Solvothermal synthesis of InP quantum dots and their enhanced luminescent efficiency by post-synthetic treatments

InP quantum dots (QDs) were solvothermally synthesized by using a greener phosphorus source of P(N(CH(3))(2))(3) instead of highly toxic P(TMS)(3) widely used, and subsequently subjected to a size-sorting processing. While as-grown QDs showed an undetectably low emission intensity, post-synthetic treatments such as photo-etching, photo-radiation, and photo-assisted ZnS shell coating gave rise to a substantial increase in emission efficiency due to the effective removal and passivation of surface states. The emission efficiency of the photo-etched QDs was further enhanced by a consecutive UV photo-radiation, attributable to the photo-oxidation at QD surface. Furthermore, a relatively thick ZnS shell on the surface of InP QDs that were surface-modified with hydrophilic ligands beforehand was photochemically generated in an aqueous solution at room temperature. The resulting InP/ZnS core/shell QDs, emitting from blue to red wavelengths, were more efficient than the above photo-treated InP QDs, and their luminescent properties (emission bandwidth and quantum yield) were comparable to those of InP QDs synthesized with P(TMS)(3). Structural, size, and compositional analyses on InP/ZnS QDs were also conducted to elucidate their core/shell structure.     

Enhancing the device performance of a blue light‐emitting copolymer using CdSe/ZnS quantum dots

An alternating triarylamine‐functionalized fluorene‐based copolymer synthesized using a Suzuki–Miyaura cross‐coupling procedure is used as blue emitting layer in polymer light‐emitting diodes (PLEDs). Subsequently, the effects of CdSe/ZnS quantum dots (QDs) on the optoelectronic properties of the copolymer are investigated. Therefore, CdSe/ZnS QDs are embedded into the copolymer matrix and hybrid PLEDs are fabricated. The devices comprised of CdSe/ZnS QDs reveal enhanced performances, yielding about 3.4 times more luminous efficiency than that of the device without QDs. Further enhancement is achieved by using electron transport layer; the luminous efficiency rose from 0.065 to 1.740 cd A^?1 for the hybrid PLEDs, corresponding to a superb 27‐fold intensification of the efficiency. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 147–156     

Synthesis of Multifunctional Mn‐Doped CdTe/ZnS Core/Shell Quantum Dots

The synthesis of a novel water‐soluble Mn‐doped CdTe/ZnS core‐shell quantum dots using a proposed ultrasonic assistant method and 3‐mercaptopropionic acid (MPA) as stabilizer is descried. To obtain a high luminescent intensity, post‐preparative treatments, including the pH value, reaction temperature, reflux time and atmosphere, have been investigated. For an excellent fluorescence of Mn‐doped CdTe/ZnS, the optimal conditions were pH 11, reflux temperature 100°C and reflux time 3 h under N₂ atmosphere. While for phosphorescent Mn‐doped CdTe/ZnS QDs, the synthesis at pH 11, reflux temperature 100°C and reflux time 3 h under air atmosphere gave the best strong phosphorescence. The characterizations of Mn‐doped CdTe/ZnS QDs were also identified using AFM, IR, powder XRD and thermogravimetric analysis. The data indicated that the photochemical stability and the photoluminescence of CdTe QDs are greatly enhanced by the outer inorganic ZnS shell, and the doping Mn²⁺ ions in the as‐prepared quantum dots contribute to strong luminescence. The strong luminescence of Mn‐doped CdTe/ZnS QDs reflected that Mn ions act as recombination centers for the excited electron‐hole pairs, attributing to the transition from the triplet state (⁴T₁) to the ground state (⁶A₁) of the Mn²⁺ ions. All the experiments demonstrated that the surface states played important roles in the optical properties of Mn‐doped CdTe/ZnS core‐shell quantum dots.     

基于元素磷源的InP量子点的制备

以白磷作为磷源、醋酸铟为铟源、硬脂酸为表面包覆剂、十八烯为溶剂,采用胶体化学法合成了InP量子点。X射线衍射(XRD)和透射电子显微镜(TEM)分析测试显示InP量子点属于立方闪锌矿结构,并且是直径约为5 nm的球状纳米晶。紫外可见光谱和荧光光谱分析表明,InP量子点表现出明显的激子吸收和带边发射特征,荧光发射光谱在415~517 nm范围内连续可调,呈现明显的量子尺寸效应。     

Luminescence Enhancement based Sensing of L‐Cysteine by Doped Quantum Dots

The interaction of a presynthesized orange emitting Mn²⁺‐doped ZnS quantum dots (QDs) with L‐Cysteine (L?Cys) led to enhance emission intensity (at 596 nm) and quantum yield (QY). Importantly, the Mn²⁺‐doped ZnS QDs exhibited high sensitivity towards L?Cys, with a limit of detection of 0.4±0.02 μM (in the linear range of 3.3–13.3 μM) and high selectivity in presence of interfering amino acids and metal ions. The association constant of L?Cys was determined to be 0.36×10⁵ M^?1. The amplified passivation of the surface of Mn²⁺‐doped ZnS QDs following the incorporation and binding of L?Cys is accounted for the enhancement in their luminescence features. Moreover, the luminescence enhancement‐based detection will bring newer dimension towards sensing application.     

Crafting Core/Graded Shell–Shell Quantum Dots with Suppressed Re‐absorption and Tunable Stokes Shift as High Optical Gain Materials

The key to utilizing quantum dots (QDs) as lasing media is to effectively reduce non‐radiative processes, such as Auger recombination and surface trapping. A robust strategy to craft a set of CdSe/Cd_1?xZn_xSe_1?yS_y/ZnS core/graded shell–shell QDs with suppressed re‐absorption, reduced Auger recombination rate, and tunable Stokes shift is presented. In sharp contrast to conventional CdSe/ZnS QDs, which have a large energy level mismatch between CdSe and ZnS and thus show strong re‐absorption and a constrained Stokes shift, the as‐synthesized CdSe/Cd_1?xZn_xSe_1?yS_y/ZnS QDs exhibited the suppressed re‐absorption of CdSe core and tunable Stokes shift as a direct consequence of the delocalization of the electron wavefunction over the entire QD. Such Stokes shift‐engineered QDs with suppressed re‐absorption may represent an important class of building blocks for use in lasers, light emitting diodes, solar concentrators, and parity‐time symmetry materials and devices.     

Synthesis of CdTe Quantum Dots with Tunable Photoluminescence Using Tellurium Dioxide as Tellurium Source

A simple and convenient method has been developed for synthesis of water‐soluble CdTe quantum dots (QDs) under ambient atmospheric conditions. In contrast to the traditional aqueous synthesis, green to red emitting CdTe QDs were prepared by using TeO₂ to replace Te or Al₂Te₃ as tellurium source in this method. The influences of experimental variables, including pH value, 3‐mercaptopropionic acid (MPA)/Cd and Te/Cd molar ratios, on the emission peak and photoluminescence (PL) quantum yield (QY) of the obtained CdTe QDs have been systematically investigated. Experimental results indicate that green to red emitting CdTe QDs with a maximum photoluminescence quantum yield of 35.4% can be prepared at pH 11.3 and n_(Cd):n_(Te):n_(MPA)=1:0.1:1.7.     

水溶性InP/ZnS量子点的合成及其在指纹显现中的应用

以磷化锌、氯化铟为原料,以十二烷胺为溶剂,在150～200℃下合成了InP量子点,通过相转移和紫外光照得到了巯基乙酸修饰的水溶性InP/ZnS量子点.利用X射线衍射仪、透射电镜、高分辨透射电镜、荧光光谱仪等分析了不同温度下合成的量子点的粒径、形貌、荧光性能及指纹显现效果.结果表明,合成的InP和InP/ZnS量子点为球...     

Electrophoretic properties of BSA-coated quantum dots

Low toxic InP/ZnS quantum dots (QDs), ZnS:Mn²⁺/ZnS nanocrystals and CdSe/ZnS nanoparticles were rendered water-dispersible by different ligand-exchange methods. Eventually, they were coated with bovine serum albumin (BSA) as a model protein. All particles were characterised by isotachophoresis (ITP), laser Doppler velocimetry (LDV) and agarose gel electrophoresis. It was found that the electrophoretic mobility and colloidal stability of ZnS:Mn²⁺/ZnS and CdSe/ZnS nanoparticles, which bore short-chain surface ligands, was primarily governed by charges on the nanoparticles, whereas InP/ZnS nanocrystals were not charged per se. BSA-coated nanoparticles showed lower electrophoretic mobility, which was attributed to their larger size and smaller overall charge. However, these particles were colloidally stable. This stability was probably caused by steric stabilisation of the BSA coating.     

Energy Relay from an Unconventional Yellow Dye to CdS/CdSe Quantum Dots for Enhanced Solar Cell Performance

A new design for a quasi‐solid‐state Forster resonance energy transfer (FRET) enabled solar cell with unattached Lucifer yellow (LY) dye molecules as donors and CdS/CdSe quantum dots (QDs) tethered to titania (TiO₂) as acceptors is presented. The Forster radius is experimentally determined to be 5.29 nm. Sequential energy transfer from the LY dye to the QDs and electron transfer from the QDs to TiO₂ is followed by fluorescence quenching and electron lifetime studies. Cells with a donor–acceptor architecture (TiO₂/CdS/CdSe/ZnS‐LY/S^2?‐multi‐walled carbon nanotubes) show a maximum incident photon‐to‐current conversion efficiency of 53 % at 530 nm. This is the highest efficiency among Ru‐dye free FRET‐enabled quantum dot solar cells (QDSCs), and is much higher than the donor or acceptor‐only cells. The FRET‐enhanced solar cell performance over the majority of the visible spectrum paves the way to harnessing the untapped potential of the LY dye as an energy relay fluorophore for the entire gamut of dye sensitized, organic, or hybrid solar cells.     

Low temperature synthesis of cubic phase zinc sulfide quantum dots

In this study, we report on a new method for the synthesis of ZnS quantum dots (QDs). The synthesis was carried out at low temperature by a chemical reaction between zinc ions and freshly reduced sulfide ions in ethanol as reaction medium. Zinc chloride and elemental sulfur were used as zinc and sulfur sources, respectively and hydrazine hydrate was used as a strong reducing agent to convert elemental sulfur (S₈) into highly reactive sulfide ions (S²⁻) which react spontaneously with zinc ions. This facile, less toxic, inexpensive route has a high yield for the synthesis of high quality metal sulfide QDs. Transmission electron microscopy (TEM) image analysis and selected area electron diffraction (SAED) reveal that ZnS QDs are less than 3 nm in diameter and are of cubic crystalline phase. The UV-Vis absorption spectrum shows an absorption peak at 253 nm corresponding to a band gap of 4.9 eV, which is high when compared to the bulk value of 3.68 eV revealing strong quantum confinement. PL emission transitions are observed at 314 nm and 439 nm and related to point defects in ZnS QDs.     

Highly Luminescent and Ultrastable CsPbBr3 Perovskite Quantum Dots Incorporated into a Silica/Alumina Monolith

We successfully prepared QDs incorporated into a silica/alumina monolith (QDs‐SAM) by a simple sol–gel reaction of an Al–Si single precursor with CsPbBr₃ QDs blended in toluene solution, without adding water and catalyst. The resultant transparent monolith exhibits high photoluminescence quantum yields (PLQY) up to 90 %, and good photostability under strong illumination of blue light for 300 h. We show that the preliminary ligand exchange of didodecyl dimethyl ammonium bromide (DDAB) was very important to protect CsPbBr₃ QDs from surface damages during the sol–gel reaction, which not only allowed us to maintain the original optical properties of CsPbBr₃ QDs but also prevented the aggregation of QDs and made the monolith transparent. The CsPbBr₃ QDs‐SAM in powder form was easily mixed into the resins and applied as color‐converting layer with curing on blue light‐emitting diodes (LED). The material showed a high luminous efficacy of 80 lm W⁻¹ and a narrow emission with a full width at half maximum (FWHM) of 25 nm.     

油溶性CuInS2/ZnS量子点的制备及其温敏性聚丙烯酰胺胶束介导的水相转移

采用非热注法成功制备了高质量的油溶性CuInS₂/ZnS核壳量子点, 量子点的荧光发射峰在可见光到近红外范围内可调(550~800 nm), 且荧光量子产率最高达80%。本文进一步利用具有温敏特性的聚丙烯酰胺胶束作相转移剂, 成功地将油溶性的CuInS₂/ZnS核壳量子点转移入水相。水相中自组装形成的CuInS₂/ZnS量子点-胶束复合物不仅具有良好的荧光性质, 而且胶束原有的灵敏的热响应性被保留。这些研究初步表明, 无镉的低毒的CuInS₂/ZnS量子点可作为纳米胶束的荧光示踪探针。     

油溶性CuInS2/ZnS量子点的制备及其温敏性聚丙烯酰胺胶束介导的水相转移

采用非热注法成功制备了高质量的油溶性CuInS2/ZnS核壳量子点,量子点的荧光发射峰在可见光到近红外范围内可调(550～800 nm),且荧光量子产率最高达80%。本文进一步利用具有温敏特性的聚丙烯酰胺胶束作相转移剂,成功地将油溶性的CuInS2/ZnS核壳量子点转移入水相。水相中自组装形成的CuInS2/ZnS量子点-胶束复合物不仅具有良好的荧光性质,而且胶束原有的灵敏的热响应性被保留。这些研究初步表明,无镉的低毒的CuInS2/ZnS量子点可作为纳米胶束的荧光示踪探针。     

Characterizing mixed phosphonic acid ligand capping on CdSe/ZnS quantum dots using ligand exchange and NMR spectroscopy

The ligand capping of phosphonic acid functionalized CdSe/ZnS core–shell quantum dots (QDs) was investigated with a combination of solution and solid‐state ³¹P nuclear magnetic resonance (NMR) spectroscopy. Two phosphonic acid ligands were used in the synthesis of the QDs, tetradecylphosphonic acid and ethylphosphonic acid. Both alkyl phosphonic acids showed broad liquid and solid‐state ³¹P NMR resonances for the bound ligands, indicative of heterogeneous binding to the QD surface. In order to quantify the two ligand populations on the surface, ligand exchange facilitated by phenylphosphonic acid resulted in the displacement of the ethylphosphonic acid and tetradecylphosphonic acid and allowed for quantification of the free ligands using ³¹P liquid‐state NMR. After washing away the free ligand, two broad resonances were observed in the liquids' ³¹P NMR corresponding to the alkyl and aromatic phosphonic acids. The washed samples were analyzed via solid‐state ³¹P NMR, which confirmed the ligand populations on the surface following the ligand exchange process. Copyright © 2015 John Wiley & Sons, Ltd.     

CdSe/ZnS量子点敏化太阳能电池电子注入与光伏性能表征

合成了CdSe/ZnS核壳结构量子点(QDs), 将其作为光敏剂吸附在TiO2纳米晶薄膜上, 组装成量子点敏化太阳能电池(QDSSCs), 从电子注入速率和电池性能两方面对QDSSCs进行了表征. 为了定量研究ZnS层包覆对电子注入的影响, 运用飞秒瞬态光谱技术, 测试了包覆ZnS前后, CdSe-TiO₂体系的电子注入速率. 实验测得ZnS包覆前后电子注入速率分别为7.14×10¹¹s^-1和2.38×10^-11s^-1, 可以看出包覆后电子注入速率明显降低, 仅为包覆前的1/3. 电池器件J-V性能测试表明, ZnS作为绝缘层包覆在CdSe的表面有效提高了QDSSCs的填充因子和稳定性, 但同时也导致了效率的降低. 上述结果说明了电子注入速率的降低是导致电池电流和效率下降的重要原因, 为今后优化核壳结构QDSSCs的电流和效率提供了依据.     

Electrochemiluminescence resonance energy transfer between quantum dots (QDs) as the donor and Cy5 dye molecules as the acceptor in QD-Cy5 conjugates with biomolecules as the linker

Electrochemiluminescence resonance energy transfer (ECRET) between CdSe/Zns quantum dots (QDs) as the donor and cyanine dye (Cy5) molecules as the acceptor in QD-Cy5 conjugates with DNA or protein as the linker was reported. When a negative potential was applied, the excited-state CdSe/ZnS* was produced in 0.1 mol/L phosphate buffer (pH 7.4) containing 0.1 mol/L K₂S₂O₈ and 0.1 mol/L KNO₃ (PB-K₂S₂O₈). The CdSe/ZnS* went back to the ground-state CdSe/ZnS to emit light at 590 nm or to transfer energy to proximal ground-state Cy5 molecules. The resultant excited-state Cy5 molecules relaxed to their ground state by emitting a light at 675 nm. The ECRET between QDs and Cy5 was used to evaluate interactions between DNAs and to measure conformational changes of DNAs and proteins.     

Interface effects and relaxation processes in nanocomposites based on CdSe/ZnS semiconductor quantum dots and porphyrin molecules

Controllable self-assembly and properties of nanocomposites based on CdSe/ZnS semiconductor quantum dots (QDs) and tetrapyridylporphyrin molecules (H₂P) as well as the dynamics of relaxation processes in these systems were studied for solutions and single nanoobjects in the temperature range of 77–295 K. It was proved that the formation of surface states of different nature is crucial to nonradiative relaxation of exciton excitation in QDs. The efficiency of QD→Н₂Р energy transfer was shown to be at most 10–15%. Regularities of photoluminescence (PL) quenching for QDs in nanocomposites in solutions of different polarity correlate with the dependences of PL blinking for single QDs. A scheme was proposed of excited states and main relaxation channels of exciton excitation energy in semiconductor QDs and QD–Н₂Р nanocomposites.     

A Novel One‐Pot Synthesis of UV‐Blue ZnSe Nanocrystals in Aqueous Solution

Described herein is a novel one‐pot aqueous synthesis of ZnSe nanocrystals has featuring the utilization of Na₂SeO₃ and Zn(AC)₂×2H₂O as Se and Zn source, glutathione (GSH) as stabilizing agent and reducing agent. By this approach, the UV‐blue ZnSe QDs with quantum yield (QYs) up to 19% have been synthesized with a molar ratio of Se/Zn/GSH at 1:4:8.5 under aqueous conditions at 110 °C. XRD and TEM show the ZnSe QDs are zinc cubic structure particles with an average diameter of 3–5 nm.     

Fluorescent cellulose aerogels containing covalently immobilized (ZnS)x(CuInS2)1−x/ZnS (core/shell) quantum dots

Photoluminiscent (PL) cellulose aerogels of variable shape containing homogeneously dispersed and surface-immobilized alloyed (ZnS)_x(CuInS₂)_1?x/ZnS (core/shell) quantum dots (QD) have been obtained by (1) dissolution of hardwood prehydrolysis kraft pulp in the ionic liquid 1-hexyl-3-methyl-1H-imidazolium chloride, (2) addition of a homogenous dispersion of quantum dots in the same solvent, (3) molding, (4) coagulation of cellulose using ethanol as antisolvent, and (5) scCO₂ drying of the resulting composite aerogels. Both compatibilization with the cellulose solvent and covalent attachment of the quantum dots onto the cellulose surface was achieved through replacement of 1-mercaptododecyl ligands typically used in synthesis of (ZnS)_x(CuInS₂)_1?x/ZnS (core–shell) QDs by 1-mercapto-3-(trimethoxysilyl)-propyl ligands. The obtained cellulose—quantum dot hybrid aerogels have apparent densities of 37.9–57.2 mg cm^?3. Their BET surface areas range from 296 to 686 m² g^?1 comparable with non-luminiscent cellulose aerogels obtained via the NMMO, TBAF/DMSO or Ca(SCN)₂ route. Depending mainly on the ratio of QD core constituents and to a minor extent on the cellulose/QD ratio, the emission wavelength of the novel aerogels can be controlled within a wide range of the visible light spectrum. Whereas higher QD contents lead to bathochromic PL shifts, hypsochromism is observed when increasing the amount of cellulose at constant QD content. Reinforcement of the cellulose aerogels and hence significantly reduced shrinkage during scCO₂ drying is a beneficial side effect when using α-mercapto-ω-(trialkoxysilyl) alkyl ligands for QD capping and covalent QD immobilization onto the cellulose surface.