Photodarkening and anti-Stokes photoluminescence from PbSe and Sr2+-doped PbSe quantum dots in silicate glasses

Photoluminescence (PL) properties of PbSe and Sr²⁺-doped PbSe quantum dots (QDs) doped in silicate glasses were investigated by changing the excited laser wavelength and intensity. When BaO was replaced by SrO, the Sr²⁺-doped PbSe QDs formed and showed large blue-shifts in both absorption and PL bands compared to the PbSe QDs. It is attributed to the increasing in band gap resulted by the incorporation of Sr²⁺ ions into PbSe QDs. These two kinds of QDs were excited by the laser with the wavelengths of 1319 and 1532 nm. When rising the pumping intensity up to 1000 mW, the PL intensity from Sr²⁺-doped PbSe QDs monotonically increased, while, the PL intensity from PbSe QDs reached maximum at pumping intensity at ~200 mW (λ_ex = 1319 nm) and ~300 mW (λ_ex = 1532 nm). The good resistance to photodarkening of Sr²⁺-doped PbSe QDs is indicated passivation effect on the surface defects from Sr²⁺ ions doping. For Sr²⁺-doped PbSe QDs the anti-Stokes photoluminescence (ASPL) were observed when using both 1319 and 1532 nm excitation. The integrated intensity of the ASPL is linear with the excitation intensity, which indicates that the ASPL belongs to the phonon-assisted one-photon process. And the ASPL intensity as a function of excitation intensity shows a size dependence of the QDs.     

Matrix Manipulation of Directly-Synthesized PbS Quantum Dot Inks Enabled by Coordination Engineering

The direct-synthesis of conductive PbS quantum dot (QD) ink is facile, scalable, and low-cost, boosting the future commercialization of optoelectronics based on colloidal QDs. However, manipulating the QD matrix structures still is a challenge, which limits the corresponding QD solar cell performance. Here, for the first time a coordination-engineering strategy to finely adjust the matrix thickness around the QDs is presented, in which halogen salts are introduced into the reaction to convert the excessive insulating lead iodide into soluble iodoplumbate species. As a result, the obtained QD film exhibits shrunk insulating shells, leading to higher charge carrier transport and superior surface passivation compared to the control devices. A significantly improved power-conversion efficiency from 10.52% to 12.12% can be achieved after the matrix engineering. Therefore, the work shows high significance in promoting the practical application of directly synthesized PbS QD inks in large-area low-cost optoelectronic devices.     

Effect of annealing temperature on optical and electrical properties of lead sulfide thin films

Lead sulfide (PbS) thin films with 150 nm thickness were prepared onto ultra-clean quartz substrate by the RF-sputtering deposition method. Deposited thin films of PbS were annealed at different temperatures 100 °C, 150 °C, 200 °C, 250 °C and 300 °C. X-ray diffraction pattern of thin films revealed that thin films crystallized at 150 °C. Crystalline thin films had cubic phase and rock salt structure. The average crystallite size of crystalline thin films was 22 nm, 28 nm and 29 nm for 150 °C, 200 °C and 250 °C respectively. From 150 °C to 250 °C increase in annealing temperature leads to increase in crystallite arrangement. FESEM images of thin films revealed that crystallite arrangement improved by increasing annealing temperature up to 250 °C. Increase in DC electrical conductivity by increasing temperature confirmed the semiconductor nature of crystalline thin films. Increase in dark current by increasing annealing temperature showed the effect of crystallite arrangement on carrier transport. Photosensitivity decreased by increasing annealing temperature for crystalline thin films that it was explained at the base of thermal quenching of photoconductivity and adsorption of oxygen at the surface of thin films that leads to the formation of PbO at higher temperatures.     

Highly Efficient,Bright, and Stable Colloidal Quantum Dot Short‐Wave Infrared Light‐Emitting Diodes

Unbalanced charge injection is deleterious for the performance of colloidal quantum dot (CQD) light‐emitting diodes (LEDs) as it deteriorates the quantum efficiency, brightness, and operational lifetime. CQD LEDs emitting in the infrared have previously achieved high quantum efficiencies but only when driven to emit in the low‐radiance regime. At higher radiance levels, required for practical applications, the efficiency decreased dramatically in view of the notorious efficiency droop. Here, a novel methodology is reported to regulate charge supply in multinary bandgap CQD composites that facilitates improved charge balance. The current approach is based on engineering the energetic potential landscape at the supra‐nanocrystalline level that has allowed to report short‐wave infrared PbS CQD LEDs with record‐high external quantum efficiency in excess of 8%, most importantly, at a radiance level of ≈5 W sr^?1 m², an order of magnitude higher than prior reports. Furthermore, the balanced charge injection and Auger recombination reduction has led to unprecedentedly high operational stability with radiance half‐life of 26 068 h at a radiance of 1 W sr^?1 m^?2.     

Ultrasmall Pb:Ag2S Quantum Dots with Uniform Particle Size and Bright Tunable Fluorescence in the NIR‐II Window

Ag₂S quantum dots (QDs) are well‐known near‐infrared fluorophores and have attracted great interest in biomedical labeling and imaging in the past years. However, their photoluminescence efficiency is hard to compete with Cd‐, Pb‐based QDs. The high Ag⁺ mobility in Ag₂S crystal, which causes plenty of cation deficiency and crystal defects, may be responsible mainly for the low photoluminescence quantum yield (PLQY) of Ag₂S QDs. Herein, a cation‐doping strategy is presented via introducing a certain dosage of transition metal Pb²⁺ ions into Ag₂S nanocrystals to mitigate this intrinsic shortcoming. The Pb‐doped Ag₂S QDs (designated as Pb:Ag₂S QDs) present a renovated crystal structure and significantly enhanced optical performance. Moreover, by simply adjusting the levels of Pb doping in the doped nanocrystals, Pb:Ag₂S QDs with bright emission (PLQY up to 30.2%) from 975 to 1242 nm can be prepared without altering the ultrasmall particle size (≈2.7–2.8 nm). Evidently, this cation‐doping strategy facilitates both the renovation of crystal structure of Ag₂S QDs and modulation of their optical properties.     

Efficient Infrared Solar Cells Employing Quantum Dot Solids with Strong Inter-Dot Coupling and Efficient Passivation

Lead chalcogenide quantum dot (QD) infrared (IR) solar cells are promising devices for breaking through the theoretical efficiency limit of single-junction solar cells by harvesting the low-energy IR photons that cannot be utilized by common devices. However, the device performance of QD IR photovoltaic is limited by the restrictive relation between open-circuit voltages (V_OC) and short circuit current densities (J_SC), caused by the contradiction between surface passivation and electronic coupling of QD solids. Here, a strategy is developed to decouple this restriction via epitaxially coating a thin PbS shell over the PbSe QDs (PbSe/PbS QDs) combined with in situ halide passivation. The strong electronic coupling from the PbSe core gives rise to significant carrier delocalization, which guarantees effective carrier transport. Benefited from the protection of PbS shell and in situ halide passivation, excellent trap-state control of QDs is eventually achieved after the ligand exchange. By a fine control of the PbS shell thickness, outstanding IR J_SC of 6.38 mA cm⁻² and IR V_OC of 0.347 V are simultaneously achieved under the 1100 nm-filtered solar illumination, providing a new route to unfreeze the trade-off between V_OC and J_SC limited by the photoactive layer with a given bandgap.     

生物免疫传感器检测迟缓爱德华氏菌研究

迟缓爱德华氏菌(E.tarda)是最为严重的水产动物致病菌之一,准确、即时的检测手段是预防控制该菌传播的关键所在.通过量子点(QDs)标记E.tarda单克隆抗体(Ab),利用生物免疫传感器技术实现E.tarda的快速、特异性检测.结果显示,QDs-Ab的荧光通过加入氧化石墨烯(GO)产生淬灭,构建了捕获目标细菌的探针,GO最适淬灭浓度为60μg/L.细菌捕获探针中加入E.tarda后,能够检测到重新恢复强度的橙色荧光.针对E.tarda设计的生物免疫传感器的特异性,选取灿烂弧菌、溶藻胶弧菌、副溶血弧菌和嗜水气单胞菌作为对照,结果显示,对照组不能明显引起荧光强度的改变,而实验组却能显著提高荧光强度.本研究建立的基于荧光能量共振转移(FRET)的具有高灵敏度和特异性的生物传感器检测方法在细菌的早期诊断中有良好的应用潜质.     

Effect of Pb:S molar ratio in precursor solution on the properties of lead sulphide thin films by ultrasonic spray pyrolysis

In this work, PbS thin films were deposited onto glass substrate at 225 °C by spraying precursor solution prepared with different molar ratio of lead acetate and thiourea as a source of Pb²⁺ and S^2- respectively in order to investigate the effect of Pb:S molar ratio in the precursor solution on the physical properties of PbS thin films. Structural investigations carried out by X-ray diffractometer have shown that all films have fcc cubic structure and the average crystal size increased from 11 nm to 25 nm with the increasing the thiourea ratio in the precursor solution. In order to analyze the surface morphology of PbS thin films, AFM and SEM images were taken and elemental analysis of the films was performed by EDS. Optical transmittance and absorption spectra show that all deposited films have fairly low transmittance and high absorbance in the visible region. Additionally, it was determined that optical band gap of the deposited films were varied between 1.18 eV and 1.37 eV. As a consequence of electrical investigations, it was seen that all films have p-type conductivity and electrical resistivity decreased by increasing thiourea molar ratio in the precursor solution. All examinations have revealed that the molar ratio of lead acetate and thiourea has a significant effect on the physical properties of PbS thin films.     

Study of some physical properties of ultrasonically spray deposited silver doped lead sulphide thin films

In this study, undoped and Ag doped PbS thin films at different concentrations were deposited onto glass substrates at 225 °C by using ultrasonic spray pyrolysis technique, in order to investigate the effect of Ag doping on the physical properties of PbS thin films. Structural investigations revealed that all doped PbS:Ag thin films have cubic structure and Ag doping enhances crystalline level of PbS thin films. It was determined that average crystallite size of PbS:Ag thin films increased from 24 nm to 49 nm by increasing Ag doping concentration. Morphological studies showed that surfaces of the films become denser after Ag doping. Optical transmittance and absorption spectra revealed that all deposited thin films have low transmission and high absorbance within the visible region and band gap energy of the PbS:Ag thin films were determined to be in the range of 1.37 eV and 1.28 eV by means of optical method. Electrical conductivity type of PbS:Ag films was determined to be p-type and calculated electrical resistivity was found to be lowest for Ag-doped PbS thin films at 2%.