Direct synthesis of high-density lead sulfide nanowires on metal thin films towards efficient infrared light conversion

We report chemical-vapor-deposition (CVD) synthesis of high-density lead sulfide (PbS) nanowire arrays and nano pine trees directly on Ti thin films, and the fabrication of photovoltaic devices based upon the PbS nanowires. The as-grown nanowire arrays are largely vertically aligned to the substrates and are uniformly distributed over a relatively large area. Field effect transistors incorporating single PbS nanowires show p-type conduction and high mobilities. These catalytic metal thin films also serve as photocarrier collection electrodes and greatly facilitate device integration. For the first time, we have fabricated Schottky junction photovoltaic devices incorporating PbS nanowires, which demonstrate the capability of converting near-infrared light to electricity. The PbS nanowire devices are stable in air and their external quantum efficiency shows no significant decrease over a period of 3?months in air. We have also compared the photocurrent direction and quantum efficiencies of photovoltaic devices made with different metal electrodes, and the results are explained by band bending at the Schottky junction. Our research shows that PbS nanowires are promising building blocks for collecting near-infrared solar energy.     

PbS量子点能级结构的尺寸和配体依赖性及其对异质结电池性能的影响

通过电化学循环伏安测试和吸收光谱测试, 确定了有机配体(油酸)和原子配体(四正丁基碘化铵, TBAI)钝化的不同粒径(2.6~4.5 nm)PbS量子点的导带和价带能级, 并研究了量子点尺寸对PbS/TiO₂异质结电池(空气气氛中制备)性能的影响。结果表明：PbS量子点的能级结构受其粒径大小和表面配体特性的影响。当PbS量子点尺寸从2.6 nm增加至4.5 nm时, 油酸包覆PbS量子点的导带底从-3.67 eV减小到-4.0 eV, 价带顶从-5.19 eV增加到-4.97 eV; 而对于TBAI配体置换的PbS量子点, 其导带底和价带顶则分别从-4.15 eV和-5.61 eV变化至-4.51 eV和-5.46 eV。粒径为3.9 nm的PbS量子点所制备的电池性能最优, 其能量转化效率达到2.32%, 这可归因于其适宜的禁带宽度、结晶质量和良好的PbS/TiO₂界面能级匹配度。     

Scanning tunneling spectroscopy of lead sulfide quantum wells fabricated by atomic layer deposition

We report the use of scanning tunneling spectroscopy (STS) to investigate one-dimensional quantum confinement effects in lead sulfide (PbS) thin films. Specifically, quantum confinement effects on the band gap of PbS quantum wells were explored by controlling the PbS film thickness and potential barrier height. PbS quantum well structures with a thickness range of 1-20?nm were fabricated by atomic layer deposition (ALD). Two barrier materials were selected based on barrier height: aluminum oxide as a high barrier material and zinc oxide as a low barrier material. Band gap measurements were carried out by STS, and an effective mass theory was developed to compare the experimental results. Our results show that the band gap of PbS thin films increased as the film thickness decreased, and the barrier height increased from 0.45 to 2.19?eV.     

Scanned probe imaging of quantum dots inside InAs nanowires

We show how a scanning probe microscope (SPM) can be used to image electron flow through InAs nanowires, elucidating the physics of nanowire devices on a local scale. A charged SPM tip is used as a movable gate. Images of nanowire conductance versus tip position spatially map the conductance of InAs nanowires at liquid-He temperatures. Plots of conductance versus backgate voltage without the tip present show complex patterns of Coulomb-blockade peaks. Images of nanowire conductance identify their source as multiple quantum dots formed by disorder along the nanowire--each dot is surrounded by a series of concentric rings corresponding to Coulomb blockade peaks. An SPM image locates the dots and provides information about their size. In this way, SPM images can be used to understand the features that control transport through nanowires. The nanowires were grown from metal catalyst particles and have diameters approximately 80 nm and lengths 2-3 microm.     

Correlation between structural and optical properties of 30 nm and 60 nm lead sulfide nanowires

PbS nanowires with 30 nm and 60 nm diameter fabricated under the same condition of electrochemical deposition with sulfuric and oxalic anodic alumina membranes (AAM), respectively, have been successfully prepared in order to study their optical properties in relation to their size. Scanning electron microscopy indicates that the 60 nm PbS nanowire arrays have the same shape with the 30 nm. X-ray diffraction result shows that 60 nm PbS nanowires are crystalline and have a highly (200) preferential orientation like 30 nm ones. UV spectrum considers the nanowire size decrease as the absorption peak shifts to the blue. The quantum confinement effects compared between 30 nm and 60 nm PbS nanowire arrays were observed by the measurements of ultraviolet-visible absorption spectroscopy (UV-vis).     

Optically bright quantum dots in single Nanowires

We fabricate and demonstrate optically active quantum dots embedded in single nanowires. Observation of photon antibunching proves the zero dimensionality of these heterostructures that can be epitaxially grown on various substrates, including silicon. We show that the nanowire dots are intense single photon sources, typically an order of magnitude brighter than self-assembled quantum dots. Due to control over their composition, size, and position, nanowire dots are ideal building blocks for fully controlled quantum dot molecules.     

Quantum Dot-Siloxane Anchoring on Colloidal Quantum Dot Film for Flexible Photovoltaic Cell

Lead sulfide (PbS) colloidal quantum dots (CQDs) are promising materials for next-generation flexible solar cells because of near-infrared absorption, facile bandgap tunability, and superior air stability. However, CQD devices still lack enough flexibility to be applied to wearable devices owing to the poor mechanical properties of CQD films. In this study, a facile approach is proposed to improve the mechanical stability of CQDs solar cells without compromising the high power conversion efficiency (PCE) of the devices. (3-aminopropyl)triethoxysilane (APTS) is introduced on CQD films to strengthen the dot-to-dot bonding via QD-siloxane anchoring, and as a result, crack pattern analysis reveals that the treated devices become robust to mechanical stress. The device maintains 88% of the initial PCE under 12 000 cycles at a bending radius of 8.3 mm. In addition, APTS forms a dipole layer on CQD films, which improves the open circuit voltage (V_OC) of the device, achieving a PCE of 11.04%, one of the highest PCEs in flexible PbS CQD solar cells.     

Quantum dot size dependent J-V characteristics in heterojunction ZnO/PbS quantum dot solar cells

The current-voltage (J-V) characteristics of ZnO/PbS quantum dot (QD) solar cells show a QD size-dependent behavior resulting from a Schottky junction that forms at the back metal electrode opposing the desirable diode formed between the ZnO and PbS QD layers. We study a QD size-dependent roll-over effect that refers to the saturation of photocurrent in forward bias and crossover effect which occurs when the light and dark J-V curves intersect. We model the J-V characteristics with a main diode formed between the n-type ZnO nanocrystal (NC) layer and p-type PbS QD layer in series with a leaky Schottky-diode formed between PbS QD layer and metal contact. We show how the characteristics of the two diodes depend on QD size, metal work function, and PbS QD layer thickness, and we discuss how the presence of the back diode complicates finding an optimal layer thickness. Finally, we present Kelvin probe measurements to determine the Fermi level of the QD layers and discuss band alignment, Fermi-level pinning, and the V(oc) within these devices.     

Bilayer PbS Quantum Dots for High‐Performance Photodetectors

Due to their wide tunable bandgaps, high absorption coefficients, easy solution processabilities, and high stabilities in air, lead sulfide (PbS) quantum dots (QDs) are increasingly regarded as promising material candidates for next‐generation light, low‐cost, and flexible photodetectors. Current single‐layer PbS‐QD photodetectors suffer from shortcomings of large dark currents, low on–off ratios, and slow light responses. Integration with metal nanoparticles, organics, and high‐conducting graphene/nanotube to form hybrid PbS‐QD devices are proved capable of enhancing photoresponsivity; but these approaches always bring in other problems that can severely hamper the improvement of the overall device performance. To overcome the hurdles current single‐layer and hybrid PbS‐QD photodetectors face, here a bilayer QD‐only device is designed, which can be integrated on flexible polyimide substrate and significantly outperforms the conventional single‐layer devices in response speed, detectivity, linear dynamic range, and signal‐to‐noise ratio, along with comparable responsivity. The results which are obtained here should be of great values in studying and designing advanced QD‐based photodetectors for applications in future flexible optoelectronics.     

Millisecond‐Timescale Monitoring of PbS Nanoparticle Nucleation and Growth Using Droplet‐Based Microfluidics

The early‐time kinetics (<1 s) of lead sulfide (PbS) quantum dot formation are probed using a novel droplet‐based microfluidic platform, which allows for high‐throughput and real‐time optical analysis of the reactive process with millisecond time resolution. The reaction platform enables the concurrent investigation of the emission characteristics of PbS quantum dots and a real‐time estimation of their size and concentration during nucleation and growth. These investigations reveal a two‐stage mechanism for PbS nanoparticle formation. The first stage corresponds to the fast conversion of precursor species to PbS crystals, followed by the growth of the formed particles. The growth kinetics of the PbS nanoparticles follow the Lifshitz–Slyozov–Wagner model for Ostwald ripening, allowing direct estimation of the rate constants for the process. In addition, the extraction of absorption spectra of ultrasmall quantum dots is demonstrated for first time in an online manner. The droplet‐based microfluidic platform integrated with online spectroscopic analysis provides a new tool for the quantitative extraction of high temperature kinetics for systems with rapid nucleation and growth stages.     

Controlling electron overflow in phosphor-free InGaN/GaN nanowire white light-emitting diodes

We have investigated for the first time the impact of electron overflow on the performance of nanowire light-emitting diodes (LEDs) operating in the entire visible spectral range, wherein intrinsic white light emission is achieved from self-organized InGaN quantum dots embedded in defect-free GaN nanowires on a single chip. Through detailed temperature-dependent electroluminescence and simulation studies, it is revealed that electron leakage out of the device active region is primarily responsible for efficiency degradation in such nanowire devices, which in conjunction with the presence of nonradiative surface recombination largely determines the unique emission characteristics of nanowire light-emitting diodes. We have further demonstrated that electron overflow in nanowire LEDs can be effectively prevented with the incorporation of a p-doped AlGaN electron blocking layer, leading to the achievement of phosphor-free white light-emitting diodes that can exhibit for the first time virtually zero efficiency droop for injection currents up to ~2200 A/cm(2). This study also provides unambiguous evidence that Auger recombination is not the primary mechanism responsible for efficiency droop in GaN-based nanowire light-emitting diodes.     

量子点材料应用于发光二极管的研究进展

量子点材料因具有独特的光学特性而被广泛应用于发光领域,用其作发光层可制成量子点发光二极管。与有机电致发光二极管相比,量子点发光二极管具有发光光谱窄、色域广、稳定性好、寿命长、制作成本低等优势。本文介绍了量子点发光器件在国内外的热点研究方向及取得的成果,并对其发展前景进行展望。     

Bright infrared quantum-dot light-emitting diodes through inter-dot spacing control

Infrared light-emitting diodes are currently fabricated from direct-gap semiconductors using epitaxy, which makes them expensive and difficult to integrate with other materials. Light-emitting diodes based on colloidal semiconductor quantum dots, on the other hand, can be solution-processed at low cost, and can be directly integrated with silicon. However, so far, exciton dissociation and recombination have not been well controlled in these devices, and this has limited their performance. Here, by tuning the distance between adjacent PbS quantum dots, we fabricate thin-film quantum-dot light-emitting diodes that operate at infrared wavelengths with radiances (6.4?W?sr(-1)?m(-2)) eight times higher and external quantum efficiencies (2.0%) two times higher than the highest values previously reported. The distance between adjacent dots is tuned over a range of 1.3?nm by varying the lengths of the linker molecules from three to eight CH(2) groups, which allows us to achieve the optimum balance between charge injection and radiative exciton recombination. The electroluminescent powers of the best devices are comparable to those produced by commercial InGaAsP light-emitting diodes. By varying the size of the quantum dots, we can tune the emission wavelengths between 800 and 1,850?nm.     

Synthesis and optical properties of ordered 30 nm PbS nanowire arrays fabricated into sulfuric anodic alumina membrane

Crystalline PbS nanowire arrays have been successfully fabricated by AC applied DC electrochemical deposition from aqueous solutions of dimethylsulfoxide DMSO solution containing lead chloride and elemental sulfur into sulfuric anodic alumina membranes (AAM). These nanowires have uniform diameters of approximately 30 nm, and their lengths are up to tens of micrometers. Scanning electron microscopy indicates that the ordered PbS nanowire arrays are completely embedded. The results of X-ray diffraction show that the as-synthesized nanowires are crystalline with highly preferential orientation. Energy dispersive spectrometer analysis shows that the composition ratio is very close to 1:1. Finally PL and UV–VIS illustrate the quantum confinement effects of PbS nanowire arrays.     

Investigations on the morphology,optical and photoresponse properties of PbS/CdS binary colloidal quantum dot thin film

Binary thin film exhibits not only the quantum features of the individual building blocks but also novel collective properties through coupling of colloidal quantum dot components. In this paper, lead sulfide (PbS) and cadmium sulfide (CdS) colloidal quantum dots (CQDs) were synthesized by using oleate and oleylamine as ligand. The as-synthesized PbS and CdS CQDs were monodispersity and well passivation. The average diameter of as-synthesized PbS and CdS CQDs were about 3 nm and 6 nm, respectively. By blending PbS with CdS CQDs and utilizing ethanedithiol for ligand passivation, the responsivity and detectivity of PbS CQDs thin film was enhanced with the weight ratio of CdS CQDs increased, the optimum responsivity and detectivity were 21.9 mA/W and 2.1 × 10¹⁰ Jones, respectively. The desirable properties of binary colloidal quantum dot thin films have important applications in future electronic and optoelectronic devices.     

Interface‐Engineered Nickel Cobaltite Nanowires through NiO Atomic Layer Deposition and Nitrogen Plasma for High‐Energy,Long‐Cycle‐Life Foldable All‐Solid‐State Supercapacitors

The large‐scale application of supercapacitors (SCs) for portable electronics is restricted by low energy density and cycling stability. To alleviate the limitations, a unique interface engineering strategy is suggested through atomic layer deposition (ALD) and nitrogen plasma. First, commercial carbon cloth (CC) is treated with nitrogen plasma and later inorganic NiCo₂O₄ (NCO)/NiO core–shell nanowire arrays are deposited on nitrogen plasma–treated CC (NCC) to fabricate the ultrahigh stable SC. An ultrathin layer of NiO deposited on the NCO nanowire arrays via conformal ALD plays a vital role in stabilizing the NCO nanowires for thousands of electrochemical cycles. The optimized NCC/NCO/NiO core–shell electrode exhibits a high specific capacitance of 2439 F g^?1 with a remarkable cycling stability (94.2% over 20 000 cycles). Benefiting from these integrated merits, the foldable solid‐state SCs are fabricated with excellent NCC/NCO/NiO core–shell nanowire array electrodes. The fabricated SC device delivers a high energy density of 72.32 Wh kg^?1 at a specific capacitance of 578 F g^?1, with ultrasmall capacitance decline rate of 0.0003% per cycle over 10 000 charge–discharge cycles. Overall, this strategy offers a new avenue for developing a new‐generation high‐energy, ultrahigh stable supercapacitor for real‐life applications.     

Quantum dot/carbon nanotube/silicon double heterojunctions for multi-band room temperature infrared detection

We report on the observation of room temperature multi-band photocurrent response from a novel structure formed by interior loading of PbS quantum dots into carbon nanotubes grown on silicon. In addition to a mid infrared photoresponse band at ～ 0.22 eV due to the carbon nanotubes and one band at 1.1 eV corresponding to silicon, two bands in the mid/near infrared at 0.63 and 0.82 eV, corresponding to the first and second exciton bands of the PbS quantum dots, are observed in photocurrents measured at room temperature, in uncooled operation. We have also observed a red shift of the 0.63 and 0.82 eV bands with cooling that reflects a behavior typical for PbS and supports the hypothesis that these photoresponse bands are due to absorption in the PbS quantum dots.     

Quantum dot-based local field imaging reveals plasmon-based interferometric logic in silver nanowire networks

We show that the local electric field distribution of propagating plasmons along silver nanowires can be imaged by coating the nanowires with a layer of quantum dots, held off the surface of the nanowire by a nanoscale dielectric spacer layer. In simple networks of silver nanowires with two optical inputs, control of the optical polarization and phase of the input fields directs the guided waves to a specific nanowire output. The QD-luminescent images of these structures reveal that a complete family of phase-dependent, interferometric logic functions can be performed on these simple networks. These results show the potential for plasmonic waveguides to support compact interferometric logic operations.     

Near-infrared responsive PbS-sensitized photovoltaic photodetectors fabricated by the spin-assisted successive ionic layer adsorption and reaction method

A PbS-sensitized photovoltaic photodetector responsive to near-infrared (NIR) light was fabricated by depositing monolayered PbS nanoparticles on a mesoporous TiO(2) (mp-TiO(2)) film via the spin-assisted successive ionic layer adsorption and reaction (SILAR) method. By adjusting the size and morphology of the PbS nanoparticles through repeated spin-assisted SILAR cycles, the PbS-sensitized photovoltaic photodetector achieved an external quantum efficiency of 9.3% at 1140 nm wavelength and could process signals up to 1 kHz.     

Parallel core-shell metal-dielectric-semiconductor germanium nanowires for high-current surround-gate field-effect transistors

Core-shell germanium nanowires (GeNW) are formed with a single-crystalline Ge core and concentric shells of nitride and silicon passivation layer by chemical vapor deposition (CVD), an Al2O3 gate dielectric layer by atomic layer deposition (ALD), and an Al metal surround-gate (SG) shell by isotropic magnetron sputter deposition. Surround-gate nanowire field-effect transistors (FETs) are then constructed using a novel self-aligned fabrication approach. Individual SG GeNW FETs show improved switching over GeNW FETs with planar gate stacks owing to improved electrostatics. FET devices comprised of multiple quasi-aligned SG GeNWs in parallel are also constructed. Collectively, tens of SG GeNWs afford on-currents exceeding 0.1 mA at low source-drain bias voltages. The self-aligned surround-gate scheme can be generalized to various semiconductor nanowire materials.