Mechanistic Aspects of Quantum Dot Based Probing of Cu (II) Ions: Role of Dendrimer in Sensor Efficiency

Selective quenching of luminescence of quantum dots (QDs) by Cu²⁺ ions vis-à-vis other physiologically relevant cations has been reexamined. In view of the contradiction regarding the mechanism, we have attempted to show why Cu²⁺ ions quench QD-luminescence by taking CdS and CdTe QDs with varying surface groups. A detailed study of the solvent effect and also size dependence on the observed luminescence has been carried out. For a 13% decrease in particle diameter (4.3 nm →3.7 nm), the quenching constant increased by a factor of 20. It is established that instead of surface ligands of QDs, conduction band potential of the core facilitates the photo-induced reduction of Cu (II) to Cu (I) thereby quenching the photoluminescence. Taking the advantage of biocompatibility of dendrimer and its high affinity towards Cu²⁺ ions, we have followed interaction of Cu²⁺-PAMAM and also dendrimer with the CdTe QDs. Nanomolar concentration of PAMAM dendrimer was found to quench the luminescence of CdTe QDs. In contrast, Cu²⁺-PAMAM enhanced the fluorescence of CdTe QDs and the effect has been attributed to the binding of Cu²⁺-PAMAM complex to the CdTe particle surface. The linear portion of the enhancement plot due to Cu²⁺-PAMAM can be used for determination of Cu²⁺ ions with detection limit of 70 nM.     

Green Luminescent CdTe Quantum Dot Based Fluorescence Nano-Sensor for Sensitive Detection of Arsenic (III)

Arsenic (As³⁺) is a hazardous and ubiquitous element; hence the quantitative detection of arsenic in various kinds of environmental sample is an important issue. Herein, we reported L-cysteine capped CdTe Quantum dot based optical sensor for the fluorometric detection of arsenic (III) in real water sample. The method is based on the fluorescence quenching of QDs with the addition of arsenic solution that caused the reduction in fluorescence intensity due to strong interaction between As³⁺ and L-cysteine to form As(Cys)₃. The calibration curve was linear over 2.0 nM-0.5 μM arsenic with limit of detection (LOD) of 2.0 nM, correlation coefficient (r²) of 0.9698, and relative standard deviation (RSD %) of 5.2%. The Stern-Volmer constant for the quenching of CdTe QDs with As³⁺ at optimized condition was evaluated to be 1.17 × 10⁸ L mol^?1 s^?1. The feasibility of the sensor has been analyzed by checking the inference of common metal ions available in the water such as K⁺, Na⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, Ni²⁺, Zn²⁺, Al³⁺, Co²⁺, Cr²⁺, Fe³⁺ and its higher oxidation state As⁵⁺.

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Graphical Abstract Schematic representation of As³⁺ detection by L-Cysteine capped CdTe QDs

     

Interaction of Folic Acid with Mn2+ Doped CdTe/ZnS Quantum Dots: In Situ Detection of Folic Acid

To utilize the nanomaterials as an effective carrier for the drug delivery applications, it is important to study the interaction between nanomaterials and drug or biomolecules. In this study GSH functionalized Mn²⁺-doped CdTe/ZnS QDs has been utilized as a model nanomaterial due to its high luminescence property. Folic acid (FA) gradually quenches the FL of GSH functionalized Mn²⁺???doped CdTe/ZnS QDs. The Stern-Volmer quenching constant (K_sv), binding constant (K_s) and effective quenching constant (Ka) for the FA-QDs system is calculated to be 1.32?×?10⁵ M^?1, 1.92?×?10⁵ and 0.27?×?10⁵ M^?1, respectively under optimized condition (Temp. 300 K, pH 8.0, incubation time 40 min.). The effects of temperature, pH, and incubation time on FA-QDs system have also been studied. Statistical analysis of the quenched FL intensity versus FA concentration revealed a linear range from 1?×?10^?7 to 5.0?×?10^?5 for FA detection. The LOD of the current nano-sensor for FA was calculated to be 0.2 μM. The effect of common interfering metal ions and other relevant biomolecules on the detection of FA (12.0 μM) have also been investigated. L-cysteine and glutathione displayed moderate effect on FA detection. Similarly, the common metal ions (Na⁺, K⁺, Ca²⁺ and Mg²⁺) produced minute interference while Zn²⁺ Cu²⁺ and Fe³⁺ exert moderate interference. Toxic metal ions (Hg²⁺ and Pb²⁺) produced severe interferences in FA detection.

Graphical abstract

GSH-Mn²⁺ CdTe/ZnS QDs based Fluorescence Nanosensor for Folic acid

     

Electrostatic assembly of CdTe quantum dots with different charged ligands into TiO2 porous film for solar cells

We have demonstrated an approach for the electrostatic assembly of CdTe quantum dots (QDs) with different charged ligands as sensitizers, achieving high coverage and good dispersion in TiO₂ porous films. The CdTe QD-sensitized TiO₂ porous films were subjected to thermal annealing in a high vacuum chamber to remove the ligand linker, resulting in the formation of direct heterojunctions between the bare CdTe QDs and TiO₂ for a favorable charge transfer. The as-received CdTe QD-sensitized TiO₂ porous films were employed as photoanodes for quantum dot-sensitized solar cells (QSSCs), and the photocurrent density reached as high as 4.69 mA/cm² under a standard illumination condition of simulated AM 1.5G (100 mW/cm²).     

Determination of l-proline based on anodic electrochemiluminescence of CdTe quantum dots

A novel flow injection method for detection of l-proline was proposed in the presence of CdTe quantum dots (QDs). This method is based on the enhanced anodic electrochemiluminescence (ECL) emission of CdTe QDs l-proline in aqueous system. CdTe QDs were modified with thioglycolic acid to obtain stable water-soluble QDs and intensive anodic ECL emission in Na₂CO₃–NaHCO₃ buffer solution at an indium tin oxide (ITO) electrode, which was used for the sensitive detection of ECL enhancement using our homemade flow cell. Under the optimal conditions, the ECL intensity was correlated linearly with the concentration of l-proline over the range of 1.0×10^?8?1.0×10^?4 g mL^?1 (r=0.9996) and the detection limit was 5.0×10^?9 g mL^?1. The relative standard deviation was 1.12% for 6.0×10^?5 g mL^?1 l-proline (n=11). The possible mechanism was discussed. This method put forward a new efficient ECL methodology for enhancement-related determination of l-proline successfully.     

Wet chemical etched CdTe thin film solar cells

Wet chemical etching process on as-deposited CdTe surface using nitric-phosphoric (NP) acid improved the efficiency of CdS/CdTe solar cells from 10.1% to 13.8%. Nitric-phosphoric (NP) acid solution etched native oxide (TeO₂) layer and resolved excess cadmium on CdTe surface. After the heat treatment process activated the CdCl₂, CdO layer which was believed to be a diffusion barrier of chlorine did not grow on the etched CdTe surface and new (V_Cd^2?–2Cl_Te¹⁺)⁰ complexes was located at E_V + 0.045 eV. New (V_Cd^2?–2Cl_Te¹⁺)⁰ complexes acted as a shallow acceptors and induced to improve V_oc and J_sc. The surface of CdTe thin film has been studied using Scanning Electron Microscope (SEM), X-ray Diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and low temperature Photoluminescence (PL).     

Deep level transient spectroscopy investigation of deep levels in CdS/CdTe thin film solar cells with Te:Cu back contact

Deep levels in Cds/CdTe thin film solar cells have a potent influence on the electrical property of these devices. As an essential layer in the solar cell device structure, back contact is believed to induce some deep defects in the CdTe thin film. With the help of deep level transient spectroscopy (DLTS), we study the deep levels in CdS/CdTe thin film solar cells with Te:Cu back contact. One hole trap and one electron trap are observed. The hole trap H1, localized at E_v+0.128~eV, originates from the vacancy of Cd (V_Cd. The electron trap E1, found at E_c-0.178~eV, is considered to be correlated with the interstitial Cu_i⁼ in CdTe.     

基于CdTe量子点荧光猝灭-恢复方法测定依诺沙星的研究

水相合成了巯基丙酸保护的CdTe量子点。根据在Cu2+存在的情况下,CdTe量子点荧光恢复程度与依诺沙星浓度成正比的现象,建立了基于CdTe量子点荧光猝灭-恢复测定依诺沙星的新方法。考察了溶液pH值以及Cu2+浓度等对检测体系的影响。在p H=10的硼砂缓冲溶液中,在Cu2+浓度为2.3×10-5mol/L的条件下,依诺沙星浓度在8.0×10-7~3.0×10-5mol/L范围内与量子点荧光恢复程度呈良好的线性关系,检出限为7.2×10-8mol/L。该方法用于实际样品中依诺沙星的检测,回收率为95.5%~105.0%。     

CdTe量子点荧光猝灭法测定微量铅

以CdTe量子点作为荧光探针,基于荧光猝灭法对铅进行了定量检测,考察了缓冲溶液体系、量子点浓度、反应时间等多种因素的影响。实验结果表明,在pH 7.5的0.2mol/L Na2HPO4-NaH2PO4缓冲液中,反应时间为10min,铅浓度为2.0×10-6—3.5×10-5mol/L范围时,其线性回归方程为ΔF=26.35+11.47C(×10-6mol/L),相关系数和检出限分别为0.9991和1.8×10-8mol/L。该方法灵敏度高,为铅的测定提供了新的方法。     

Fast responsive fluorescence turn-on sensor for Cu2+ and its application in live cell imaging

A new effective fluorescent sensor based on rhodamine was synthesized, which was induced by Cu²⁺ in aqueous media to produce turn-on fluorescence. The new sensor 1 exhibited good selectivity for Cu²⁺ over other heavy and transition metal (HTM) ions in H₂O/CH₃CN(7:3, v/v). Upon addition of Cu²⁺, a remarkable color change from colorless to pink was easily observed by the naked eye, and the dramatic fluorescence turn-on was corroborated. Furthermore, kinetic assay indicates that sensor 1 could be used for real-time tracking of Cu²⁺ in cells and organisms. In addition, the turn-on fluorescent change upon the addition of Cu²⁺ was also applied in bioimaging.     

Microwave-assisted rapid synthesis of tetragonal Cu2SnS3 nanoparticles for solar photovoltaics

A simple and rapid process for the synthesis of Cu₂SnS₃ (CTS) nanoparticles by microwave heating of metal–organic precursor solution is described. X-ray diffraction and Raman spectroscopy confirm the formation of tetragonal CTS. X-ray photoelectron spectroscopy indicates the presence of Cu, Sn, S in +1, +4, ?2 oxidation states, respectively. Transmission electron microscopy divulges the formation of crystalline tetragonal CTS nanoparticles with sizes ranging 2–25 nm. Diffuse reflectance spectroscopy in the 300–2,400 nm wavelength range suggests a band gap of 1.1 eV. Pellets of CTS nanoparticles show p-type conduction and the carrier transport in temperature range of 250–425 K is thermally activated with activation energy of 0.16 eV. Thin film solar cell (TFSC) with architecture: graphite/Cu₂SnS₃/ZnO/ITO/SLG is fabricated by drop-casting dispersion of CTS nanoparticles which delivered a power conversion efficiency of 0.135 % with open circuit voltage, short circuit current and fill factor of 220 mV, 1.54 mA cm^?2, 0.40, respectively.     

Cu2S nanocrystals incorporated highly efficient non-fullerene ternary organic solar cells

Here, we report Cu₂S nanocrystals based non-fullerene ternary polymer solar cells by incorporating Cu₂S in conjugated polymer (PBDB-T: poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b′]dithiophene))-alt-(5,5-(1′,3′-di-2-thienyl-5′,7′-bis(2-ethylhexyl) benzo[1′,2′-c:4′,5′-c′]dithiophene-4,8-dione))]) and small molecule non-fullerene compound (ITIC:3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene). The devices were fabricated in inverted configuration i.e. ITO/ZnO/PBDB-T: Cu₂S NCs: ITIC/MoO₃/Ag. Effect of concentration of Cu₂S nanocrystals on the performance parameters of PBDB-T: ITIC based organic solar cells is studied. An enhancement in the power conversion efficiency from 8.24% to 9.53% is achieved for the optimum concentration of Cu₂S nanocrystals in the organic photoactive blend. The cause of improvement in the performance parameters of the device is investigated by means of the light intensity dependent electrochemical impedance spectroscopy and atomic force microscopy. It is found that the devices with Cu₂S nanocrystals have less trap-assisted recombination.     

Resonant Raman scattering from CdTe/ZnTe self-assembled quantum dot structures

We report resonant Raman scattering results of CdTe/ZnTe self-assembled quantum dot (QD) structures. Photoluminescence spectra reveal that the band gap energies of the CdTe QDs decrease with the increase of CdTe thickness from 2.0 to 3.5 monolayers, which indicates that the size of the QDs increases. When the CdTe/ZnTe QD structures are excited by non-resonant excitation, a longitudinal optical (LO) phonon response from the ZnTe barrier material is observed at 206 cm⁻¹. In contrast, when the CdTe/ZnTe QD structures are resonantly excited near the band gap energy of the QDs, additional phonon modes emerge at 167 and 200 cm⁻¹, while the ZnTe LO phonon response completely disappears. The 167 cm⁻¹ mode corresponds to the LO phonon of the CdTe QDs. A spatially resolved Raman scattering from the cleaved edge of the QD sample reveals that the 200 cm⁻¹ mode is strongly localized at the interface between the CdTe QDs and ZnTe cap layer. This phonon mode is attributed to the interface optical (IO) phonon. The analytically calculated value of the IO phonon energy using a dielectric continuum approach, assuming a spherical dot boundary, agrees well with the experimental value.     

Dependence of the interband transition and the activation energy on the ZnTe spacer thickness in CdTe/ZnTe double quantum dots

Photoluminescence (PL) measurements were carried out to investigate the interband transition and the activation energy in CdTe/ZnTe double quantum dots (QDs). While the excitonic peaks corresponding to the interband transition from the ground electronic subband to the ground heavy-hole (E₁-HH₁) in the CdTe/ZnTe double QDs shifted to higher energy with decreasing ZnTe spacer thickness from 30 to 10 nm due to transformation from CdTe QDs to Cd_xZn_1−xTe QDs, the peaks of the (E₁-HH₁) transitions shifted to lower energy with decreasing spacer thickness from 10 to 3 nm due to the tunneling effects of the electrons between CdTe double QDs. The decrease in the activation energy with decreasing ZnTe spacer thickness might originate from an increase in the number of defects in the ZnTe spacer. The present results can help improve the understanding of the interband transition and the activation energy in CdTe/ZnTe double QDs.     

The double-effect mechanism between Fe3O4 nanoparticles and MSA-capped CdTe QDs

Water-soluble mercaptosuccinic acid (MSA)-capped CdTe quantum dots (QDs) of two sizes and superparamagnetic Fe₃O₄ nanoparticles have been synthesized and used to investigate the effect of the mechanism of Fe₃O₄ nanoparticles on the fluorescence intensity of QDs. In the presence of a low concentration of Fe₃O₄ nanoparticles, the CdTe QDs with smaller particle size exhibit fluorescence quenching while fluorescence enhancement of CdTe QDs with larger particle size was observed, and the fluorescence intensity changes with the excitation wavelength and the concentration of Fe₃O₄ nanoparticles. The mechanism study shows that there is a double-effect between the Fe₃O₄ and CdTe QDs: one is the fluorescence quenching effect due to Fe₃O₄ strong absorption of excitation and emission light, the other is the fluorescence enhancement effect resulting from a localized electromagnetic field caused by the absorption of exciting light. The fluorescence of CdTe QDs with lower concentration of Fe₃O₄ nanoparticles was determined via the synergy of the double-effect. To our best knowledge, this is the first systematic study on the interaction between Fe₃O₄ nanoparticles and CdTe QDs, which finds the fluorescence enhancement effect in the presence of low concentration of Fe₃O₄.     

Silica-encapsulated CdTe/MPA quantum dots: microstructural,thermal, and chemical stability characterization

In this paper, we describe the synthesis of silica-encapsulated CdTe/MPA quantum dot (QD) nanocomposites (CdTe/MPA@SiO₂) at room temperature starting from water-soluble CdTe QDs capped with 3-mercaptopropionic acid (MPA) as surface ligand (CdTe/MPA), followed by their encapsulation with a thin layer of silica using the sol–gel process. The objective of this work was to evaluate the microstructural, thermal, and chemical properties of the encapsulated material as a way to evaluate these characteristics for possible applications in different technological areas. Transmission electron microscopy results proved that CdTe QDs (2.5 nm in size) were inside the SiO₂ nanoparticles, and the spherical CdTe/MPA@SiO₂ nanocomposite with a 69-nm thick shell. The photoluminescence intensity was evaluated as a function of pH in the range of 2–12. The CdTe/MPA@SiO₂ nanocomposite showed better chemical stability and greater intensity of photoluminescence in the pH 2–12 range than CdTe/MPA. In addition, the CdTe/MPA@SiO₂ nanocomposites showed good heat stability up to 125 °C. The changes in their optical properties were also evaluated by means of photoluminescence spectroscopy. The materials were also characterized by diffuse reflectance spectroscopy, X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis.

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Graphical abstract ?

     

CdTe太阳电池前电极SnO2:F/SnO2复合薄膜性能分析

减薄CdS窗口层是提高CdS/CdTe太阳电池转换效率的有效途径之一,减薄窗口层会对器件造成不利的影响,因此在减薄了的窗口层与前电极之间引入过渡层非常必要.利用反应磁控溅射法在前电极SnO₂:F薄膜衬底上制备未掺杂的SnO₂薄膜形成过渡层,并将其在N₂/O₂=4 ∶1,550 ℃环境进行了30 min热处理,利用原子力显微镜、X射线衍射仪、紫外分光光度计对复合薄膜热处理前后的形貌、结构、光学性能进行了表征,同时分析了复     

Two distinct photoluminescence responses of CdTe quantum dots to Ag (I)

Four sizes of water-soluble thiol-capped CdTe quantum dots (QDs) have been synthesized and used to investigate the photoluminescence (PL) responses to Ag⁺ ions. For small particles, the CdTe QDs exhibit PL enhancement in the presence of lower concentration of Ag⁺ but show obvious quenching with the further increase of Ag⁺; for larger particles, however, PL of CdTe QDs is quenched all the time with the Ag⁺ addition, no PL enhancement is observed. Mechanism study shows that small QDs with more traps on the particle surface are effectively passivated by initial adsorbed Ag⁺, which accounts for the PL enhancement observed; after the initial traps are saturated, the excess Ag⁺ facilitates nonradiative recombination, resulting in PL quenching. For larger particles, the nonradiative recombination dominates the whole process even for the lower concentration of Ag⁺, due to the fewer traps on the QD surface. Compared with larger particles, the small CdTe QDs are more suitable for sensing Ag⁺ because of the more sensitive and selective PL response. To our best knowledge, this is the first systematical study on the interaction of Ag⁺ with different-sized CdTe QDs.     

CdTe太阳电池的不同背电极和背接触层的特性研究

用Ni替代Au来作为CdTe太阳电池的背电极，比较了Ni,Ni/Au,Au/Ni及Au背电极对电池性能的影响.发现Ni作为背电极和ZnTe/ZnTe:Cu复合层接触，电池的开路电压V_oc略有降低，填充因子FF有增有减，变化幅度不大，但因短路电流I_sc有较大的提高，转换效率η平均增长4％.测试了不同背电极的CdTe太阳电池的暗I-V和C-V特性，对背电极剥离后的样品进行了XPS测试分析.结果表明，Ni扩散到ZnTe/ZnTe:Cu复合层的深度比Au多，且大多呈离子态，与ZnTe/ZnTe:Cu复合层中的富Te离子形成Ni_xTe，提高了掺杂浓度，使电池性能获得改善. 关键词： 金属背电极 复合背接触层 转换效率 CdTe太阳电池     

Sonoelectrochemical synthesis of water-soluble CdTe quantum dots

A facile and fast one-pot method has been developed for the synthesis of CdTe quantum dots (QDs) in aqueous phase by a sonoelectrochemical route without the protection of N₂. The morphology, structure and composition of the as-prepared products were investigated by high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and energy dispersive X-ray spectrometer (EDS). The influences of current intensity, current pulse width, and reaction temperature on the photoluminescence (PL) and quantum yield (QY) of the products were studied. The experimental results showed that the water-soluble CdTe QDs with high PL qualities can be conveniently synthesized without precursor preparation and N₂ protection, and the PL emission wavelength and QY can be effectively controlled by adjusting some parameters. This method can be expected to prepare other QDs as promising building blocks in solar cell, photocatalysis and sensors.