Charge Trapping Defects in CdSe Nanocrystal Quantum Dots

Thiosulfate-terminated CdSe quantum dots for improving the performance and stability of perovskite solar cells

Unique properties of quantum dots (QDs) are controlled by their customizable particle sizes which can be engineered to suit local need. One-pot organometallic injection synthesis of cadmium selenide (CdSe) QDs is reported. The operation started with the injection of a week old selenium (Se) precursor into a boiling non-coordinating octadecene (ODE) at 195oC resulting in the formation of monodispersed size tunable CdSe QDs with discrete homogeneous nucleation. Differences in the injection and withdrawal time of the sample resulted to the dissimilarity in the shape, size and the opto-electronic properties of the QDs. The effect of oxygen on the synthesized CdSe QDs was studied by exposing freshly prepared sample to atmospheric oxygen for 206 days. The samples were characterized using optical absorption spectroscopy (UV-vis), optical photoluminescence (PL), X-ray diffraction (XRD), atomic force microscopy (AFM) and transmission electron microscopy (TEM), electron dispersive X-ray (EDX) X-ray diffraction spectroscopy (XRD), and X-ray photoelectron spectroscopy (XPS). Noticeable deformation on the size, shape and the crystalline orientation of the CdSe QDs were observed on the oxygen-interacted sample.Although the synthesis method is safe and produced good quality CdSe QDs, the interaction of the sample with oxygen degrades their opto-electronic quality.

The structure and physical properties of materials, such as elementary exciton processes, are closely interrelated. Doping copper ions in colloidal semiconductor quantum dots (QDs) has been shown to suppress hot electron relaxation. However, the relationship between the local environment of the heterometal ions in the host crystal and the physical properties has been insufficiently explored. In this study, CdSe and InP QDs were synthesized in the presence of heterometal ions. Copper ions were doped into CdSe QDs and segregated into InP QDs, as confirmed by X-ray absorption fine structure measurements, leading to hot electron relaxation being suppressed only in the CdSe QDs. On the basis of these findings, we developed a design strategy and successfully suppressed hot electron relaxation in InP QDs by introducing chromium ions. Understanding the local structure of dopants in QDs is essential for elucidating their physical properties and enabling the rational design of dopants to achieve novel functionalities.

Control of spin state in CdSe quantum dots by coupling with magnetic semiconductor quantum dots

Semiconductor quantum dots (QDs) are promising photocatalysts for water splitting due to the large specific area, but the influence of surface trap states on the photocatalytic activity of QDs is still not fully understood yet. To answer this question, CdSe QDs with the same morphology, diameter, crystal structure, and energy level are prepared following a hydrazine hydrate (N2H4) promoted synthesis strategy and conventional hydrothermal synthesis method. Through various characterizations and analysis, it is found that the conventional hydrothermal synthesized CdSe QDs (H-CdSe QDs) have a high concentration of Cd-involved shallow electron trap states, which seriously hinder the charge separation and transfer between CdSe and cocatalysts. In contrast, the N2H4 promoted synthesis strategy provides an energy-saving, low-cost, and facile pathway to eliminate the surface shallow electron traps, ensuring an efficient charge separation and H2 production in CdSe QDs. As a result, the N2H4-promoted synthesized CdSe QDs (N-CdSe QDs) produce 44.5 mL (1998 μmol) H2 in 7 h, roughly 1.6 times higher than that of H-CdSe QDs (27.5 mL, 1236 μmol). Because the surface trap states are widespread in semiconductor QDs, it is believed that our study provides valuable guidance on the design and preparation of QDs for photocatalysis.

Colloidal CdSe quantum dots (QDs) are suitable as electron acceptors in polymer/nanoparticle bulk heterojunction hybrid solar cells. For this application, a thick organic ligand shell which is typically surrounding the QDs after synthesis needs to be removed. Ligand exchange with pyridine is the most widely used method for this purpose. Although this approach is already 15 years old, detailed studies on the effectiveness of ligand exchange with pyridine for solar cell applications are still missing. In the present work hybrid solar cells were prepared from CdSe QDs initially capped with oleic acid (OA), and the impact of single and multiple pyridine treatment was thoroughly investigated. NMR was applied to determine the composition of the ligand shell as well as to distinguish the bound and free ligands before and after ligand exchange. It is shown that after a single pyridine treatment some amount of OA is still present in the samples. By using thermal gravimetric analysis (TGA) we could obtain also quantitative information about the effectiveness of subsequent pyridine treatments. In a series of one-, two-, and threefold ligand exchange, the estimated surface coverage by OA decreased from 26% to 12%, whereas that of pyridine increased from 54% to 80%. Laboratory solar cells with pyridine-capped CdSe QDs and poly(3-hexylthiophene) (P3HT) were characterized by current−voltage (I−V) measurements, and in order to get deeper insight into charge carrier generation and recombination processes, CdSe/P3HT blends were studied by light-induced electron spin resonance (l-ESR). Although repeated pyridine treatment was found to have a beneficial effect in the sense that more complete ligand exchange was achieved, which in turn enabled more efficient charge transfer, the performance of the solar cells was found to be reduced. This fact correlates with increased aggregation tendency of repeatedly pyridine-treated particles, negatively influencing the morphology of the blends, as well as with a larger amount of surface defects in particles stabilized by the weak pyridine ligand shell.

We investigate the self-assembly of a cylinder-forming polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) mixed with trioctylphosphine oxide (TOPO) capped cadmium selenide (CdSe) quantum dots (QDs). The QDs were found to be enthalpically compatible with the P4VP chains via ligand displacement of TOPO from the QD surface. However, the QDs were found to localize preferentially at the PS/P4VP interphase plausibly to gain translational entropy in order to further lower the energetics of the self-assembled structure. Interestingly, the morphological transformation observed with increasing weight fraction of the QDs in the BCP/QD composite was driven by the migration of the displaced TOPO from the QD surface to the PS phase, effectively increasing its total volume fraction. Hence, the PS-b-P4VP BCP with PS as the minority block displayed lamellar morphology in its composite with QDs. Furthermore, the preferred localization of the QDs at the PS/P4VP interface led to the formation of a trilayer lamellar morphology which was deduced from the suppression of the primary scattering peak, relative to higher order peaks in the SAXS data. The morphological transformation was accompanied by a significant increase in the domain spacing due to excessive stretching of the longer P4VP chains of the asymmetric block copolymer. However, in the PS-b-P4VP/CdSe composites with P4VP as the minority block, cylindrical morphology was retained and the domain spacing decreased due to dominance of the co-surfactant effect as well as interfacial localization of CdSe QDs. We also demonstrate that these PS-b-P4VP/CdSe self-assembled hybrid materials could further be used to obtain isolated core-shell nanoobjects, such as nanofibers and nanosheets, containing CdSe QDs. The nanoobjects so obtained exhibited photoluminescence properties typical of CdSe quantum dots. These photoluminescent polymer nanoobjects could have potential applications in biological targeting and fluorescence labeling.

Quantum dots (QDs) of semiconductors are promising materials for light emission applications due to their size-tunable optoelectronic properties. We present results of direct quantum dot (QD) formation from precursors inside a polymer matrix using laser irradiation. The method is important because it provides a simple means of patterning nanocomposite material within selected regions of a polymer, as required for device design. Several combinations of polymer/precursors films were treated with a picosecond laser at wavelength of 266 nm in order to verify the formation of the QDs inside the polymeric matrix. Precursors for CdS and CdSe QDs were used in experiments. The structural studies of laser-irradiated samples carried out by means of transmission electron microscopy (TEM) showed the QD formation. The size of QDs and the clusters depended on the laser irradiation dose transferred to the film. The QDs were collected to clusters including 10-60 QDs of different size. The mean size of QDs was less than 10nm. The optical analysis carried out by means of UV-VIS and optical microscopy confirmed the formation of the QDs after laser processing. The time-resolved photoluminescence revealed the energy transfer from the organic host to QDs. However, the charge separation was present due to a certain energy level alignment. Modification of the polymer/precursor blends is still required to prevent imbalance of carrier injection to QDs. Photo-luminescent spectroscopy and fluorescence microscopy have revealed that even if the QDs are not emissive, in certain polymer/QDs combinations the PL emission of the polymer is restored after laser treatment. © 2013 Copyright SPIE.

Synthesis of surface modified quantum dots (QDs) having potential biological activities are great important in biomedicinal chemistry. Here, we have synthesized mercapto propanoic acid (MPA) and thiolactic acid (TLA) coated water soluble cadmium selenide (CdSe) QDs having biological activity. Dispersion of QDs into a biological fluid can form protein corona. Hence, the binding of CdSe QDs with the carrier protein, human serum albumin (HSA) have been executed using spectroscopic methods. The binding affinity order of CdSe QDs‐HSA complexes were found in the order of 10 5 M −1 at 298 K. CdSe QDs are also affects the binding affinities of dietary polyphenols (naringin: NG and naringenin: NRG) towards HSA. The synthesized CdSe QDs was employed to sensing of antibiotic lomefloxacin by fluorescence quenching mechanism. The detection limit was found 0.70‐1.83 μg mL −1 . The CdSe QDs also demonstrate the detection of lomefloxacin under uv light based on color change of the solutions.

Elucidating the population dynamics of correlated electron-hole pairs (bound excitons) in semiconducting quantum dots (QDs) is key for developing our fundamental understanding of nanoscale photophysics as well as for the optimal design of devices, such as lasers. For decades, it was assumed that holes did not contribute to band edge bleach signals in QDs. Here, we employ two-dimensional electronic spectroscopy to monitor electron and hole dynamics in both CdSe and CdSe/CdS/ZnS QDs to probe electron and hole dynamics. Based on a combination of time and frequency resolution, we observe a previously unresolved bleaching signal in CdSe QDs on timescales faster than 30 fs due to hole cooling. Atomistic semiempirical pseudopotential calculations are used to rationalize the order of magnitude difference in the observed hole dynamics in CdSe and CdSe/CdS/ZnS QDs. This picture advances our understanding of QD excitonics past the prevailing continuum effective mass theories generally used to describe QD electronic structure and dynamics.

Reduction or oxidation reactions at colloidal semiconductor nanocrystal quantum dot (QD) surfaces are critical mechanistic steps for charge trapping or for photoinduced charge transfer. However, measuring and controlling the redox potentials of the surface is nontrivial. Here, monoanionic metal carbonyl complexes are used as electronically tunable X-type ligands for CdSe and CdS QD surfaces. IR spectroscopy of the frequencies of the C-O stretching vibrations of the anionic metal carbonyl species enable quantitative measurement of anion dissociation correlated to QD surface reduction. Spectral redox titration and spectroelectrochemical experiments show that coordination of more Lewis basic anions shifts the surface reduction potentials to more negative values, spanning a range of more than 1 V. Based on these results, complexation energies are a critical factor in controlling surface charge storage. This concept extends generally to other types of QD supporting ligands and to other QD materials. As proof-of-concept, anion exchange was used to control chemical surface reduction and photochemical electronic doping in CdSe QDs.

Impact of Quantum-size effects of an electron-hole system confined in semiconductors is studied theoretically by computational modeling. Here we proposed a formula to relate particle size with decay time and oscillator strength using the concept of transition probability. The theory modeled is for CdSe and CdS semi-conductor quantum dots in the strong confinement region only where the particle size is less than Bohr's radius and the oscillator strength per volume is expected to increase with 1/r3 for the first excited state, r being the radius of spherical nano particle. As the experimental data needed to co-relate the modeled theory is available only for CdSe and CdS quantum dots only, therefore the theory is modeled for these two quantum dots only. The decay time for such spherical quantum dots is reduced thereby causing faster decay of luminescence. On the other hand it is also observed from the calculations that for same size of two different spherical quantum dots the decay time as well as oscillator strength varies depending upon the bulk oscillator strength of the material.

Semiconductor quantum dots (QDs) exhibit exciting photophysical properties for a wide variety of applications in the field of energy conversion, lighting, and more recently quantum communication. The photophysics underpinning these applications at ambient conditions strongly depends on atomistic details of their dynamic surface. Neutral organic ligands used in surface passivation play a critical role in determining the structural and optoelectronic properties of these QDs. Small sizes and irregular atomic arrangements make these QD surface–ligand interfaces challenging to explore at the atomistic level. Here, we combine several computational simulation techniques to study thermally induced geometrical fluctuations in stable cadmium selenide (CdSe) QDs with and without ligand passivation. We find that structural fluctuations of surface atoms significantly depend on passivating molecules. The bulky and strongly binding ligands such as phosphine oxides induce a higher extent of interfacial dynamics. Though these stoichiometric QDs do not possess any permanent in-gap states, significant thermal distortion of QD–ligand interfaces can induce fluctuating defectlike states near band edges. Such vibronic dynamics in these QDs also modifies band-edge state positions on sub-picosecond timescale, impacting their functional properties. Our results further suggest that primary amine ligands are optimal choices for QD passivation. These insights may be helpful to make design principles for screening and optimizing passivating ligands best suited for various QD applications, such as for quantum communication technologies.

In this paper, we report distinct enhancement of surface-state emissions (SSEs) of colloidal CdSe quantum dots (QDs) via coupling to localized plasmons (LPs) in Ag nanostructures. The roles of oleic acid (OA) ligand on QDs in the formation of Ag nanostructures and in the intense enhancement of SSEs of CdSe QDs are explored. We find that OA ligand on CdSe QDs plays a critical role in modifying the morphology of the contacted Ag, which consequently impacts the coupling of QD emitters with LPs in Ag. A systematic study of size effect of QDs on coupling of SSEs with LPs shows that as-deposited small Ag particles favorably enhance the SSEs of small-size CdSe QDs. The OA ligand on QDs yields better Ag crystallinity and clear corners during the annealing process; therefore, it promotes reshaping of small Ag particles into larger ones, favorable to enhance the SSEs of large-size CdSe QDs. The annealed QDs/Ag hybrid structures are more stable than the unannealed ones due to the loss of the OA ligand in the heating process. The selective coupling of QD emitters with LPs in Ag nanostructures allows feasible realization of microscale fluorescent color patterns. The approach of OA-assisted modification of plasmonic properties of Ag nanostructures provides a new route to synthesizing bright luminescence materials and devices that use colloidal QDs.

The understanding of ultrafast carrier relaxation process in doped semiconductor quantum dots (QDs) is very important for their potential applications in light-emitting diodes, optoelectronics. Here, we have studied the change in electronic properties of Cu-doped CdSe QDs upon light illumination. The light-induced effect leads to the enhancement of the band edge decay time and reduces the decay time of the dopant emission due to photocorrosion of Cu-doped CdSe QDs. The bleaching recovery kinetics and the hot electron cooling dynamics have been studied by using femtosecond transient absorption spectroscopy. It is observed that the electron cooling process of doped CdSe QDs is dependent on the dopant concentration and the cooling kinetics of doped CdSe QDs are found to be slower than undoped QDs. After light irradiation, the cooling processes of hot electron and recovery process in doped systems are modified.