand on charge transport parameters was investigated by replacing the conventional trioctylphosphine oxide (TOPO) surfactant with pyridine to provide closer contact between the organic and inorganic components. Electrical parameters of FETs with an active layer made of P3HT:CdSe QDs blend were determined, showing field-effect hole mobilities up to 1.1×10^?4 cm²/Vs. Incorporation of TOPO covered CdSe QDs decreased the charge carrier mobility while the pyridine covered CdSe QDs did not alter this transport parameter significantly.     

Effect of capping agents on optical and antibacterial properties of cadmium selenide quantum dots

Cadmium selenide quantum dots (CdSe QDs) were synthesized in aqueous phase by the freezing temperature injection technique using different capping agents (viz. thioglycolic acid, 1-thioglycerol, L-cysteine). Absorption spectra of CdSe QDs exhibited a blue shift as compared to its bulk counterpart, which is an indication of quantum confinement effect. The photoluminescence spectra of CdSe QDs confirmed that the particles are poly-dispersed and possess enhanced luminescent property, depending upon the chemical nature of capping agents. The QDs have been characterized by Fourier-transform infrared spectroscopy, atomic absorption spectroscopy and transmission electron microscopy. Further, antimicrobial activity of as-prepared QDs has also been investigated using the disk diffusion method.     

Study on the photoluminescence character of water-soluble CdSe nanocrystals under ambient conditions

Water soluble, thioglycolic acid (TGA) modified CdSe nanocrystals (NCs) have been prepared in aqueous media by the reaction between Cd2+ and NaHSe. Although initially these quantum dots (QDs) display photoluminescence (PL) with very low quantum yields (QY), upon prolonged exposure to ambient light, a strong PL enhancement by illumination is observed which leads to water soluble QDs with high luminescence. This result may have important application potential in biological or other fields. The primary reason for the luminescence enhancement is concluded to be the incorporation of sulfide ions from TGA into the lattice of CdSe NCs and the subsequent formation of alloy structures. Moreover, the CdSe/CdS core-shell structured QDs synthesized in aqueous solutions also consolidate this conclusion.     

Influence of capping ligands on the assembly of quantum dots and their properties

In order to understand the effect of capping ligand on optical and electrical properties of semiconductor quantum dots (QDs), we have added liquid crystal (8CB) to the CdSe/CdS/ZnS QDs monolayer formed via the Langmuir Blodgett technique And studied emission spectra and conducting properties of resulting QDs. The assembly of QDs monolayer modified by liquid crystal (8CB) can be tuned by varying the temperature. The mechanism of the influence of capping ligands on the gap energy, dipole moment and charge distribution within (CdSe)₁₃ cluster was studied via quantum chemical calculations, i.e. we have used density functional theory to systematically investigate the equilibrium configuration of QDs passivated by oleic acid and liquid crystal ligands.     

Histidine functionalised biocompatible CdS quantum dots synthesised by sonochemical method

Histidine functionalised CdS quantum dots (QDs) have been synthesised by sonochemical method. Transmission Electron Microscopy (TEM) observation shows that the histidine functionalised CdS QDs are well-defined, nearly spherical particles. The X-ray diffraction pattern indicates formation of cubic phase of CdS/histidine QDs. The absorption spectra confirm quantum confinement of histidine functionalised CdS QDs. The photoluminescence property of CdS/histidine QDs is found better than that of CdS QDs. Histidine functionalised CdS QDs, in which histidine acts as a biocompatibiliser, can find potential applications in the biological fields.     

Loosening quantum confinement: observation of real conductivity caused by hole polarons in semiconductor nanocrystals smaller than the bohr radius

We report on the gradual evolution of the conductivity of spherical CdTe nanocrystals of increasing size from the regime of strong quantum confinement with truly discrete energy levels to the regime of weak confinement with closely spaced hole states. We use the high-frequency (terahertz) real and imaginary conductivities of optically injected carriers in the nanocrystals to report on the degree of quantum confinement. For the smaller CdTe nanocrystals (3 nm < radius < 5 nm), the complex terahertz conductivity is purely imaginary. For nanocrystals with radii exceeding 5 nm, we observe the onset of real conductivity, which is attributed to the increasingly smaller separation between the hole states. Remarkably, this onset occurs for a nanocrystal radius significantly smaller than the bulk exciton Bohr radius a(B) ～ 7 nm and cannot be explained by purely electronic transitions between hole states, as evidenced by tight-binding calculations. The real-valued conductivity observed in the larger nanocrystals can be explained by the emergence of mixed carrier-phonon, that is, polaron, states due to hole transitions that become resonant with, and couple strongly to, optical phonon modes for larger QDs. These polaron states possess larger oscillator strengths and broader absorption, and thereby give rise to enhanced real conductivity within the nanocrystals despite the confinement.     

Synthesis and size dependent optical studies in CdSe quantum dots via inverse micelle technique

Cadmium selenide quantum dots (CdSe QDs) were successfully synthesized without using trioctylphosphine (TOP). The XRD pattern showed zinc-blend phase of the CdSe QDs. The absorption and PL spectra exhibit a strong blue shift as the QDs size decreases due to the quantum confinement effect. In addition, the quantum efficiency of CdSe QDs with TOP capping is higher than CdSe QDs with oleic acid capping. TEM image shows a spherical shape, compact and dense structure of CdSe QDs. A good agreement between the Tauc's model and experimentally measured absorption spectra of CdSe QDs is achieved. The FTIR peak at ～1712 cm^?1 spectra confirms the influence of oleic acid as a capping agent.     

Optimization of CdSe layer on modified ZnO hierarchical spheres by spin-SILAR for efficient CdS/CdSe co-sensitized solar cells

In this study, after CdS quantum dots sensitized ZnO hierarchical spheres (ZnO HS), we used a simple process to deposit CdSe QDs on ZnO by spin-coating-based SILAR, and applied to photoanodes of quantum dots-sensitized solar cells. Before CdS and CdSe QDs deposition, the ZnO HS photoanodes were modified by Zn(CH₃COO)₂·2H₂O methanol solution to further enhance the open-circuit voltage and power conversion efficiency (PCE). The program of modifying photoanodes and the number of CdSe spin-SILAR cycles are evaluated on the optical and electrochemical properties of the cells. As a result, a high energy conversion efficiency of 2.49 % was obtained by using modified ZnO HS/CdS photoanode under AM 1.5 illumination of 100 mW cm^?2. And further decorated by the CdSe QDs, the ZnO HS/CdS/CdSe cell achieved a PCE of 5.36 % due to the modification of ZnO HS nanostructure, the enhanced absorption in the visible region, the lower recombination reaction and higher electron lifetime.     

Ultrafast electronic relaxation and charge-carrier localization in CdS/CdSe/CdS quantum-dot quantum-well heterostructures

The relaxation and localization times of excited electrons in CdS/CdSe/CdS colloidal quantum wells were measured using subpicosecond spectroscopy. HRTEM analysis and steady-state PL demonstrate a narrow size distribution of 5-6 nm epitaxial crystallites. By monitoring the rise time of the stimulated emission as a function of pump intensity, the relaxation times of the electron from the CdS core into the CdSe well are determined and assigned. Two-component rise times in the stimulated emission are attributed to intraband relaxation of carriers generated directly within the CdSe well (fast component) and charge transfer of core-localized carriers across the CdS/CdSe interface (slow component). This is the first reported observation of simultaneous photon absorption in the core and well of a quantum-dot heterostructure. With increasing pump intensity, the charge-transfer channel between the CdS core CdSe well contributes less to the stimulated emission signal because of filling and saturation of the CdSe well state, making the interfacial charge-transfer component less efficient. The interfacial charge-transfer time of the excited electron was determined from the slow component of the stimulated emission build-up time and is found to have a value of 1.2 ps.     

Enhanced electron transfer rate for quantum dot sensitized solar cell based on CNT-TiO2 film

In this paper, we have fabricated a quantum dot sensitized solar cell (QDSSC) based on carbon nanotube (CNT) doped TiO2 mesopores film. As revealed by field emission scanning electron microscopy and absorption spectra, the CdSe QDs were adsorbed onto CNT-TiO2 nanocomposite. An improved efficiency is achieved for the CNT-TiO2/CdSe devices compared to that of TiO2/CdSe, which is due to the increased surface area and reduced charge recombination in TiO2 film by the presence of CNTs. A power conversion efficiency of the as-prepared QDSSC of 0.98% was obtained under 100 mW/cm2 solar irradiation. The emission decay profile demonstrates that the electrons transfer from CdSe QDs to CNT-TiO2 is faster than that from CdSe QDs to TiO2, resulting in the reduction of the charge recombination, leading to a higher FF value in QDSSC. The average lifetime of CdSe QDs adsorbed on TiO2 doped with CNT is 6.2 ns and the electron transfer rate constant of 1.1 x 10(8) s(-1) can be calculated.     

Enhanced photovoltaic performance of solar cell based on front-side illuminated CdSe/CdS double-sensitized TiO2 nanotube arrays electrode

Free-standing TiO₂ nanotube (NT) arrays have been prepared by a two-step anodization method. These translucent TiO₂ NT arrays can be transferred to the fluorine-doped tin oxide glass substrates to form front-side illuminated TiO₂ NT electrodes. The TiO₂ NT electrodes were double-sensitized by CdSe/CdS quantum dots (QDs) through successive ionic layer adsorption and reaction (SILAR) process. The absorption range of the TiO₂ NT electrode was extended from ~380 to 700 nm after sensitization with CdSe/CdS QDs. The SILAR cycles were investigated to find out the best combination of CdS and CdSe QDs for photovoltaic performance. The power conversion efficiency of 2.42 % was achieved by the CdSe(10)/CdS(8)/TiO₂ NT solar cell. A further improved efficiency of 2.57 % was obtained with two cycles of ZnS overlayer on the CdSe(10)/CdS(8)/TiO₂ NT electrode, which is 45.19 % higher than that of back-side illuminated solar cell. Furthermore, the ZnS(2)/CdSe(10)/CdS(8)/TiO₂ NT solar cell possesses a higher stability than CdSe(10)/CdS(8)/TiO₂ NT solar cell during the same period. The better photovoltaic performance of the ZnS(2)/CdSe(10)/CdS(8)/TiO₂ NT solar cell has demonstrated the promising value to design quantum dots-sensitized solar cells with double-sensitized front-side illuminated TiO₂ NT arrays strategy.     

Efficient quasi-stationary charge transfer from quantum dots to acceptors physically-adsorbed in the ligand monolayer

Alkanoate-coated CdSe/CdS core/shell quantum dots(QDs)with near-unity photoluminescence(PL)quantum yield and monoexponential PL decay dynamics are applied for studying quasi-stationary charge transfer from photo-excited QDs to quinone derivatives physically-adsorbed within the ligand monolayer of a QD.Though PL quenching efficiency due to electron transfer can be up to>80%,transient PL and transient absorption spectra reveal that the charge transfer rate ranges from single-digit nanoseconds to sub-nanoseconds,which is~3 orders of magnitude slower than that of static charge transfer and?2 orders of magnitude faster than that of collisional charge transfer.The physically-adsorbed acceptors can slowly(500-1,000 min dependent on the size of the quinone derivatives)desorb from the ligand monolayer after removal of the free acceptors.Contrary to collisional charge transfer,the efficiency of quasi-stationary charge transfer increases as the ligand length increases by providing additional adsorption compartments in the elongated hydrocarbon chain region.Because ligand monolayer commonly exists for a typical colloidal nanocrystal,the quasi-stationary charge transfer uncovered here would likely play an important role when colloidal nanocrystals are involved in photocatalysis,photovoltaic devices,and other applications related to photo-excitation.     

Plasmon-phonon coupling in charged n-type CdSe quantum dots: A THz time-domain spectroscopic study

This work aims to experimentally determine the polarizability of confined electron in CdSe quantum dots (QD). The dielectric response of uncharged and charged CdSe quantum dots (3.2 and 6.3 nm) has been measured using terahertz time-domain spectroscopy in the frequency range of 2.0-7.0 THz. A strong coupling between the surface plasmon and surface phonons appears upon charging the QDs. The absolute polarizability of an electron in 3.2 and 6.3 nm charged QDs are experimentally determined to be 0.5 +/- 0.1 x 10(3) A3 and 14.6 +/- 0.3 x 10(3) A3, respectively, and the values agree reasonably well with theory and the previous experiment. The observed plasmon-phonon coupling is expected to play an important role in electron relaxation in absence of a hole in CdSe QDs.     

Size tuning of MAA capped CdSe and CdSe/CdS quantum dots and their stability in different pH environments

The present work reports synthesis of mercaptoacetic acid capped CdSe nanoparticles soluble in water at different temperatures and with different precursor ratios. This enabled to tune the particle size of QDs from 2.7 to 5.8 nm. The particles consist of nanocrystals; with mixed phase, hexagonal wurtzite as well as sphalerite cubic and are luminescent with quantum yield 10%. The quantum yield up to 20% has been obtained by growing a shell of CdS over the CdSe. HR-TEM images, XRD patterns and the photoluminescence excitation spectra shows epitaxial growth of CdS shell over CdSe and with average size 3.2 ± 1.2 and 4.7 ± 1.2 nm for CdSe and CdSe/CdS quantum dots respectively. FT-IR spectrum and the negative zeta potential value together confirms the attachment of mercaptoacetic acid to the QD surface, where the carboxylic acid group is facing towards solvent and provides stability due to electrostatic hindrance. Further, the QDs are checked for their stability and the luminescence in environments of different pH (4–11 pH). Both CdSe and CdSe/CdS agglomerate with total elimination of fluorescence for 4 pH medium, and no shift in the fluorescence emission peak observed for the 6–9 pH, therefore QDs can be applicable as the fluorescence tags in this specific range of pH.     

Peculiarities of the thermal activation of carriers in CdSe/ZnSe QD structures

The results of experimental and theoretical investigations of thermal quenching of quantum dot (QD) photoluminescence (PL) in CdSe/ZnSe heterostructures are presented. It is found that at low temperatures, when carriers are strongly localized in QDs, QD PL intensity depends linearly on excitation power, but at higher temperatures, when carriers are thermally excited to the wetting layer, this dependence becomes superlinear. The activation energy of thermal quenching of QD PL intensity is found to be smaller than the sum of QD electron and hole potential depths. It is shown that these facts are explained satisfactorily by the model of independent electron and hole capture (escape) in QDs.