Nanocrystal Quantum Dots Research Articles

In situ capping for size control of monochalcogenide (ZnS, CdS and SnS) nanocrystals produced by anaerobic metal-reducing bacteria

Metal monochalcogenide quantum dot nanocrystals of ZnS, CdS and SnS were prepared by anaerobic, metal-reducing bacteria using in situ capping by oleic acid or oleylamine. The capping agent preferentially adsorbs on the surface of the nanocrystal, suppressing the growth process in the early stages, thus leading to production of nanocrystals with a diameter of less than 5 nm.

High Efficiency Hybrid Solar Cells Using Nanocrystalline Si Quantum Dots and Si Nanowires.

We report on an efficient hybrid Si nanocrystal quantum dot modified radial p-n junction thinner Si solar cell that utilizes the advantages of effective exciton collection by energy transfer from nanocrystal-Si (nc-Si) quantum dots to underlying radial p-n junction Si nanowire arrays with excellent carrier separation and propagation via the built-in electric fields of radial p-n junctions. Minimization of recombination, optical, and spectrum losses in this hybrid structure led to a high cell efficiency of 12.9%.

Quantum-dot-in-perovskite solids.

Heteroepitaxy-atomically aligned growth of a crystalline film atop a different crystalline substrate-is the basis of electrically driven lasers, multijunction solar cells, and blue-light-emitting diodes. Crystalline coherence is preserved even when atomic identity is modulated, a fact that is the critical enabler of quantum wells, wires, and dots. The interfacial quality achieved as a result of heteroepitaxial growth allows new combinations of materials with complementary properties, which enables the design and realization of functionalities that are not available in the single-phase constituents. Here we show that organohalide perovskites and preformed colloidal quantum dots, combined in the solution phase, produce epitaxially aligned 'dots-in-a-matrix' crystals. Using transmission electron microscopy and electron diffraction, we reveal heterocrystals as large as about 60 nanometres and containing at least 20 mutually aligned dots that inherit the crystalline orientation of the perovskite matrix. The heterocrystals exhibit remarkable optoelectronic properties that are traceable to their atom-scale crystalline coherence: photoelectrons and holes generated in the larger-bandgap perovskites are transferred with 80% efficiency to become excitons in the quantum dot nanocrystals, which exploit the excellent photocarrier diffusion of perovskites to produce bright-light emission from infrared-bandgap quantum-tuned materials. By combining the electrical transport properties of the perovskite matrix with the high radiative efficiency of the quantum dots, we engineer a new platform to advance solution-processed infrared optoelectronics.

The Photophysical Properties of CdTe/ZnS Core/Shell Quantum Dots

The distinctive fluorescent properties of semiconductor nanocrystal quantum dots (QDs) make them advantageous for use in optoelectronic and biological applications. We report on experiments done to characterize the optical properties and the general photostability of CdTe QDs with varying ZnS shell thicknesses. Steady-state and time-resolved absorption and fluorescence spectroscopy measurements indicate that increasing the ZnS shell thickness results in longer absorption and emission wavelengths, increased quantum yield, and improved photostability.

Quantum Optical Signature of Plasmonically Coupled Nanocrystal Quantum Dots.

Small clusters of two to three silica-coated nanocrystals coupled to plasmonic gap-bar antennas can exhibit photon antibunching, a characteristic of single quantum emitters. Through a detailed analysis of their photoluminescence emissions characteristics, it is shown that the observed photon antibunching is the evidence of coupled quantum dot formation resulting from the plasmonic enhancement of dipole-dipole interaction.

High-Power Genuine Ultraviolet Light-Emitting Diodes Based On Colloidal Nanocrystal Quantum Dots.

Thin-film ultraviolet (UV) light-emitting diodes (LEDs) with emission wavelengths below 400 nm are emerging as promising light sources for various purposes, from our daily lives to industrial applications. However, current thin-film UV-emitting devices radiate not only UV light but also visible light. Here, we introduce genuine UV-emitting colloidal nanocrystal quantum dot (NQD) LEDs (QLEDs) using precisely controlled NQDs consisting of a 2.5-nm-sized CdZnS ternary core and a ZnS shell. The effective core size is further reduced during the shell growth via the atomic diffusion of interior Cd atoms to the exterior ZnS shell, compensating for the photoluminescence red shift. This design enables us to develop CdZnS@ZnS UV QLEDs with pure UV emission and minimal parasitic peaks. The irradiance is as high as 2.0-13.9 mW cm(-2) at the peak wavelengths of 377-390 nm, several orders of magnitude higher than that of other thin-film UV LEDs.

Soft contact transplanted nanocrystal quantum dots for light-emitting diodes: effect of surface energy on device performance.

To realize the full-color displays using colloidal nanocrystal quantum dot (QD)-based light emitting diodes (QLEDs), the emissive QD layer should be patterned to red (R), green (G), and blue (B) subpixels on a micrometer scale by the solution process. Here, we introduced a soft contact QD-transplanting technique onto the vacuum-deposited small molecules without pressure to pattern the QD layer without any damage to the prior organic layers. We examined the patternability of QDs by studying the surface properties of various organic layers systematically. As a result, we found that the vacuum-deposited 4,4',4″-tri(N-carbazolyl)triphenylamine (TCTA) layer is suitable for QD-transplanting. A uniform and homogeneous QD patterns down to 2 μm could be formed for all the RGB QDs (CdSe/CdS/ZnS, CdSe@ZnS, and Cd1-xZnxS@ZnS, respectively) with this method. Finally, we demonstrated the R, G, and B QLEDs by transplanting each QD onto the soft TCTA layer, exhibiting higher brightness (2497, 14 102, and 265 cd m(-2), respectively) and efficiency (1.83, 8.07, and 0.19 cd A(-1), respectively) than those of the previous QLEDs fabricated by other patterning methods. Because this pressure-free technique is essential for patterning and stacking the QDs onto the soft organic layer, we believe that both fundamental study and the engineering approach presented here are meaningful for the realization of the colloidal QD-based full-color displays and other optoelectronic devices.

A jack-of-all-trades: 2-mercaptosuccinic acid.

2-Mercaptosuccinic acid (MS) is an important and versatile substance for diverse fields of applications of which the most significant are surveyed in this article. Biological, chemical, and physical properties of MS as well as the knowledge of its synthesis and microbial degradation are illustrated. In addition, exemplary structural analogs of the organic sulfur compound are commented. The key application of MS in nanotechnology is discussed in detail with particular emphasis on quantum dots (nanocrystals) and self-assembled monolayers in combination with gold or silver. Furthermore, some medical and pharmaceutical applications are given, inter alia in bioimaging, as a nanocarrier, and with regard to the antimicrobial activity of MS-silver and MS-gold nanoparticles. Moreover, biological and chemical applications of MS are exemplified: the thiol compound can serve as an inhibitor for glutathione peroxidase, or the toxicity of substances can be increased due to the presence of MS in the respective cells or tissues. In the field of cosmetics, MS is widely utilized as a reducing agent for numerous products as explained in this article. Additionally, the microbial utilization of MS as a carbon and energy source for growth is elucidated in-depth, providing insight into different catabolic mechanisms.

Flow through Fluorescence Detection of Phosphate in Human Saliva Based on Sensitized Turn-On Photoluminescence of CdS Quantum Dots

ABSTRACTThe development of fluorescent turn-on probes for the determination of inorganic anions based on fluorescent semiconductor nanocrystals (quantum dots) has recently attracted great attention. Methods reported so far enable anion sensing at elevated concentration levels and usually with low selectivity against other abundant matrix components. In this work, we describe an alternative approach that combines the appropriate modulation of nanocrystal surface chemistry (i.e., stabilization) with rational design and modulation of the experimental conditions (i.e., flow injection analysis) in order to deliver an expedient flow through method that enables the determination of phosphate at low concentration levels and with good selectivity. The developed method was successfully applied to the determination of phosphate in artificial and human saliva with good analytical features in terms of reproducibility and repeatability (2.3–9.2%), recoveries from fortified samples (96.0–112.0%), linearity of response curves to phosphate concentrations (R2 > 0.99), and satisfactory sensitivity (<1 µM), providing a significant improvement to previous fluorescent turn-on quantum dot probes.

Investigating low volume planar surface fluorescent immunoassays with QDs for spatial and spectral multiplexing

The simultaneous detection of two analytes, chicken IgY (IgG) and Staphylococcal enterotoxin B (SEB), in a single spot of a planar surface fluorescent immunoassay was demonstrated using luminescent semiconductor quantum dot nanocrystal (QD) tracers. This spectral multiplexing is made possible by employing one laser to serve as the excitation source for detecting two distinct QD signals from different analytes. Spatial multiplexing – detection of two analytes in different regions of the planar surface – was also demonstrated using fluid handling constructs that allowed for very low solution volumes when performing the assay. The limits of detection for detecting both chicken IgG and SEB within a single spot were 25ng/mL and 1.6ng/mL, respectively. A novel slide reading detection platform involving evanescent wave excitation of a planar surface was created in-house for assay measurement. This platform is potentially more amenable to a point-of-care (POC) environment than conventional slide readers because of its modular design architecture and lack of moving parts. The result is a platform which is simple to repair using primarily off-the-shelf consumer components.

Chemical synthesis and optical characterization of regular and magic-sized CdS quantum dot nanocrystals using 1-dodecanethiol

Abstract

Photoluminescence Blinking from Single CdSeS/ZnS Quantum Dots in a Conducting Polymer Matrix

Quantum dot nanocrystals (NQDs) present within organic conducting (polymer) host environments form hybrid organic–inorganic materials that are applied in a range of technologies such as light emitt...

Efficiency of hole transfer from photoexcited quantum dots to covalently linked molecular species.

Hole transfer from high photoluminescence quantum yield (PLQY) CdSe-core CdS-shell semiconductor nanocrystal quantum dots (QDs) to covalently linked molecular hole acceptors is investigated. (1)H NMR is used to independently calibrate the average number of hole acceptor molecules per QD, N, allowing us to measure PLQY as a function of N, and to extract the hole transfer rate constant per acceptor, kht. This value allows for reliable comparisons between nine different donor-acceptor systems with variant shell thicknesses and acceptor ligands, with kht spanning over 4 orders of magnitude, from single acceptor time constants as fast as 16 ns to as slow as 0.13 ms. The PLQY variation with acceptor coverage for all kht follows a universal equation, and the shape of this curve depends critically on the ratio of the total hole transfer rate to the sum of the native recombination rates in the QD. The dependence of kht on the CdS thickness and the chain length of the acceptor is investigated, with damping coefficients β measured to be (0.24 ± 0.025) Å(-1) and (0.85 ± 0.1) Å(-1) for CdS and the alkyl chain, respectively. We observe that QDs with high intrinsic PLQYs (>79%) can donate holes to surface-bound molecular acceptors with efficiencies up to 99% and total hole transfer time constants as fast as 170 ps. We demonstrate the merits of a system where ill-defined nonradiative channels are suppressed and well-defined nonradiative channels are engineered and quantified. These results show the potential of QD systems to drive desirable oxidative chemistry without undergoing oxidative photodegradation.

Carrier density dependence of plasmon-enhanced nonradiative energy transfer in a hybrid quantum well-quantum dot structure.

An array of Ag nanoboxes fabricated by helium-ion lithography is used to demonstrate plasmon-enhanced nonradiative energy transfer in a hybrid quantum well-quantum dot structure. The nonradiative energy transfer, from an InGaN/GaN quantum well to CdSe/ZnS nanocrystal quantum dots embedded in an ~80 nm layer of PMMA, is investigated over a range of carrier densities within the quantum well. The plasmon-enhanced energy transfer efficiency is found to be independent of the carrier density, with an efficiency of 25% reported. The dependence on carrier density is observed to be the same as for conventional nonradiative energy transfer. The plasmon-coupled energy transfer enhances the QD emission by 58%. However, due to photoluminescence quenching effects an overall increase in the QD emission of 16% is observed.

The Core/Shell Structure of CdSe/ZnS Quantum Dots Characterized by X‐Ray Absorption Fine Spectroscopy

Understanding the chemical and physical properties of core/shell nanocrystal quantum dots (QDs) is key for their use in light‐emission applications. In this paper, a single‐step injection‐free scalable synthetic method is applied to prepare high‐quality core/shell QDs with emission wavelengths of 544 nm, 601 nm, and 634 nm. X‐ray absorption fine structure spectra are used to determine the core/shell structure of CdSe/ZnS quantum dots. Moreover, theoretical XANES spectra calculated by FEFF.8.20 are used to determine the structure of Se and S compounds. The QD samples displayed nearly spherical shapes with diameters of approximately 3.4 ± 0.5 nm (634 nm), 4.5 ± 0.4 nm (601 nm), and 5.5 ± 0.5 nm (544 nm). With XANES results and MS calculations, it is indicated that sphalerite ZnS capped with organic sulfur ligands should be the shell structure. Wurtzite CdSe is the main core structure with a Cd‐Se bond length of 2.3 Å without phase shift. This means that different emission wavelengths are only due to the crystal size with single‐step injection‐free synthesis. Therefore, single‐step injection‐free synthesis could generate a nearly ideal core/shell structure of CdSe/ZnS QDs capped with an organic sulfur ligand.

The composition effect on the optical properties of aqueous synthesized Cu-In-S and Zn-Cu-In-S quantum dot nanocrystals.

Multiternary quantum dots (QDs), because of the large degree of freedom in their structure and composition, have a wide tunability in their bandgap but also exhibit an increased uncertainty and complexity in their optical properties. In this work, we synthesized the ternary Cu-In-S (CIS) and quaternary Zn-Cu-In-S (ZCIS) QDs with different composition ratios via a facile aqueous route. The CIS QDs show multi-peak photoluminescence with their peak intensity dependent on the Cu : In ratio, which was illustrated using a donor-acceptor pair recombination process. Upon incorporation of Zn into the CIS QDs under similar conditions, the acquired ZCIS QDs exhibit blue-shifted photoluminescence (PL) spectra with an enhanced emission intensity and a narrowed spectral width (∼100 nm). A comparative study reveals that, reducing the Cu : In ratio in the CIS QDs and increasing the Zn content in the alloyed ZCIS QDs are both feasible strategies for bandgap engineering, although the influences on optical properties of the QDs were different. The XRD and EDX spectra revealed that the widening of the bandgap of the ZCIS QDs was correlated with the alloyed nanostructures and the preferential substitution of Cu by Zn. Compared to the Cu : In ratio variation, incorporation of Zn into CIS QDs is an effective strategy to achieve a more homogeneous absorption band and a wide range of emission wavelength tunability. After ZnS shell coating, the ZCIS/ZnS QDs show a further enhanced PL intensity with a prolonged fluorescence lifetime. Unlike CIS QDs, the blue shift in PL upon the shell growth was not pronounced for ZCIS QDs, for which a surface reconstruction mechanism was proposed and discussed. Finally, the as-prepared ZCIS/ZnS QDs were employed for in vitro cell imaging and exhibited good biocompatibility to macrophage cells.

Hybrid light sensor based on ultrathin Si nanomembranes sensitized with CdSe/ZnS colloidal nanocrystal quantum dots.

We report the observation of a large enhancement of the wavelength-dependent photocurrent in ultrathin silicon nanomembranes (SiNM) decorated with colloidal CdSe/ZnS nanocrystal quantum dots (NQDs). Back-gated, field-effect transistor structures based on 75 nm-thick SiNMs are functionalized with self-assembled monolayers (SAMs) preventing surface oxidation and minimizing the surface defect densities. NQDs are drop cast on the active region of the device and the photocurrent is measured as a function of the excitation wavelength across the NQD absorption region. Photocurrent enhancement on the order of several hundred nA's is observed for NQD/SAM/SiNM devices compared to reference SAM/SiNM structures, with the device peak response closely correlated to the NQD absorption peak. We propose light-induced gating of the surface electrostatic potential and forward self-biasing of the FET channel as the two key mechanisms leading to the large photocurrent increase. Our findings open the possibility of employing silicon-nanocrystal hybrid structures for light sensing applications.

Plasmonics: Hybrid Graphene–Giant Nanocrystal Quantum Dot Assemblies with Highly Efficient Biexciton Emission (Advanced Optical Materials 1/2015)

When giant nanocrystal quantum dots (g-NQDs) are coupled to graphene, pairs of excitons optically excited in the g-NQDs experience efficient recombination and subsequent simultaneous emission of photon pairs. This enhancement is provided by a localized plasmon supported by a charge puddle that forms underneath the photocharged g-NQD. On page 39, H. Htoon and co-workers reveal the tremendous potential of graphene-g-NQD hybrids for lasing and entangled photon source applications.

Performance Improvement of P3HT:CdSe Hybrid Solar Cell by Modifying Hole Injection Layer

Hybrid inorganic-organic solar cells based on bulk heterojunction structures are promising devices in the field of clean energy. Employing quantum dot nanocrystals such as CdS, CdSe, and CdTe have shown great potential in improving their photovoltaic performance because of their stability and tunability. Numerical study of these devices can provide more modifications in their structures. In this work, the performance dependency of ITO/PEDOT:PSS/ P3HT:CdSe/Al hybrid solar cell on hole conducting layer properties is investigated. First, hybrid cell with mentioned structure is simulated by solving Poisson's equations and using Poole- Frenkel mobility and Langevin recombination models. Then, in order to improve the hole injection process, the work function of hole injection layer (PEDOT:PSS) is changed by doping the layer. Calculated photovoltaic performance shows that by decreasing the work function from 5 .1eV to 4.9eV, the short circuit current (Jsc) and fill factor (FF) are enhanced, and lead power conversion efficiency increases. The achieved improvement is because of the more efficient hole injection between highest occupied molecular orbital (HOMO) level of P3HT and PEDOT:PSS Fermi level.

Electrically driven assembly of CdTe quantum dots into photoconductive microwires

Low energy, low cost quantum dot nanocrystal assembly into one-dimensional microwires for optoelectronic device applications.