High‐Efficient Deep‐Blue Light‐Emitting Diodes by Using High Quality ZnxCd1‐xS/ZnS Core/Shell Quantum Dots

High‐quality violet‐blue emitting Zn_xCd_1‐xS/ZnS core/shell quantum dots (QDs) are synthesized by a new method, called “nucleation at low temperature/shell growth at high temperature”. The resulting nearly monodisperse Zn_xCd_1‐xS/ZnS core/shell QDs have high PL quantum yield (near to 100%), high color purity (FWHM) <25 nm), good color tunability in the violet‐blue optical window from 400 to 470 nm, and good chemical/photochemical stability. More importantly, the new well‐established protocols are easy to apply to large‐scale synthesis; around 37 g Zn_xCd_1‐xS/ZnS core/shell QDs can be easily synthesized in one batch reaction. Highly efficient deep‐blue quantum dot‐based light‐emitting diodes (QD‐LEDs) are demonstrated by employing the Zn_xCd_1‐xS/ZnS core/shell QDs as emitters. The bright and efficient QD‐LEDs show a maximum luminance up to 4100 cd m^?2, and peak external quantum efficiency (EQE) of 3.8%, corresponding to 1.13 cd A^?1 in luminous efficiency. Such high value of the peak EQE can be comparable with OLED technology. These results signify a remarkable progress, not only in the synthesis of high‐quality QDs but also in QD‐LEDs that offer a practicle platform for the realization of QD‐based violet‐blue display and lighting.     

Green synthesis of yellow emitting PMMA–CdSe/ZnS quantum dots nanophosphors

We herein report the fabrication of highly fluorescent yellow emitting nanophosphors using CdSe/ZnS quantum dots (QDs) dispersed in polymethyl methacrylate (PMMA). The QDs were synthesised via a simple, non-phosphine and one pot synthetic method in the absence of an inert atmosphere. The as-prepared nanocrystallites were characterised by Fourier transform infrared spectroscopy (FTIR), ultraviolet–visible (UV–vis) and photoluminescence spectroscopy, energy-dispersive spectroscopy (EDS), Raman spectroscopy, transmission electron microscopy (TEM) and high resolution TEM (HRTEM) microscopy. Optical analysis confirmed that the as-synthesised CdSe/ZnS QDs were of high quality with sharp absorption peaks, bright luminescence, narrow emission width and high PL quantum yield (up to 74%). The electron microscope images showed that the QDs are small and spherical in shape with narrow size distributions while the HRTEM micrograph confirmed the high crystallinity of the material. The Raman analysis of the QDs revealed the formation of core–shell structure and the energy dispersive spectroscopy confirmed the presence of the corresponding elements (i.e., Cd, Se, Zn and S). The dispersion of the core–shell QDs in PMMA matrix led to the red-shifting of the emission position from 393 nm in the neat PMMA to 592 nm in the nanocomposite. The fabricated highly fluorescent yellow emitting PMMA–CdSe/ZnS core–shell QDs polymer nanocomposite film display excellent optical properties without loss of luminescence. Furthermore, the as-synthesised organic soluble CdSe/ZnS QDs were successfully converted into highly water soluble QDs after ligand exchange with mercaptoundecanoic acid (MUA) without the loss of their emission properties. The simplicity of the method and the quality of the as-synthesised nanocomposite make it a promising material for the large scale fabrication of diverse optical devices.     

Highly Stable Colloidal “Giant” Quantum Dots Sensitized Solar Cells

Colloidal quantum dots (QDs) are widely studied due to their promising optoelectronic properties. This study explores the application of specially designed and synthesized “giant” core/shell CdSe/(CdS)_x QDs with variable CdS shell thickness, while keeping the core size at 1.65 nm, as a highly efficient and stable light harvester for QD sensitized solar cells (QDSCs). The comparative study demonstrates that the photovoltaic performance of QDSCs can be significantly enhanced by optimizing the CdS shell thickness. The highest photoconversion efficiency (PCE) of 3.01% is obtained at optimum CdS shell thickness ≈1.96 nm. To further improve the PCE and fully highlight the effect of core/shell QDs interface engineering, a CdSe_x S_1?x interfacial alloyed layer is introduced between CdSe core and CdS shell. The resulting alloyed CdSe/(CdSe_x S_1?x )₅/(CdS)₁ core/shell QD‐based QDSCs yield a maximum PCE of 6.86%, thanks to favorable stepwise electronic band alignment and improved electron transfer rate with the incorporation of CdSe_x S_1?x interfacial layer with respect to CdSe/(CdS)₆ core/shell. In addition, QDSCs based on “giant” core/CdS‐shell or alloyed core/shell QDs exhibit excellent long‐term stability with respect to bare CdSe‐based QDSCs. The giant core/shell QDs interface engineering methodology offers a new path to improve PCE and the long‐term stability of liquid junction QDSCs.     

Facile synthesis of high-quality ZnS,CdS, CdZnS,and CdZnS/ZnS core/shell quantum dots: characterization and diffusion mechanism

Binary CdS and ZnS and ternary CdZnS alloy quantum dots (QDs) were synthesized via a simple, inexpensive, and reproducible route using sulfur, cadmium stearate, and zinc stearate as precursors and N-oleoylmorpholine as the reaction medium and solvent. Both binary and ternary QDs exhibited a narrow size distribution and high crystallinity as confirmed TEM and HRTEM images. The alloy QDs exhibited excellent composition-dependent optical properties and a narrow full-width at half maximum of 19–21 nm. UV-visible absorbance and photoluminescence (PL) emission spectra of the CdZnS QDs showed a blue shift during growth, indicating the formation of alloy QDs. ZnS shells were successively coated onto the alloy core via decomposition of zinc diethyldithiocarbamate at a relatively low temperature. The CdZnS/ZnS core/shell QDs obtained showed a significant increase in size and exhibited strong band edge emission with a significant increase in PL quantum yield. XRD patterns revealed that all the QDs had a zinc blende structure. The QD diffraction peaks gradually shifted to higher angle in the order CdS < CdZnS < CdZnS/ZnS < ZnS. The mechanism for the synthesis of CdZnS alloy and CdZnS/ZnS core/shell QDs is discussed.     

Improving the Power Conversion Efficiency of Organic Solar Cell by Blending with CdSe/ZnS Core–Shell Quantum Dots

We have blended poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) with CdSe/ZnS core–shell quantum dots (QDs) as the active layer to produce organic solar cells (OSC). The size of the CdSe/ZnS core–shell QDs was determined to be about 4 nm using transmission electron microscopy. The OSC were characterized by measuring the absorption spectra, current–voltage characteristics, and external quantum efficiency (EQE) spectra. The samples doped with 0.5 wt.% CdSe/ZnS core–shell QDs exhibited higher power conversion efficiency (PCE) than samples doped with other concentrations of QDs. The PCE of the OSC increases from 2.10% to 2.38% due to an increase of the short circuit current density (J _sc) from 6.00 mA/cm² to 6.25 mA/cm². The open circuit voltage (V _oc) was kept constant when comparing OSC that were undoped and doped with 0.5 wt.% CdSe/ZnS core–shell QDs. These CdSe/ZnS core–shell QDs can increase optical absorption as well as provide extra exciton dissociation and additional electric pathways in hybrid OSC.     

核/壳结构ZnS:Mn/ZnS量子点光发射增强研究

利用水溶性前驱体材料在水性介质中制备了ZnS:Mn和ZnS:Mn/ZnS核/壳结构量子点(QDs,quantum dots),并用X射线衍射(XRD)、光致发光(PL)对ZnS:Mn和ZnS:Mn/ZnS核/壳结构QDs的结构和发光性能进行研究.ZnS:Mn和ZnS:Mn/ZnS QDs XRD谱与标准谱吻合,根据De...     

Dielectric confinement on exciton binding energy and nonlinear optical properties in a strained Zn1-xinMgxinSe/Zn1-xoutMgxoutSe quantum well

The band offsets for a Zn1-xinMgxin Se/Zn1-xoutMgxout Se quantum well heterostructure are determined using the model solid theory.The heavy hole exciton binding energies are investigated with various M...     

Highly Efficient Green ZnAgInS/ZnInS/ZnS QDs by a Strong Exothermic Reaction for Down‐Converted Green and Tripackage White LEDs

Highly efficient bright green‐emitting Zn?Ag?In?S (ZAIS)/Zn?In?S (ZIS)/ZnS alloy core/inner‐shell/shell quantum dots (QDs) are synthesized using a multistep hot injection method with a highly concentrated zinc acetate dihydrate precursor. ZAIS/ZIS/ZnS QD growth is realized via five sequential steps: a core growth process, a two‐step alloying–shelling process, and a two‐step shelling process. To enhance the photoluminescence quantum yield (PLQY), a ZIS inner‐shell is synthesized and added with a band gap located between the ZAIS alloy‐core and ZnS shell using a strong exothermic reaction. The synthesized ZAIS/ZIS/ZnS QDs shows a high PLQY of 87% with peak wavelength of 501 nm. Tripackage white down‐converted light‐emitting diodes (DC‐LEDs) are realized using an InGaN blue (B) LED, a green (G) ZAIS/ZIS/ZS QD‐based DC‐LED, and a red (R) Zn?Cu?In?S/ZnS QD‐based DC‐LED with correlated color temperature from 2700 to 10 000 K. The red, green, and blue tripackage white DC‐LEDs exhibit high luminous efficacy of 72 lm W^?1 and excellent color qualities (color rendering index (CRI, R_a) = 95 and the special CRI for red (R₉) = 93) at 2700 K.     

CdTe/CdS、CdTe/ZnS核壳结构半导体量子点制备及荧光特性

核壳半导体量子点材料因其在修复单量子点表面缺陷方面的特殊性能,极大地提高了量子点的光学性能而受到人们的研究。改进了CdTe核心的制作方法,使用小型三口瓶替代传统的小烧瓶作为反应容器,制备碲氢化钠,合成了不同核心尺寸、不同壳层厚度与不同壳层材料的10种CdTe/CdS、CdTe/ZnS核壳结构半导体量子点。对10种核壳结构半导体量子点材料进行紫外可见吸收光谱及荧光光谱测试,并分析其荧光特性。量子点在紫外可见波段的吸收光谱表明随着量子点尺寸的增大,吸收峰发生红移。通过实验结果与分析可推断出CdTe/CdS量子点荧光寿命和强度的不同是由于核心和壳层尺寸的不同量子点在I型和II型中相互转换;CdTe/ZnS的壳层厚度增加时,由于ZnS的壳层降低了核心外表的悬空键和表面缺陷态的数量,使电子空穴对复合机率加大,使得荧光峰位产生了红移。     

Variations in the characteristics of CdxZn1-xS films deposited with little Cd-containing solutions

In order to prepare Cd_xZn_1-xS films with lower cadmium content and better performance as a buffer layer for copper indium gallium selenide(CIGS) solar cells, the performance of Cd_xZn_1-xS films deposited in a mixture of solutions containing extremely low cadmium sources was systematically investigated by chemical bath deposition(CBD) with the synergy of chemical experiments and numerical simulations. The experimental results show that the films have the...     

Nonlinear Optical Properties of CdS/ZnS Quantum Dots in a High-Molecular-Weight Polyvinylpyrrolidone Matrix

Sols containing core/shell CdS/ZnS semiconductor quantum dots are synthesized and their nonlinear properties, which are interesting for a large variety of applications in nanophotonics, are studied. The quantum dots produced are smaller in dimensions than the exciton Bohr radius and, therefore, exhibit a well-pronounced quantum-confinement effect. The nonlinear optical properties of low-concentration sols are studied upon exposure to laser pulses with an emission wavelength of 532 nm and a duration of 5 ns by the z-scan technique. The dependences of nonlinear optical coefficients on the concentration of CdS/ZnS quantum dots are obtained. The intensity dependence of two-photon absorption coefficients is presented. The dependence determines the boundary of the influence of high-order nonlinearities on the nonlinear transmittance of the samples. The mechanisms of optical limitation exhibited by sols, specifically, two-photon absorption, nonlinear refraction, and nonlinear scattering are discussed.     

Photoluminescence Tuning in Stretchable PDMS Film Grafted Doped Core/Multishell Quantum Dots for Anticounterfeiting

The development of new luminescent materials for anticounterfeiting is of great importance, owing to their unique physical, chemical, and optical properties. The authors report the use of color‐tunable colloidal CdS/ZnS/ZnS:Mn²⁺/ZnS core/multishell quantum dots (QDs)‐functionalized luminescent polydimethylsiloxane film (LPF) for anticounterfeiting applications. Both luminescent QDs and as‐fabricated, stretchable, and transparent LPF show blue and orange emission simultaneously, which are ascribed to CdS band‐edge emission and the ⁴T₁ → ⁶A₁ transition of Mn²⁺, respectively; their emission intensity ratios are dependent on the power‐density of a single‐wavelength excitation source. Additionally, photoluminescence tuning of CdS/ZnS/ZnS:Mn²⁺/ZnS QDs in hexane or embedded in LPF can also be realized under fixed excitation power due to a resonance energy transfer effect. Tunable photoluminescence of these flexible LPF grafted doped core/shell QDs can be finely controlled and easily realized, depending on outer excitation power and intrinsic QD concentration, which is intriguing and inspires the fabrication of many novel applications.     

Highly Efficient Green Zn?Ag?In?S/Zn?In?S/ZnS QDs by a Strong Exothermic Reaction for Down‐Converted Green and Tripackage White LEDs

Highly efficient bright green‐emitting Zn? Ag? In? S (ZAIS)/Zn? In? S (ZIS)/ZnS alloy core/inner‐shell/shell quantum dots (QDs) are synthesized using a multistep hot injection method with a highly concentrated zinc acetate dihydrate precursor. ZAIS/ZIS/ZnS QD growth is realized via five sequential steps: a core growth process, a two‐step alloying–shelling process, and a two‐step shelling process. To enhance the photoluminescence quantum yield (PLQY), a ZIS inner‐shell is synthesized and added with a band gap located between the ZAIS alloy‐core and ZnS shell using a strong exothermic reaction. The synthesized ZAIS/ZIS/ZnS QDs shows a high PLQY of 87% with peak wavelength of 501 nm. Tripackage white down‐converted light‐emitting diodes (DC‐LEDs) are realized using an InGaN blue (B) LED, a green (G) ZAIS/ZIS/ZS QD‐based DC‐LED, and a red (R) Zn? Cu? In? S/ZnS QD‐based DC‐LED with correlated color temperature from 2700 to 10 000 K. The red, green, and blue tripackage white DC‐LEDs exhibit high luminous efficacy of 72 lm W^?1 and excellent color qualities (color rendering index (CRI, R _a) = 95 and the special CRI for red (R ₉) = 93) at 2700 K.     

Sub‐kilogram‐Scale One‐Pot Synthesis of Highly Luminescent and Monodisperse Core/Shell Quantum Dots by the Successive Injection of Precursors

The one‐pot synthesis of core/shell quantum dots (QDs) represents an attractive alternative to conventional synthesis techniques, where the core CdSe QDs are first purified and then an epitaxial shell of the desired thickness is obtained by the slow addition of shell precursors to a solution of the purified QDs at high temperature. We have developed a one‐pot synthesis procedure involving the successive injection of deliberately selected core‐ and shell‐forming reagents at appropriate temperatures. Sub‐kilogram quantities of highly luminescent and monodisperse core/shell QDs with desirable optical properties (full width at half maximum of photoluminescence (PL) band is ca. 30 nm) have been produced by the sequential growth of the core and shell in a controlled manner. This one‐pot method has also been extended to form water‐soluble core/double‐shell CdSe/ZnSe/ZnS QDs exhibiting high PL efficiency and stability.     

应变纤锌矿ZnO/MgxZn1-xO量子点中离子施主束缚激子的光学性质

Within the framework of the effective-mass approximation and the dipole approximation, considering the three-dimensional confinement of the electron and hole and the strong built-in electric field(BEF) in strained wurtzite Zn O/Mg0:25Zn0:75O quantum dots(QDs), the optical properties of ionized donor-bound excitons(D+, X)are investigated theoretically using a variational method. The computations are performed in the case of finite band offset. Numerical results indicate that the optical properties of(D+, X) complexes sensitively depend on the donor position, the QD size and the BEF. The binding energy of(D+, X) complexes is larger when the donor is located in the vicinity of the left interface of the QDs, and it decreases with increasing QD size. The oscillator strength reduces with an increase in the dot height and increases with an increase in the dot radius. Furthermore, when the QD size decreases, the absorption peak intensity shows a marked increment, and the absorption coefficient peak has a blueshift. The strong BEF causes a redshift of the absorption coefficient peak and causes the absorption peak intensity to decrease remarkably. The physical reasons for these relationships have been analyzed in depth.     

GaN1?xBix合金的电子与光学性质的第一性原理计算

The electronic and optical properties of the ternary Ga N1 xBix alloys in the zinc-blende structure are theoretically investigated by first principles calculations. Geometric optimization is performed before all the simulations to get accurate results. The band gaps of the alloys are found to be direct even with xD6.25%, and would become smaller when increasing the Bi compositions. The decrease ratio of band gaps is approximately 227 me V when 1% of N is replaced by Bi in the range of xD0–6.25%. Meanwhile, the absorption coefficient is shown to be significantly changed induced by the incorporation of Bi. These interesting properties indicate that Ga N1 xBix alloys could be a promising candidate in future optoelectronic applications.     

Over 30% External Quantum Efficiency Light‐Emitting Diodes by Engineering Quantum Dot‐Assisted Energy Level Match for Hole Transport Layer

In the study of hybrid quantum dot light‐emitting diodes (QLEDs), even for state‐of‐the‐art achievement, there still exists a long‐standing charge balance problem, i.e., sufficient electron injection versus inefficient hole injection due to the large valence band offset of quantum dots (QDs) with respect to the adjacent carrier transport layer. Here the dedicated design and synthesis of high luminescence Zn_1?x Cd_xSe/ZnSe/ZnS QDs is reported by precisely controlled shell growth, which have matched energy level with the adjacent hole transport layer in QLEDs. As emitters, such Zn_1?xCd_xSe‐ based QLEDs exhibit peak external quantum efficiencies (EQE) of up to 30.9%, maximum brightness of over 334 000 cd m^?2, very low efficiency roll‐off at high current density (EQE ≈25% @ current density of 150 mA cm^?2), and operational lifetime extended to ≈1 800 000 h at 100 cd m^?2. These extraordinary performances make this work the best among all solution‐processed QLEDs reported in literature so far by achieving simultaneously high luminescence and balanced charge injection. These major advances are attributed to the combination of an intermediate ZnSe layer with an ultrathin ZnS outer layer as the shell materials and surface modification with 2‐ethylhexane‐1‐thiol, which can dramatically improve hole injection efficiency and thus lead to more balanced charge injection.     

Study of capping agent effect on the structural,optical and photocatalytic properties of zinc sulfide quantum dots

In this work, the effect of capping agent type on the structural, optical and photocatalytic properties of pure zinc sulfide (ZnS) quantum dots (QDs) has been investigated. ZnS QDs were prepared by a simple, fast and water based chemical precipitation method, in the presence of various capping agents including 2-mercaptoethanol, thiourea, and l-cysteine. The obtained QDs have been characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), and UV–visible absorption spectroscopy. The results revealed that the optical absorption band of ZnS nanostructures varied by capping agents. In the photocatalytic investigations, the prepared ZnS QDs were applied for the photodecolorization of crystal violet (CV) as a model molecule. Influence of affecting parameters on the decolorization efficiency of the capped ZnS QDs was studied and optimized. The results indicated that the prepared QDs can effectively remove different concentrations of CV dye at alkaline pH, in the presence of low concentrations of QDs. According to the photocatalytic results, the presented method can be considered as a green, quick and efficient strategy for photobleaching of organic pollutants based on the high performance photocatalytic behavior of ZnS QDs capped by different capping agents.     

Characterization of GaAs/ InxGa1−x As quantum-dot heterostructures by electrical and optical methods

Results of electrical and optical studies of GaAs/In_xGa_1−x As heterostructures are reported. The aim of these studies was to identify the quantum dots and develop a technology of their growth by spontaneous transformation of an In_xGa_1−x As layer. The surface charge at the depth of the quantum dots and their surface density as a function of the deposition time of this narrow-band material are estimated by C-V profiling. A photoluminescence study of the quantum dots revealed peculiarities of the filling of their electron states at various excitation levels. The influence of Coulomb interactions on the optical properties of the quantum dots is discussed. Fiz. Tekh. Poluprovodn. 32, 111–116 (January 1998)     

Directly assembled quantum dots on one dimension ordered TiO2 nanostructure in aqueous solution for improving photocatalytic activity

One dimension (1D) ordered titanium dioxide (TiO2) nanostructured photocatalysts sensitized by quantum dots (QDs) are fabricated. Their morphologies, crystal structures and photocatalytic properties are characterized by scanning elec-tron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and ultraviolet-visible-near infrared (UV-vis-NIR) absorption spectroscopy, respectively. Compared with the original TiO2 nanostructure, the nanostructured TiO2 sensitized by QDs exhibits a good photocatalytic activity for the degradation of methyl orange (MO). The QDs with core-shell structure can reduce the photocatalytic ability due to the higher potential barrier of carrier transport in ZnS shell layer. The results indicate that the proposed photocatalyst shows promising potential for the application in organic dye degradation.