Thick-shell Quantum Dots Research Articles

Well-type thick-shell quantum dots combined with double hole transport layers device structure assisted realization of high-performance quantum dot light-emitting diodes

Quantum dot (QD) light-emitting diodes (QLEDs) are promising for next-generation lighting and displays. Considering the optimization design of both the QD and device structure is expected to improve the QLED's performance significantly but has rarely been reported. Here, we use the thick-shell QDs combined with a dual-hole transport layer device structure to construct a high-efficiency QLED. The optimized thick-shell QDs with CdS/CdSe/CdS/ZnS seed/spherical quantum well/shell/shell geometry exhibit a high photoluminescence quantum yield of 96% at a shell thickness of 5.9 nm. The intermediate emissive CdSe layer with coherent strain ensures defect-free growth of the thick CdS and ZnS outer shells. Based on the orthogonal solvents assisted Poly-TPD&PVK dual-hole transport layer device architecture, the champion QLED achieved a maximum external quantum efficiency of 22.5% and a maximum luminance of 259955 cd m-2, which are 1.6 and 3.7 times that of thin-shell QDs based devices with single hole transport layer, respectively. Our study provides a feasible idea for further improving the performance of QLED devices.

Unlocking Invisible Defects of ZnSe Alloy Shells in Giant Quantum Dots with Near Unity Quantum Yield

AbstractPhotoluminescence quantum yield (PL QY) of colloidal quantum dots (QDs) can be improved by growing a shell, but it is rather limited if the shell thickness exceeds a threshold. Lattice mismatch between the core and shell is known to determine this critical shell thickness, securing QDs from defect formation through strain release. However, it cannot explain the recently reported high efficiency QDs with giant shells. Based on CdSe/ZnSe thick shell QDs, this study aims to identify the culprit limiting PL QY. In the shell growth process, the gradual reduction in PL QY is accompanied by a low‐energy tail emission, but the additional compressive strain by the outmost shell eliminates such abnormalities. It is revealed that the zinc vacancy in the shell provides shallow hole trap states. The computational study successfully explains the hole‐accepting zinc vacancy states above the CdSe 1Shh state, raised by compressive strain along radial direction. Additional hydrostatic compressive strain lifts the 1Shh state for this strained heterostructure to minimize the energetic gap with the zinc vacancy states. The finding suggests that critical shell thickness can be limited by atomic vacancy incorporated during shell growth, not by formation of misfit dislocation caused by strain release.

A facile route to synthesize CdSe/ZnS thick-shell quantum dots with precisely controlled green emission properties: towards QDs based LED applications

In recent, the quantum yield (QY) and stability of green quantum dots (QDs) have been significantly improved. However, most of the progresses were achieved by using alloyed QDs, and the control of green emission QDs still remains challenging. Herein, we report a novel method for synthesizing thick-shell structure quantum dots (TSQDs) with saturated green-emitting where tri-n-octylphosphine (TOP) was used as both ligand and solvent to extract the redundant ions from the QDs surface and remove the lattice imperfections before any surface inorganic layer-by-layer coating. The as-prepared TSQDs demonstrate enhanced luminescent properties including high QY reaching up to 75%, full width at half maximum (FWHM) remaining close to 26 nm and tunable precise emission properties (532 nm), which can be utilized to perform 91% of the International Telecommunication Union (ITU) Recommendation BT. 2020 (Rec. 2020) for high definition and color gamut displays.

Quantum-confined stark effect in the ensemble of phase-pure CdSe/CdS quantum dots.

Colloidal semiconductor quantum dots (QDs) have recently attracted great attention in electric field sensing via the quantum-confined Stark effect (QCSE), but they suffer from the random local electric field around the charged QDs through the Auger process or defect traps. Here, QCSE in the ensemble of phase-pure wurtzite CdSe/CdS QDs was studied by applying a uniform external electric field. We observed clear field-dependent photoluminescence (PL) and absorption characteristics in thick-shell CdSe/CdS QDs with 11 CdS monolayers (11 MLs) including a pronounced spectral redshift in PL of ∼2.3 nm and absorption of ∼2.1 nm. The time-dependent PL intensity traces implied that the thick-shell QDs were conducive to realize the Stark shift in QD ensembles due to the effective suppression of the main sources of the local field. These findings were in stark contrast to those of moderate-shell (5 MLs) and ultrathick-shell (15 MLs) CdSe/CdS QDs. The measurement value of exciton polarizability was smaller than the theoretical value, which may be influenced by very few exciton traps. Moreover, the amplified stimulated emission also exhibited obvious optical modulations under the electric field with decreased emission intensity and an increased ultrafast lifetime. Finally, the temporal evolution of the multiexciton process in thick-shell CdSe/CdS QDs indicated that the multiexciton state induced a higher energy state near the band edge, which may weaken the QCSE of a single exciton. Therefore, it was demonstrated that efficient field control over the optical properties of these nanomaterials is feasible and this can open up potential applications in field-controlled electro-optic modulators.

Ultrafast Carrier Trapping in Thick-Shell Colloidal Quantum Dots.

It has previously been found that Auger processes can lead to femtosecond carrier trapping in quantum dots, limiting their performance in optoelectronic applications that rely on radiative recombination. Using atomistic simulations, we investigate whether a shell can protect carriers from Auger-assisted trapping. For these studies we investigate CdSe/CdS core-shell quantum dots having total diameters reaching up to 10 nm. We find trapping lifetimes as fast as 1 ps for 2 nm shells, and we report that shells as thick as 6 nm are required to suppress trapping fully. The most efficient recombination mechanism is found to proceed through shallow empty traps, suggesting it can be suppressed by filling the traps through doping or external electrochemical potential. Our findings suggest that to achieve efficient light emission, surface traps have to be completely eliminated, even in thick-shell quantum dots.

A self-assembly aptasensor based on thick-shell quantum dots for sensing of ochratoxin A.

A novel self-assembling aptasensor was fabricated by precisely attaching three phosphorothioate-modified capture aptamers onto a single thick-shell quantum dot in a controllable manner for monitoring of ochratoxin A (OTA), a poisonous contaminant widespread in foodstuffs. Herein, CdSe/CdS QDs coated in ten layer CdS shells were synthesized using a continual precursor injection method. Analysis of the prepared CdSe/CdS QDs showed a zinc-blende structure, high photoluminescence quantum yields (>80%), and a photoemission peak with a narrow full-width at half-maximum (about 29 nm), all qualities that render them as a superior choice for optical applications. By adjusting the number of phosphorothioate bases in the anchor domain, the tunable-valency aptasensor was able to self-assemble. In the sensing strategy, the thick-shell quantum dot was provided as an acceptor while OTA itself was used as a donor. In the presence of OTA, the capture aptamers drive the aptasensor function into a measurable signal through a fluorescence resonance energy transfer (FRET) system. The newly developed aptasensor had a detection limit as low as 0.5 ng mL(-1), with a linear concentration in the range of 1 to 30 ng mL(-1), and therefore meets the requirements for rapid, effective, and anti-interference sensors for real-world applications. Moreover, the high quality thick-shell QDs provide an ideal alternative for highly sensitive imaging and intensive illumination in the fields of biotechnology and bioengineering.

Detection of the pesticide by functionalised quantum dots as fluorescence-based biosensor

In this paper, we present the new results of biosensor that is made from the surface–modified quantum dots with acetylcholinesterase enzymes (AChE) for optical detection of the pesticides. The quantum dots (QDs) mentioned in this study are CdTe, CdSe/ZnS and CdSe/ZnSe/ZnS - the thick shell QDs are totally new. The results pointed out that all of the quantum dots are fit for the role of transducers in biosensor. In the biosensor, the QD– streptavidine - AChE is used as the substrate for the detection of pesticide. The pesticides used in this work are Parathion Methyl (PM) and Acetamiprid. The acetylthiocholine (ATCh) is used as an indicator of the activity of the AChE enzyme. Alternatively, the organophosphorus (OP) pesticides are the inhibitor for the AChE enzymes. Therefore, the mixture of the pesticide and ATCh is used for the goal of the specification of pesticide. We can detect pesticides by the change in PL intensity of QDs biosensor, with the content ranges from 0.05 ppb to 10 ppb.

Optical Detection of the Pesticide by Functionalized Quantum Dots as Fluorescence-Based Biosensor

In this work, the results on using biosensor composed from quantum dots as transducer and acetylcholinesterase enzymes (AChE) to detect pesticides optically are presented. The used quantum dots were CdTe, CdSe/ZnS 10 monolayer (ML) and CdSe/ZnSe2ML/ZnS 8 ML – the brand new thick-shell quantum dots (QD). The study results pointed out that the CdSe/ZnS 10 ML and CdSe/ZnSe 2ML/ZnS 8ML quantum dots best fit for the role of transducers in biosensors. In the biosensor, acetylthiocholine (ATCh) is used as indicator for the AChE enzymes to work, since it is a very powerful hydrolyte with the presence of AChE enzymes. Moreover, the organophosphorus (OP) pesticides are the inhibitors for the AChE enzymes, thus, by the biosensors that we designed, we can detect pesticides by the change in photoluminescence (PL) intensity of QDs, with the detection of OP like parathion methyl is 0.05 ppm, and acetamiprid is 2.5 ppm.

Towards controlled synthesis and better understanding of highly luminescent PbS/CdS core/shell quantum dots

A two-step cation exchange procedure has been developed for synthesizing PbS/CdS core/shell quantum dots (QDs) with a much thicker shell than previously reported, which expands the flexibility of the current cation exchange approach. The thick-shell QDs allow relatively easy observation of the core/shell morphology by transmission electron microscopy as well as exhibiting characteristic absorption and emission of CdS when the shell thickness reaches 1.8 nm. X-ray diffraction patterns show gradual transformation from a rock salt PbS pattern to a zinc blend CdS pattern with increasing shell thickness and the overall diffraction pattern is indeed the same as that of the CdS standard when the shell is thicker than 3.6 nm. The thick-shell QDs were further analyzed by energy dispersive X-ray spectrometry. It is found that Pb only exists in the core region and is essentially absent in the shell region. All of these results consistently suggest that the shell is made of CdS, instead of ternary PbxCd1−xS alloy in thick-shell QDs. As direct experimental identification of the shell composition in thin-shell QDs is difficult, experimental data and calculations are combined to indirectly probe this issue. The comparison of band gap versus core size plots of different compositional models indicates that it is highly likely that the thin shell is also made of CdS. Importantly, these core/shell PbS/CdS QDs not only show significantly increased quantum yield up to 67% at the optimal shell thickness of about 0.7 nm, they are also much more photostable and thermally stable than the shell-free PbS QDs.