Quantum Dot Emission Research Articles

Enhanced photoluminescence of CdS quantum dots thin films on Cu and Ag nanoparticles

Fluorescent nanoparticles (NPs) exhibit unique optical properties which are utilized to prepare highly sensitive sensors. This paper illustrates the enhancement of luminescence emission of CdS quantum dots (QDs) from self-assembled metallic NPs of Cu and Ag. Metallic NPs, especially of Cu, Ag and Au exhibit unique and tunable plasmonic properties which are further manipulated by varying their size and shape. In the present study, plasmonic NPs were fabricated on glass substrate heated at 400 °C for the conversion of metallic layers into homogeneous NPs so as to create plasmonic response from these uniform NPs. The bimetallic layers of Ag and Cu NPs form a composite material having higher thermal conductivity, higher chemical stability and lower value of thermal expansion than monometallic layer of NPs. The photo-luminescence enhancement of CdS QDs thin films deposited on Cu and Ag NPs would find applications as light emitters and sensing devices. The attachment of CdS QDs on these bimetallic layers was confirmed by studying their optical properties. The morphology of the three prepared samples was analysed by scanning electron microscopy, which confirms the homogeneous deposition of spherical Cu and Ag NPs having size ranging from 20 to 55 nm (approximately). The above obtained outcomes illustrate the localized surface plasmon resonance characteristic of metal NPs which can be applied further for chemical and biological sensing

Optical-Gain-based Sensing Using Inorganic-Ligand-Passivated Colloidal Quantum Dots.

Thanks to their extremely large surface-to-volume ratio, colloidal quantum dots are potential high-performance sensing materials. However, previous sensing works using their spontaneous emission suffer from low sensitivities. The absence of an amplification process and the presence of the steric hindrance of long-chain organic ligands are two possible causations. Herein we propose that these two issues can be circumvented by using the amplified spontaneous emission of colloidal quantum dots capped by short-chain inorganic ligands. To exemplify this concept, we performed humidity sensing and observed a ∼31 times enhancement in sensitivity. Meanwhile, we found that the amplified spontaneous emission threshold power was reduced by 34% in a high humidity environment. On the basis of our transient absorption measurements, we attribute these observations to the mitigation of ultrafast subpicosecond trapping processes, which are enabled by the absorption of water molecules.

Metamorphic Buffer Layer Platform for 1550 nm Single-Photon Sources Grown by MBE on (100) GaAs Substrate.

We demonstrate single-photon emission with a low probability of multiphoton events of 5% in the C-band of telecommunication spectral range of standard silica fibers from molecular beam epitaxy grown (100)-GaAs-based structure with InAs quantum dots (QDs) on a metamorphic buffer layer. For this purpose, we propose and implement graded In content digitally alloyed InGaAs metamorphic buffer layer with maximal In content of 42% and GaAs/AlAs distributed Bragg reflector underneath to enhance the extraction efficiency of QD emission. The fundamental limit of the emission rate for the investigated structures is 0.5 GHz based on an emission lifetime of 1.95 ns determined from time-resolved photoluminescence. We prove the relevance of a proposed technology platform for the realization of non-classical light sources in the context of fiber-based quantum communication applications.

Optically Driven Giant Superbunching from a Single Perovskite Quantum Dot

AbstractPhoton superbunching is a signature of a strong correlation between photons, which is a crucial resource needed in quantum communication and computation. As such, a superbunched photon source based on a material with high quantum efficiency, like cesium lead halide perovskite, is highly desirable. Utilizing the large dark–bright exciton splitting in CsPbBr3quantum dot (QD), the authors achieve a superbunching with a large g(2)(0) ≈ 30 from an optically driven single CsPbBr3QD emission at cryogenic temperature. The cascaded emission is identified as the cause of this superbunching by utilizing second‐order cross‐correlation measurement and exploring the excitation power and temperature dependence of the bunching level. The findings have immediate implications on the basic understanding of a single perovskite QD emission and its application as a quantum light source.

Metal, dielectric and hybrid nanoantennas for enhancing the emission of single quantum dots: A comparative study

The confinement of electromagnetic energy to subwavelength volumes through nanoscale antennas can be used to enhance the spontaneous emission of quantum emitters. With this aim, different configurations of metallic and high refractive index dielectric nanoparticles have been explored. Here, we carry out a comparative analysis of planar metallic, high refractive index dielectric, and hybrid nanoantennas considering three different parameters: the Purcell factor enhancement, radiation efficiency, and directionality properties. We focus our study on different geometries and material combinations of a dimer of cylinders. A dimer made of two gold nanocylinders is the most promising candidate for improving the spontaneous emission. While most previous works have paid attention to the redirection of the scattered emission in the nanoparticle plane, our proposed nanostructure of two large gold cylinders (R=λ/4) emits most of the radiation upwards. This effect is due to the strong quadrupolar electric contribution to the resonant mode. With the aim to further improve the directionality properties, additional silicon nanocylinders are used as directors of the scattered radiation, increasing the directivity by a factor of 2.4 with respect to the gold dimer without directors. All in all, a hybrid structure composed of a gold dimer and silicon nanoparticles is proposed to enhance the spontaneous emission of a single quantum dot and to govern its emission pattern. The results shown in this work could be useful in fluorescence enhancement or in quantum photonics. They are particularly interesting for the development of single-photon sources based on quantum dots and other nanoscale emitters.

Tuning the interfacial stoichiometry of InP core and InP/ZnSe core/shell quantum dots

We demonstrate fine-tuning of the atomic composition of InP/ZnSe quantum dots (QDs) at the core/shell interface. Specifically, we control the stoichiometry of both anions (P, As, S, and Se) and cations (In and Zn) at the InP/ZnSe core/shell interface and correlate these changes with the resultant steady-state and time-resolved optical properties of the nanocrystals. The use of reactive trimethylsilyl reagents results in surface-limited reactions that shift the nanocrystal stoichiometry to anion-rich and improve epitaxial growth of the shell layer. In general, anion deposition on the InP QD surface results in a redshift in the absorption, quenching of the excitonic photoluminescence, and a relative increase in the intensity of broad trap-based photoluminescence, consistent with delocalization of the exciton wavefunction and relaxation of exciton confinement. Time-resolved photoluminescence data for the resulting InP/ZnSe QDs show an overall small change in the decay dynamics on the ns timescale, suggesting that the relatively low photoluminescence quantum yields may be attributed to the creation of new thermally activated charge trap states and likely a dark population that is inseparable from the emissive QDs. Cluster-model density functional theory calculations show that the presence of core/shell interface anions gives rise to electronic defects contributing to the redshift in the absorption. These results highlight a general strategy to atomistically tune the interfacial stoichiometry of InP QDs using surface-limited reaction chemistry allowing for precise correlations with the electronic structure and photophysical properties.

Ratiometric fluorescent sensing of mercury (II) ion based on the Pt nanozyme-triggered fluorescence resonance energy transfer between Si quantum dots and 2,3-diaminophenazine

The demand for efficient methods to determine mercury ion (Hg2+) is increasing. Herein, we developed a ratiometric fluorescence assay by the coupling of nanozyme and fluorescence resonance energy transfer (FRET) to determine Hg2+. Platinum nanoparticles (PtNPs) was synthesized as effective nanozyme to catalyze the oxidation of o-phenylenediamine (OPD) at the presence of hydrogen peroxide (H2O2) to produce 2,3-diaminophenazine (DAP). The fluorescence emission of Si quantum dots (QDs) at 414 nm (I414) was observed to be quenched by DAP (emission at 576 nm (I576)) via FRET mechanism, whereas Hg2+ can depress the catalytic activity of PtNPs to generate DAP. Based on this principle, SiQDs/PtNPs/OPD/H2O2-based ratiometric fluorescence assay was developed that the emission ratio of DAP and SiQDs (I576/I414) decreased with a higher concentration of Hg2+. Noteworthy, the sensitivity of such system was found to be related with the value of I576/I414. The developed assay offered a detection range of 20–3000 nM and a detection limit of 10.5 nM. This assay was applied to analyze Yangtze river water, and its reliability has been validated by the standard ICP-MS method. Our work provided an effective and convenient method for Hg2+ detection.

Ultrasensitive and Highly Selective Detection of Bisphenol a Using Core-Shell Magnetic Molecularly Imprinted Quantum Dots Electrochemiluminescent Probe.

The main aim of this work was to develop a magnetic molecularly imprinted polymer (MMIP)-based quantum dots electrochemiluminescent (ECL) probe for the ultrasensitive and highly selective detection of bisphenol A (BPA). The prepared core-shell Fe3O4@SiO2 exhibited superparamagnetic properties, making them easy to separate. The MIP was fabricated by the self-polymerization of dopamine on the surface of amine-terminated Fe3O4@SiO2 (Fe3O4@SiO2-NH2) magnetic nanoparticles and doped with quantum dots (QDs) to form an ECL system. The ECL intensity decrease with the concentration of BPA increased, due to the BPA molecules occupied molecularly imprinted sites and blocked the strong ECL emission of QDs. The prepared ECL sensor performed satisfactorily in the detection of BPA, with a wide linear range from 10- 4 to 10- 9mol L- 1 and a low detection limit of 3.4 × 10- 10mol L- 1 (S/N = 3). The recoveries of BPA achieved were in the range 96%-107% in the detection of actual water samples. The proposed ECL sensor displayed high sensitivity and stability, and may provide an approach for determining other important analytes.

Breaking through the Size Control Dilemma of Silver Chalcogenide Quantum Dots via Trialkylphosphine-Induced Ripening: Leading to Ag2Te Emitting from 950 to 2100 nm.

Ag2Te is one of the most promising semiconductors with a narrow band gap and low toxicity; however, it remains a challenge to tune the emission of Ag2Te quantum dots (QDs) precisely and continuously in a wide range. Herein, Ag2Te QDs emitting from 950 to 2100 nm have been synthesized via trialkylphosphine-controlled growth. Trialkylphosphine has been found to induce the dissolution of small-sized Ag2Te QDs due to its stronger ability to coordinate to the Ag ion than that of 1-octanethiol, predicated by the density functional theory. By controlling this dissolution effect, the monomer supply kinetics can be regulated, achieving precise size control of Ag2Te QDs. This synthetic strategy results in state-of-the-art silver-based QDs with emission tunability. Only by taking advantage of such an ultrawide emission has the sizing curve of Ag2Te been obtained. Moreover, the absolute photoluminescence quantum yield of Ag2Te QDs can reach 12.0% due to their well-passivated Ag-enriched surface with a density of 5.0 ligands/nm2, facilitating noninvasive in vivo fluorescence imaging. The high brightness in the long-wavelength near-infrared (NIR) region makes the cerebral vasculature and the tiny vessel with a width of only 60 μm clearly discriminable. This work reveals a nonclassical growth mechanism of Ag2Te QDs, providing new insight into precisely controlling the size and corresponding photoluminescence properties of semiconductor nanocrystals. The ultrasmall, low-toxicity, emission-tunable, and bright NIR-II Ag2Te QDs synthesized in this work offer a tremendous promise for multicolor and deep-tissue in vivo fluorescence imaging.

Red fluorescent nanoprobe based on Ag@Au nanoparticles and graphene quantum dots for H2O2 determination and living cell imaging.

A sensitive and turn-on fluorescence nanoprobe based on core-shell Ag@Au nanoparticles (Ag@AuNPs) as a fluorescence receptor and red emissive graphene quantum dots (GQDs) as a donor was fabricated. They were conjugated together through π-π stacking between the GQDs and single-strand DNA modified at the Ag@AuNPs surface. The absorption spectrum of the receptorsignificantly overlapped with the donor emission spectrum, leading to a strong Förster resonance energy transfer (FRET) and thus a dramatic quenching. The sensing mechanism relies on fluorescence recovery following DNA cleavage by •OH produced from Fenton-like reaction between the peroxidase-like Ag nanocore and H2O2. The red emissive feature (Ex/Em, 520nm/560nm) provides low background in physiological samples. The •OH production, great spectrum overlapping, and red emission together contributes to good sensitivity and living cell imaging capability. The fluorescence assay (intensity at 560nm) achieves a low detection limit of 0.49μM H2O2 and a wide linear range from 5 to 200μM, superior to most of the reported fluorescent probes. The RSD value for 100μM H2O2 was 1.4%. Thenanoprobe exhibits excellent anti-interferences and shows low cytotoxicity. The recovery of 100μM standard H2O2 in a cancer cell lysate was 85.8%. Most satisfactorily, it can realize monitoring and imaging H2O2 in living cells. This study not only presents a sensitive H2O2 probe but also provides a platform for detecting other types of reactive oxygen species.

Optimizing the PMMA Electron-Blocking Layer of Quantum Dot Light-Emitting Diodes.

Quantum dots (QDs) are promising candidates for producing bright, color-pure, cost-efficient, and long-lasting QD-based light-emitting diodes (QDLEDs). However, one of the significant problems in achieving high efficiency of QDLEDs is the imbalance between the rates of charge-carrier injection into the emissive QD layer and their transport through the device components. Here we investigated the effect of the parameters of the deposition of a poly (methyl methacrylate) (PMMA) electron-blocking layer (EBL), such as PMMA solution concentration, on the characteristics of EBL-enhanced QDLEDs. A series of devices was fabricated with the PMMA layer formed from acetone solutions with concentrations ranging from 0.05 to 1.2 mg/mL. The addition of the PMMA layer allowed for an increase of the maximum luminance of QDLED by a factor of four compared to the control device without EBL, that is, to 18,671 cd/m2, with the current efficiency increased by an order of magnitude and the turn-on voltage decreased by ~1 V. At the same time, we have demonstrated that each particular QDLED characteristic has a maximum at a specific PMMA layer thickness; therefore, variation of the EBL deposition conditions could serve as an additional parameter space when other QDLED optimization approaches are being developed or implied in future solid-state lighting and display devices.

A simple fluorometric method for rapid screening of aflatoxins after their extraction by magnetic MOF-808/graphene oxide composite and their discrimination by HPLC

Herein, a high-performance screening tool for the selective and sensitive monitoring of aflatoxins is reported based on their great quenching effect on the blue emission of graphene quantum dots (GQDs). To make a specific determination, a pre-extraction method was also developed using a new nano-sorbent based on the surface-imprinted Zr metal-organic framework on the magnetic graphene oxide (MGO/MOF-808@MIP). The adsorbing efficiency of the prepared composite was remarkably higher than the pristine MOF-808 or bare GO. The presence of GO nanosheets, as well as nanoporous MOF-808 provided a high accessible surface area to form the MIP layer. It provided a great number of MIP sites for high efficient and rapid extraction of aflatoxins. The presence of magnetic nanoparticles in the structure of nanocomposite also facilitated the extraction process using a magnetic solid-phase extraction (MSPE) system. The combination of this specific and high-performance extraction with simple fluorometric detection caused a potent screening tool for aflatoxins. The method was able to monitor the total aflatoxins content of food samples with a linear range of 0.05–8 ng mL−1, which was more sensitive than the fluorometric system without extraction (5–500 ng mL−1). More developments were made by the application of a high-performance liquid chromatography (HPLC) method for the discrimination of the extracted aflatoxins. The system showed high sensitivity and selectivity and was able to detect different aflatoxins with an acceptable resolution.

Large-area patterning of full-color quantum dot arrays beyond 1000 pixels per inch by selective electrophoretic deposition

Colloidal quantum dot (QD) emitters show great promise in the development of next-generation displays. Although various solution-processed techniques have been developed for nanomaterials, high-resolution and uniform patterning technology amicable to manufacturing is still missing. Here, we present large-area, high-resolution, full-color QD patterning utilizing a selective electrophoretic deposition (SEPD) technique. This technique utilizes photolithography combined with SEPD to achieve uniform and fast fabrication, low-cost QD patterning in large-area beyond 1,000 pixels-per-inch. The QD patterns only deposited on selective electrodes with precisely controlled thickness in a large range, which could cater for various optoelectronic devices. The adjustable surface morphology, packing density and refractive index of QD films enable higher efficiency compared to conventional solution-processed methods. We further demonstrate the versatility of our approach to integrate various QDs into large-area arrays of full-color emitting pixels and QLEDs with good performance. The results suggest a manufacture-viable technology for commercialization of QD-based displays.

Green Synthesis Of CdS Quantum Dot Using (Citrus Limon (L.) Osbeck) Leaves Extract As Stabilizing Agent And Investigate Its Emission Properties

In the current research, the CdS has been synthesized through greens method, in which lemon leaves extract acted as stabilizing agent and the characterization techniques like PXRD, SEM, EDX, FTIR, UV, DLS, CIE and BET are used to investigate CdS. PXRD confirmed the crystalline size as 3 nm with stable cubic structure of CdS. Spike like morphology was identified by SEM. The influence of lemon leaves extract on the structural and optical properties were discussed in the FTIR and UV spectra. The bandgap energy of synthesized CdS was found to be 3.07 eV. The secondary particle distribution of CdS was found to be 204 nm which confirms the quantum size effect. The CIE 1931 chromaticity diagram was analyzed to explore the dominance emission of CdS quantum dot. The pore size, pore volume and surface area of the sample were measured by BET, BJH, N2 Adsorption-Desorption Isotherms, which have revealed the synthesized compound were suitable for QDSSC and Photovoltaic application.

Effect of Cap Thickness on InAs/InP Quantum Dots Grown by Droplet Epitaxy in Metal–Organic Vapor Phase Epitaxy

InAs quantum dots (QDs) are grown on bare InP(001) via droplet epitaxy (DE) in metal–organic vapor phase epitaxy (MOVPE). Capping layer engineering, used to control QD size and shape, is explored for DE QDs in MOVPE. The method allows for the tuning of the QD emission over a broad range of wavelengths, ranging from the O‐ to the L‐band. The effect of varying the InP capping layer is investigated optically by macro‐ and micro‐photoluminescence (PL, µPL) and morphologically by transmission electron microscopy (TEM). A strong 500 nm blueshift of the QD emission wavelength is observed when the capping layer is reduced from 20 to 8 nm, which is reflected by a clear size reduction of the buried QDs.

Facile preparation of red emission Hg-doped ZnSe QDs and ratiometric determination of alkaline phosphatase based on in situ generation of dual fluorescent reporter

In this study, highly red emissive mercury-doped zinc selenide quantum dots (Hg-doped ZnSe QDs) were prepared by facile mixing of Hg2+ and ZnSe QDs. Further, a ratio fluorometric technique was designed for ultrasensitive detection of alkaline phosphatase (ALP) based on in situ generation of Hg-doped ZnSe QDs and quinoxaline derivative (QXD). Under the catalysis of ALP, ascorbic acid (AA) was generated from ascorbic acid 2-phosphate, and the as-generated AA underwent a redox reaction with Hg2+ to produce dehydroascorbic acid (DHA) and Hg, which resulted in significant suppression of red fluorescence at 635 nm because the lack of Hg2+ blocked the formation of Hg-doped ZnSe QDs. Furthermore, the occurrence of reaction between DHA and o-phenylenediamine produced fluorescent QXD, which caused the significant enhancement of blue fluorescence at 436 nm. Thus, a novel ratio nanoprobe utilizing Hg-doped ZnSe QDs and QXD as dual fluorescent reporter was fabricated for measuring ALP activity. The linear ranges were 0.001–0.02 U L−1 and 0.02–1.4 U L−1 with the detection limit of 0.001 U L−1. Furthermore, the nanoprobe enabled visual detection of ALP activity when exposed to ultraviolet light, and it exhibited satisfactory results for measuring ALP activity in human serum. This study provides a valuable method for ALP-related disease diagnosis and drug screening.

Rapid large-scale synthesis of highly emissive solid-state metal halide perovskite quantum dots across the full visible spectrum

The practical applications of solid-state inorganic CsPbX3 perovskite quantum dots (PQDs) have been restricted by their poor stability. Herein, we report an efficient large-scale synthesis of solid-state CsPbX3 PQDs across the full visible spectra using 3-Aminopropyltrimethoxysilane as ligands at room temperature in open air. The obtained green CsPbBr3 solids display outstanding optical performance with high color purity of 90% and photoluminescence quantum yield of 69.2%. Thanks to the protection of silica coating, the solid-state product shows much higher thermal stability, photo stability and long-term stability than that of naked CsPbBr3 QDs. The blue CsPb(Br/Cl)3 and yellow or red CsPb(Br/I)3 PQDs solids can be simply obtained via using alkali metal halide aqueous solution as additives. The white LED fabricated by combining the obtained green CsPbBr3 QDs solid powders and commercial red K2SiF6: Mn4+ phosphor with a blue LED chip displays high luminous efficiency of 70.47 lm/W and the color gamut can cover over 129.4% of the National Television System Committee standard.

Significant energy relaxation of quantum dot emitted hot electrons

Mesoscopic quantum dots (QDs) are ubiquitous in quantum devices as reliable sources of hot electrons. However, we have observed an unexpectedly significant energy relaxation of QD-emitted hot electrons up to $\ensuremath{\approx}55%$ of its excitation $\ensuremath{\le}1.5\phantom{\rule{4pt}{0ex}}\mathrm{meV}$ from the Fermi level. The energetics of hot electrons were obtained through transverse magnetic focusing over a few microns using both QD and quantum point contact (QPC) emitters. Unlike the QPC counterparts, QD emissions deviated substantially from Fermi gas predictions---the focusing peak appeared at lower magnetic fields, and excessive broadening was observed. The phenomenon was modeled by a capacitive interaction transferring energy from the hot electron to the QD. Model simulations reproduced the key experimental features, implying the presence of a strong yet overlooked relaxation mechanism that is intrinsic to QD emissions. Our observation calls for the prudent use of QDs as single electron sources.

Spectroscopic investigation of defect-state emission in CdSe quantum dots.

CdSe quantum dots are the most studied Cd-based quantum dots with their high quantum yield, high photostability, narrow emission band, and easy synthesis procedure. They are frequently used to develop light emitting diode (LED) due to their unique photophysical properties; however, their narrow emission band causes a challenge to design white LEDs because white light emission requires emission in multiple wavelengths with broad emission bands. Here in this study, we developed CdSe quantum dots with a narrow band-edge emission band and broad defect-state emission band through a modified two-phase synthesis method. Our results revealed that defect-state emission is directly linked to the surface of quantum dots and can be excited through exciting surfactant around the quantum dot. The effect of surfactant on emission properties of CdSe quantum dots diminished upon growing a shell around CdSe quantum dots; as a result, surface-dependent defect-state emission cannot be observed in gradient heterogeneous alloyed CdSxSe1-x quantum dots.

Nanoscale Focus Pinspot for High-Purity Quantum Emitters via Focused-Ion-Beam-Induced Luminescence Quenching.

Epitaxially grown quantum dots (QDs), especially embedded in photonic structures, play an essential role in various quantum photonic systems as on-demand single-photon sources. However, these QDs often suffer from adjacent unwanted emitters, which contribute to the background noise of the QD emission and fundamentally limit the single-photon purity. In this paper, a nanoscale focus pinspot (NFP) technique using focused-ion-beam-induced luminescence quenching enables us to improve single-photon purity from site-controlled QD as a proof-of-concept experiment. The optical quality of the QD emission is not degraded while the signal-to-noise ratio of the QD is improved. Moreover, the QD after the NFP technique reveals the single-photon nature at further elevated temperatures owing to the reduced background noise. As the NFP technique is nondestructive, it retains the apparent physical structures and photonic functions, thereby indicating its promising potential for applying diverse high-purity quantum emitters, particularly integrated in photonic devices and circuits.