Passivated Quantum Dots Research Articles

Thiol and Halometallate, Mutually Passivated Quantum Dot Ink for Photovoltaic Application.

Tunable-band-gap colloidal QDs are a potential building block to harvest the wide-energy solar spectrum. The solution-phase surface passivation with lead halide-based halometallate ligands has remarkably simplified the processing of quantum dots (QDs) and enabled the proficient use of materials for the development of solar cells. It is, however, shown that the hallometalate ligand passivated QD ink allows the formation of thick crystalline shell layer, which limits the carrier transport of the QD solids. Organic thiols have long been used to develop QD solar cells using the solid-state ligand exchange approach. However, their use is limited in solution-phase passivation due to poor dispersity of thiol-treated QDs in common solvents. In this report, a joint passivation strategy using thiol and halometallate ligand is developed to prepare the QD ink. The mutually passivated QDs show a 50% reduction in shell thickness, reduced trap density, and improved monodispersity in their solid films. These improvements lead to a 4 times increase in carrier mobility and doubling of the diffusion length, which enable the carrier extraction from a much thicker absorbing layer. The photovoltaic devices show a high efficiency of 10.3% and reduced hysteresis effect. The improvement in surface passivation leads to reduced oxygen doping and improved ambient stability of the solar cells.

A Facet-Specific Quantum Dot Passivation Strategy for Colloid Management and Efficient Infrared Photovoltaics.

Colloidal nanocrystals combine size- and facet-dependent properties with solution processing. They offer thus a compelling suite of materials for technological applications. Their size- and facet-tunable features are studied in synthesis; however, to exploit their features in optoelectronic devices, it will be essential to translate control over size and facets from the colloid all the way to the film. Larger-diameter colloidal quantum dots (CQDs) offer the attractive possibility of harvesting infrared (IR) solar energy beyond absorption of silicon photovoltaics. These CQDs exhibit facets (nonpolar (100)) undisplayed in small-diameter CQDs; and the materials chemistry of smaller nanocrystals fails consequently to translate to materials for the short-wavelength IR regime. A new colloidal management strategy targeting the passivation of both (100) and (111) facets is demonstrated using distinct choices of cations and anions. The approach leads to narrow-bandgap CQDs with impressive colloidal stability and photoluminescence quantum yield. Photophysical studies confirm a reduction both in Stokes shift (≈47 meV) and Urbach tail (≈29 meV). This approach provides a ≈50% increase in the power conversion efficiency of IR photovoltaics compared to controls, and a ≈70% external quantum efficiency at their excitonic peak.

Pulsed axial epitaxy of colloidal quantum dots in nanowires enables facet-selective passivation

Epitaxially stacking colloidal quantum dots in nanowires offers a route to selective passivation of defective facets while simultaneously enabling charge transfer to molecular adsorbates – features that must be combined to achieve high-efficiency photocatalysts. This requires dynamical switching of precursors to grow, alternatingly, the quantum dots and nanowires – something not readily implemented in conventional flask-based solution chemistry. Here we report pulsed axial epitaxy, a growth mode that enables the stacking of multiple CdS quantum dots in ZnS nanowires. The approach relies on the energy difference of incorporating these semiconductor atoms into the host catalyst, which determines the nucleation sequence at the catalyst-nanowire interface. This flexible synthetic strategy allows precise modulation of quantum dot size, number, spacing, and crystal phase. The facet-selective passivation of quantum dots in nanowires opens a pathway to photocatalyst engineering: we report photocatalysts that exhibit an order-of-magnitude higher photocatalytic hydrogen evolution rates than do plain CdS quantum dots.

Phosphorene quantum dot electronic properties and gas sensing

Density functional theory calculations are performed on phosphorene quantum dots having different shapes and edge terminations to investigate their structure stability, electronic properties, and gas sensing ability. All the selected phosphorene dots, namely hexagonal and triangular flakes with armchair and zigzag terminations, have positive binding energies which insure their stability even though the bond lengths are much longer than those in the infinite phosphorene layer. It is found that all the selected hydrogen passivated quantum dots have a wide energy gap. In contrast, the partial passivation with sulfur decreases the gap. Moreover, it transforms the system from antiferromagnetic to ferromagnetic state. The energy gap of hexagonal zigzag cluster can be additionally tuned by electric field: narrowed by about 1.7 eV for hydrogenated or broadened by 0.25 eV for partially sulfurated edges. It is shown that phosphorene quantum dots successfully adsorb H2S, CH4, CO, NH3 gas molecules either on their edge or surface. The highest adsorption energy is obtained for NH3 molecule, when it is placed over the surface. This adsorption is alleviated by in-plane electric field and hindered by perpendicular field.

Enhancement of charge transport in quantum dots solar cells by N-butylamine-assisted sulfur-crosslinking of PbS quantum dots

A novel and facile strategy to realize selective inorganic ligand (S2−) exchange on Pb-rich surface of PbS colloidal quantum dots (QDs) has been demonstrated. This was achieved via xanthate ligand decomposition at room temperature without damaging the QDs surface. This proposed method offers an amicable solution for the limitation that inorganic-terminated colloidal QDs are restricted by the specific requirement to solvents with high dielectric constant. Furthermore, Introduction of S2− to form sulfur-crosslinking PbS QDs enables reaction force-induced QDs arrays and smooth surface morphology of the spin-coated QDs film as evidenced by atomic force microscopy. Passivation of QDs by bromide combined with sulfur led to stronger electronic coupling between adjacent QDs as compared to bromide-only passivated QDs counterparts. Bromide and sulfur hybrid-capped QDs exhibited remarkably enhanced carrier mobility from 1.66 × 10−4 cm2/V s to 5.0 × 10−1 cm2/V s as evidenced by the Hall- Effect measurement. The smooth QDs film morphology and higher charge transport contributed to the boost in the power conversion efficiency of QDs solar cells up 4.96% compared that using only CTAB passivated PbS QDs solar cells (3.04%). This controlled sulfurization approach paves a potential way for improved optoelectronic properties and devices based on QDs.

Determination of Organophosphorus Pesticides in Fortified Tomatoes by Fluorescence Quenching of Cadmium Selenium – Zinc Sulfide Quantum Dots

Quantum dots (QDs) have attracted great interest in fluorescence sensing. However, due to the surface passivation of QDs, it is still challenging to develop a sensing method based on the direct use of QD without the involvement of molecular recognition receptors. In this work, a very simple but practical strategy for highly passivated commercial CdSe/ZnS core-shell QDs is proposed to directly determine phosphorothiolate pesticides. This strategy is based on the fact that thiophosphorus hydrolyzates, formed in the alkaline hydrolysis of phosphorothiolates, strongly quench the fluorescence emission of the QDs by an electron transfer mechanism. The design is very easy to implement, requiring only the addition of the analyte into the quantum dot solution at room temperature. The ‘light-off’ response shows a wide linear range from 0.0001 to 160 μg mL−1 with a detection limit of approximately 0.0967 ng mL−1 (0.00012 mg kg−1), which is considerably lower than the maximum residue limit of 0.01 mg kg−1 allowed by the European Union. More importantly, ethion may be determined directly in fortified tomatoes by this protocol, demonstrating potential broad applications in food quality control.

Empirical pseudopotential method with nonspherical passivants for the atomistic study of silicon nanostructures

Atomistic calculations of passivated nanostructures remain difficult due to the computational demands related to the high number of atoms to be typically considered. The empirical pseudopotential method (EPM) offers a good alternative in this sense, but finding trustable pseudopotentials for passivants in this method is still elusive. Following the idea of extracting nonspherically symmetric potentials from density functional theory (DFT) calculations, hydrogen pseudopotentials for silicon passivation are derived here and used to calculate the electronic states of low-dimensional structures within the EPM scheme. The single-particle Schr\odinger equation is solved with the ensuing pseudopotentials for slabs with surfaces on the (111), (110), and (100) planes, as well as for passivated quantum dots and wires of different size. In all cases, the band gap is traced as a function of the sample size, showing good convergence towards the bulk value. For the slabs, the surface local density of states is also calculated and compared successfully to experiments. The derivation of the nonspherical pseudopotentials is based on an analytic formulation of the crystal potential and its connection to a series of DFT calculations, resulting in reliable, highly transferable and first-principles based passivant pseudopotentials to be used with the EPM.

An investigation into the effective surface passivation of quantum dots by a photo-assisted chemical method

In this study, we have developed an effective amino passivation process for quantum dots (QDs) at room temperature and have investigated a passivation mechanism using a photo-assisted chemical method. As a result of the reverse reaction of the H2O molecules, the etching kinetics of the photo-assisted chemical method increased upon increasing the 3-amino-1-propanol (APOL)/H2O ratio of the etching solution. Photon-excited electron-hole pairs lead to strong bonding between the organic and surface atoms of the QDs, and results in an increase of the quantum yield (QY%). This passivation method is also applicable to CdSe/ZnSe core/shell structures of QDs, due to the passivation of mid-gap defects states at the interface. The QY% of the as-synthesized CdSe QDs is dramatically enhanced by the amino passivation from 37% to 75% and the QY% of the CdSe/ZnSe core/shell QDs is also improved by ∼28%.

Understanding the Role of Surface Capping Ligands in Passivating the Quantum Dots Using Copper Dopants as Internal Sensor

The role of ligands in passivating quantum dots has been studied in this work using Cu doping as internal sensors. This has been elucidated using the example of dodecanethiol, 3-mercaptopropionic acid, trioctylphosphine, trioctylphosphine oxide, and primary amines for the passivation of CdSe quantum dots by exchanging the original ligands. Steady state and time dependent photoluminescence spectra of the Cu emission have provided the basis for determining the role of ligands. The surface of the quantum dots with ligand exchange has been monitored using nuclear magnetic resonance spectroscopy. The results suggest that the presence of trioctylphosphine, trioctylphosphine oxide, and oleylamine ligands on CdSe quantum dot surface lead to better photoluminescence efficiency. Further, increase in the chain length of the primary amines increases the effectiveness of passivation on the CdSe quantum dot surface. We have also extended this method to the study of oleylamine capping in CdS quantum dots.

Photo-stability and time-resolved photoluminescence study of colloidal CdSe/ZnS quantum dots passivated in Al2O3 using atomic layer deposition

We report photo-stability enhancement of colloidal CdSe/ZnS quantum dots (QDs) passivated in Al2O3 thin film using the atomic layer deposition (ALD) technique. 62% of the original peak photoluminescence (PL) intensity remained after ALD. The photo-oxidation and photo-induced fluorescence enhancement effects of both the unpassivated and passivated QDs were studied under various conditions, including different excitation sources, power densities, and environment. The unpassivated QDs showed rapid PL degradation under high excitation due to strong photo-oxidation in air while the PL intensity of Al2O3 passivated QDs was found to remain stable. Furthermore, recombination dynamics of the unpassivated and passivated QDs were investigated by time-resolved measurements. The average lifetime of the unpassivated QDs decreases with laser irradiation time due to photo-oxidation. Photo-oxidation creates surface defects which reduces the QD emission intensity and enhances the non-radiative recombination rate. From the comparison of PL decay profiles of the unpassivated and passivated QDs, photo-oxidation-induced surface defects unexpectedly also reduce the radiative recombination rate. The ALD passivation of Al2O3 protects QDs from photo-oxidation and therefore avoids the reduction of radiative recombination rate. Our experimental results demonstrated that passivation of colloidal QDs by ALD is a promising method to well encapsulate QDs to prevent gas permeation and to enhance photo-stability, including the PL intensity and carrier lifetime in air. This is essential for the applications of colloidal QDs in light-emitting devices.

Dual-mode crystal-bound and X-type passivation of quantum dots.

In this report, we present a new path to the control of quantum dot surface chemistry that can lead to a better understanding of nanoscale interfaces and the development of improved photocatalysts. Control of the synthetic methodology leads to QDs that are concomitantly ligated by crystal-bound organics at the surface anion sites and small X-type ligands on the surface cation sites.

Effect of the length of ligands passivating quantum dots on the electrooptical characteristics of organic light-emitting diodes

The electrooptical characteristics of organic light-emitting diodes with quantum dots passivated with organic ligands of different lengths as emitting centers are investigated. It is established that the thickness of the ligand coating covering the quantum dots has little effect on the Forster energy transfer in the diodes, but significantly affects the direct injection of charge carriers into the quantum-dot layer. It is shown that the thickness of the passivation coating covering the quantum dots in a close-packed nanoparticle layer is deter- mined both by the length of passivating ligands and the degree of quantum-dot coverage with ligands.

Efficient passivated phthalocyanine-quantum dot solar cells.

The power conversion efficiency of CdSe and CdS quantum dot sensitized solar cells is enhanced by passivation with asymmetrically substituted phthalocyanines. The introduction of the phthalocyanine dye increases the efficiency up to 45% for CdSe and 104% for CdS. The main mechanism causing this improvement is the quantum dot passivation. This study highlights the possibilities of a new generation of dyes designed to be directly linked to QDs instead of the TiO2 electrodes.

Simple and greener synthesis of highly photoluminescence Mn 2+ -doped ZnS quantum dots and its surface passivation mechanism

Abstract In this paper, we reported a simple synthetic method of highly photoluminescent (PL) and stable Mn2+-doped ZnS quantum dots (QDs) with glutathione (GSH) as the capping molecule and focused on mechanism of the surface passivation of QDs. The Mn2+-doped ZnS QDs that was synthesized in basic solution (pH 10) at 120 °C for 5 h exhibited blue trap-state emission around 418 nm and a strong orange-red emission at about 580 nm with an excitation wavelength of 330 nm. The optimum doping concentration is determined to be 1.5 at.%, and the present Mn2+-doped ZnS QDs synthesized under the optimal reaction condition exhibited a quantum yield of 48%. High resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) indicated that the Mn2+-doped ZnS QDs were 3–5 nm in size with a zinc blend structure. More importantly, the PL intensity and chemical stability can be improved using organic ligand modification strategies, it was found that GSH could passivate surface defects very efficiently by comparing and analyzing the results of the different organic ligands modification. The cadmium-free Mn2+-doped ZnS QDs well-passivated with GSH as capping molecule acquired the advantages of strong PL and excellent chemical stability, which are important to QD applications.

Charge Trapping Dynamics in PbS Colloidal Quantum Dot Photovoltaic Devices

The efficiency of solution-processed colloidal quantum dot (QD) based solar cells is limited by poor charge transport in the active layer of the device, which originates from multiple trapping sites provided by QD surface defects. We apply a recently developed ultrafast electro-optical technique, pump-push photocurrent spectroscopy, to elucidate the charge trapping dynamics in PbS colloidal-QD photovoltaic devices at working conditions. We show that IR photoinduced absorption of QD in the 0.2-0.5 eV region is partly associated with immobile charges, which can be optically detrapped in our experiment. Using this absorption as a probe, we observe that the early trapping dynamics strongly depend on the nature of the ligands used for QD passivation, while it depends only slightly on the nature of the electron-accepting layer. We find that weakly bound states, with a photon-activation energy of 0.2 eV, are populated instantaneously upon photoexcitation. This indicates that the photogenerated states show an intrinsically bound-state character, arguably similar to charge-transfer states formation in organic photovoltaic materials. Sequential population of deeper traps (activation energy 0.3-0.5 eV) is observed on the ~0.1-10 ns time scales, indicating that most of carrier trapping occurs only after substantial charge relaxation/transport. The reported study disentangles fundamentally different contributions to charge trapping dynamics in the nanocrystal-based optoelectronic devices and can serve as a useful tool for QD solar cell development.

Lead Chalcogenide Quantum Dot‐Doped Glasses for Photonic Devices

Tunable absorption and photoluminescence (PL) of lead chalcogenide quantum dots (QDs) doped in glasses due to the quantum confinements effect have been actively investigated for application as saturable absorbers, laser sources, and fiber‐optic amplifiers. Optical properties of QDs have been carefully monitored by controlling their sizes through heat treatment and rare‐earth ion doping. Two‐ and three‐dimensional precipitation of lead chalcogenide QDs were also realized using silver ion exchange and femtosecond laser irradiation in combination with thermal treatment. Prototypes of microstructured single‐mode fibers and tapered fiber amplifiers containing QDs proved potentials of these materials for fiber‐optic amplifiers application. Further research works on QD‐doped solid core fibers, surface passivation of quantum dots and their application for the mid‐infrared optical devices are necessary.

Balancing Electron Transfer and Surface Passivation in Gradient CdSe/ZnS Core-Shell Quantum Dots Attached to ZnO.

Core-shell (CS) quantum dots (QDs) are promising light absorbers for solar cell applications mainly because of their enhanced photostability compared with bare QDs. Moreover, the superb photostability can be combined with a low number of defects by using CSQDs with a gradient composition change from the core to the shell. Here, we study electron injection from the gradient CSQDs to ZnO nanoparticles. We observe the typical exponential injection rate dependence on the shell thickness (β = 0.51 Å(-1)) and discuss it in light of previously published results on step-like CSQDs. Despite the rapid drop in injection rates with shell thickness, we find that there exists an optimum thickness of the shell layer at ∼1 nm, which combines high injection efficiency (>90%) with a superior passivation of QDs.

Carrier dynamics in quantum-dot sensitized solar cells measured by transient grating and transient absorption methods

Carrier dynamics in quantum-dot sensitized solar cells (QDSSCs) was clarified by combining the information obtained by the heterodyne transient grating (HD-TG), transient absorption (TA) and transient photocurrent (TP) measurements under the short circuit conditions in the time range from microseconds to seconds. The HD-TG signal is sensitive to the ionic species at the electrode/electrolyte interface, and the electrons in the titanium oxide layer injected from quantum dots (QDs) were monitored by the TA signal, and the photocurrent as a final output was monitored by the TP signal. By using the compensating information, the whole picture of the charge dynamics was obtained in the time region after the initial electron injection from QDs into the titanium oxide layer. In the former part of this paper, the assignment of the responses for each measurement was clarified based on the previous paper on dye sensitized solar cells (S. Kuwahara, et al. Phys. Chem. Chem. Phys., 2013, 15(16), 5975-5981). In the latter part, the effect of the device parameters for actual QDSSCs, such as electrolyte concentrations, and coating times of surface passivation of QDs were investigated.

Recent development in colloidal quantum dots photovoltaics

The increasing demand for sustainable and green energy supply spurred the surging research on high-efficiency, low-cost photovoltaics. Colloidal quantum dot solar cell (CQDSC) is a new type of photovoltaic device using lead chalcogenide quantum dot film as absorber materials. It not only has a potential to break the 33% Shockley-Queisser efficiency limit for single junction solar cell, but also possesses low-temperature, high-throughput solution processing. Since its first report in 2005, CQDSCs experienced rapid progress achieving a certified 7% efficiency in 2012, an averaged 1% efficiency gain per year. In this paper, we reviewed the research progress reported in the last two years. We started with background introduction and motivation for CQDSC research. We then briefly introduced the evolution history of CQDSC development as well as multiple exciton generation effect. We further focused on the latest efforts in improving the light absorption and carrier collection efficiency, including the bulk-heterojunction structure, quantum funnel concept, band alignment optimization and quantum dot passivation. Afterwards, we discussed the tandem solar cell and device stability, and concluded this article with a perspective. Hopefully, this review paper covers the major achievement in this field in year 2011–2012 and provides readers with a concise and clear understanding of recent CQDSC development.

Calculating Band Alignment between Materials with Different Structures: The Case of Anatase and Rutile Titanium Dioxide

A method to calculate the band alignment between materials with different structures using passivated quantum dots is proposed. By using this method, the rutile/anatase titanium dioxide band offset is determined. The valence band maxima of anatase and rutile are close to each other, whereas the conduction band minimum of anatase is found to be about 0.2 eV higher than that of rutile, which is in agreement with the experimental fact that anatase has higher photocatalytic activity. The reliability of this method is further tested on several semiconductors, and reasonable results are obtained for most cases.