Synthesis of Fe alloyed PbS thin films and investigation of their photovoltaic properties

Lead sulfide (PbS) and iron (Fe)-alloyed PbS thin films with different Fe concentrations were synthesized by chemical bath deposition (CBD) technique, which is suitable for cost on glass substrates at room temperature. The structural, elemental and optical properties of the synthesized thin films were characterized by X-ray diffraction (XRD), energy dispersive X-ray (EDX) and optical absorption measurements, respectively. It was observed that Fe dopant alters crystal size and energy band gap of PbS although it does not change the structure of PbS. PbS and Fe-alloyed PbS thin films with different Fe concentrations were grown on zinc tin oxide (Zn₂SnO₄) substrates coated on fluorine-alloyed tin oxide conductive glasses to investigate their photovoltaic properties. Incident photon-to-current efficiency (IPCE) and current density (J)–voltage (V) measurements were carried out to determine IPCE (%) and power conversion efficiency (η%) values of thin films. As a result, it was observed that as the concentration of Fe dopant is increased in Fe-alloyed PbS thin films, there is an increase in η%.     

Surface synthesis of PbS nanoparticles on silica spheres by a sonochemical approach

A simple sonochemical approach for the preparation of PbS nanoparticles homogeneously coated on sub-micrometer silica spheres has been described. The transmission electron microscopy and scanning electron microscopy images show that the PbS nanoparticles with size of 30 nm were coated on the silica spheres, without any free nanoparticles. X-ray diffraction reveals that the PbS nanoparticles are of cubic rock-salt structure. Moreover, by dissolving the silica cores with a diluted hydrofluoric acid solution, stable PbS hollow structures were obtained. It is considered that the sonochemical process in which triethanolamine acted as complex agent played an important role for the homogenouse coating of PbS nanoparticles on silica spheres.     

Growth of PbS and CdS thin films by low-pressure chemical vapour deposition using dithiocarbamates

Thin films of cadmium and lead sulphides grown by chemical vapour deposition (CVD) and remote plasma enhanced chemical vapour deposition (RPECVD) using dithiocarbamates as precursors were prepared on fused silica, sapphire, (111)Si and (111)InP substrates. These films were deposited in the temperature range 473–873 K. It was established that the activation energy of the CVD process is 191.5±1.5 kJ mol⁻¹. The structure of polycrystalline films was halenide for PbS and wurtzite for CdS. It was also found that r.f.-plasma activation of the gas phase decreases remarkably the growth temperature and orders the film structure. RPECVD sulphide films had a high degree of preferred orientation.     

PbS量子点/ZnO纳米片复合膜的制备及其光电化学性能

通过两步法合成PbS量子点(QDs)修饰ZnO纳米片复合膜. 首先利用电化学法在掺氟的SnO₂导电玻璃(FTO)上生长ZnO纳米片, 然后在ZnO纳米片上通过逐次化学浴法沉积PbS量子点形成PbS/ZnO复合膜. 利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)详细表征了样品的表面形貌和晶体结构, 并研究了PbS/ZnO复合膜作为量子点敏化太阳能电池光阳极的紫外-可见吸收谱、光电化学性能和表面光电压谱. 对比ZnO纳米片经PbS量子点修饰前后, 发现PbS量子点修饰后光阳极的光吸收和光伏响应均从紫外区拓宽到了可见光区, 同时光电化学性能有了显著提高, 短路电流密度从敏化前的0.1 mA/cm²增加到0.7 mA/cm², 效率由0.04%增加到0.57%. 与单一ZnO纳米片相比, PbS/ZnO复合膜的表面光伏响应强度明显增强, 说明PbS与ZnO之间形成了有利于光生电荷分离的异质结, 从而导致了PbS/ZnO复合膜光电性能的增加.     

Growth of PbS nanopyramidal particulate films for potential applications in quantum-dot photovoltaics and nanoantennas

We report a simple interfacial process called the liquid-liquid interface reaction technique (LLIRT) that leads to the formation of nanosized PbS particulate films with hitherto unreported pyramidal morphology. The resultant PbS films were characterized by transmission electron microscopy (TEM) with selected area electron diffraction (SAED), X-ray diffractometery (XRD), atomic force microscopy (AFM), near field scanning optical microscopy (NSOM) and UV-vis spectroscopy. The pyramidal morphology is speculated to originate from the preferred orientation of the 2 2 0 plane of cubic PbS. Our nanopyramidal PbS particulate films display remarkably sharp excitonic peak centered around 656 nm that accounts for a band gap of 1.8 eV suggesting, in turn, their potential application in QD photovoltaics. Interestingly, the feasibility of such nanopyramids to potentially act as nanoantennas (as revealed by the NSOM) is also suggested.     

Influence of Al doping on the structural,morphological and opto-electrical properties of spray deposited lead sulfide thin films

This paper reports the synthesis of Al-doped PbS (PbS:Al) thin films by spray pyrolysis technique on glass substrates. Al doping concentration is varied as 0, 2, 4, 6 and 8 at.% in undoped PbS. Undoped and doped films exhibit cubic crystal structure with a (2 0 0) preferential orientation. The 2θ value of the doped films shifts towards higher Bragg angles confirming a contraction in their unit cell volume. The crystallite size values determined using the Scherrer formula decreased from 27.88 to 25.79 nm with increase in Al doping concentration. EDX spectra confirmed the presence of Al in the doped films. Increased transparency and blue shift in the optical band gap is observed with Al doping. The resistivity range of all the films were found to be in the order of 10² Ω-cm. Increased transparency, widened band gap and decreased resistivity observed make PbS:Al films suitable for tandem solar cells which uses multilayered pn junctions.     

The influence of interlayer molecules in luminescence of self-assembled bilayer PbS quantum dot films

We synthesized organic solvent-soluble and water-soluble PbS quantum dots (QDs) with different sizes. The organic solvent-soluble PbS QDs dispersed in tetrachloroethylene were used to prepare bilayers structures of QDs bound by dithiol linkers on GaAs. The water-soluble PbS QDs were used to prepare bilayer structures of QDs on quartz based on alternating adsorption of polyelectrolyte. For bilayer films on GaAs, it was found that the stacking sequence of QDs affects the quantum yield and emission wavelength of the larger QDs. However, for bilayer films with different stacking sequences on quartz, the larger QDs show similar PL intensities and emission wavelength independent of the sequence. The probable mechanism for this difference observed is discussed in terms of charge transfer between QDs.     

Preparation of nanocrystalline PbS thin films and effect of Sn doping and annealing on their structural and optical properties

Nanocrystalline PbS and Sn doped PbS thin films were successfully deposited on suitably cleaned glass substrate at constant room temperature, using the chemical bath deposition technique. Before, adding Sn doping content, the pure PbS thin films were deposited at room temperature for several dipping times to optimize the deposition time. After deposition, the films were also annealed at 400 °C for 1 h in air. The crystal structures of the films were determined by X-ray diffraction studies. The films were adherent to the substrate and well crystallized according to cubic structure with the preferential orientation (2 0 0). The crystallite size of the pure PbS thin films at optimized deposition time 30 min was found to be 40.4 nm, which increased with Sn content in pure PbS thin film. The surface roughness was measured by AFM studies. The band gaps of the films were determined by transmission spectra. Experiments showed that the growth parameters, doping and annealing, influenced the crystal structure, and optical properties of the films.     

Hyperbranched PbS and PbSe nanowires and the effect of hydrogen gas on their synthesis

We report a chemical vapor deposition (CVD) synthesis of hyperbranched single-crystal nanowires of both PbS and PbSe using PbCl2 and S/Se as precursors under hydrogen flow. Multiple generations of nanowires grow perpendicularly from the previous generation of nanowires in an epitaxial fashion to produce dense clusters of a complex nanowire network structure. The flow rate and duration of the hydrogen co-flow in the argon carrier gas during the CVD reactions are found to have a significant effect on the morphology of the PbS/PbSe grown, from hyperbranched nanowires to micrometer-sized cubes. No intentional catalyst was employed for the nanowire synthesis, but it is suggested that elemental lead that has been reduced from the vapor by the hydrogen might serve as a vapor-liquid-solid (VLS) catalyst for the anisotropic growth of PbS/PbSe. The nanowires were also investigated with Raman spectroscopy. These PbS and PbSe nanostructures can have applications in photovoltaics because multiple exciton generation has been demonstrated in nanocrystals of both materials.     

Preparation and room temperature photoluminescence characterization of PbS/Si(100) thin films

PbS nanoparticles and smooth nanocrystalline thin films (nc-PbS) were prepared by chemical precipitation from aqueous solutions. Polyethylene oxide and isopropyl alcohol were used as additives in the aqueous solution, which results in the enhancement of the blue luminescence of PbS thin films. The introduction of isopropyl reduced the grain size and increases the optical gap of the PbS particles. The size of PbS particles was estimated to be ~ 3.5 nm. The broad emission bands exhibited were composed by a multiple overlapping peaks. The photoluminescence (PL) intensity was significantly influenced by the excitation wavelength. Indeed, intense blue luminescence was obtained under 230 nm compared to that obtained under 325 nm excitation wavelength. The PL emission from PbS nanoparticles was less intense than the luminescence of PbS thin films. The high PL intensity of the thin films was attributed to the lower density of defects introduced in the thin films during the chemical bath deposition growth process compared the defects density of PbS powder.     

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.     

Structural,optical and electrical properties of PbS and PbSe quantum dot thin films

PbS and PbSe were prepared by hot injection method. The powders were used for preparing the corresponding films by using thermal evaporation technique. The structural, optical and electrical properties of PbS and PbSe thin films were investigated. The structural properties of PbS and PbSe were investigated by X-ray diffraction, transmission electron microscopy and energy dispersive X-ray techniques (EDX). PbS and PbSe films were found to have cubic rock salt structure. The particles size ranged from 1.32 to 2.26 nm for PbS and 1.28–2.48 nm for PbSe. EDX results showed that PbS films have rich sulphur content, while PbSe films have rich lead content. The optical constants (absorption coefficient and the refractive index) of the films were determined in the wavelength range 200–2500 nm. The optical energy band gap of PbS and PbSe films was determined as 3.25 and 2.20 eV, respectively. The refractive index, the optical dielectric constant and the ratio of charge carriers concentration to its effective mass were determined. The electrical resistivity, charge carriers concentration and carriers mobility of PbS at room temperature were determined as 0.55 Ω cm, 1.7 × 10¹⁶ cm^?3 and 656 cm² V^?1 s^?1, respectively, and for PbSe films they were determined as 0.4 Ω cm, 9 × 10¹⁵ cm^?3 and 1735 cm² V^?1 s^?1, respectively. These electrical parameters were investigated as a function of temperature.     

Structural,optical and electrical properties of Ag doped PbS thin films: role of Ag concentration

The present work reports on the chemical synthesizes of (0–8 at.%) silver (Ag)-doped PbS thin films with tunable opto-electrical properties. From the X-ray diffraction analyses, it was understood that the preferred growth orientation of Ag:PbS films was dependent on the Ag doping concentration. The variation in the Ag:PbS films orientation was reflected in the film morphology as observed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). SEM studies revealed that the variation in Ag concentration lead to different grain shapes for different grain orientations. The AFM study showed that the RMS roughness of the undoped PbS film has been reduced considerably due to silver doping. From the optical studies, a widening in the optical band gap was revealed after Ag-doping due to the quantum confinement effect. It was obtained that 4 at.% Ag-doped PbS thin films display an optimum band gap value of 1.45 eV. As for electrical characterization result, the resistivity reduces and the carrier density improved with 4 at.% Ag concentration. Based on all the data, it was concluded that the 4 at.% Ag-doped PbS thin film showed the best morphological, optical and electrical behavior, which recommend it as an active layer for solar cell devices.     

Photoconductivity, photovoltaic effect and photoluminescence in chemically deposited films of (Cd0.95–Pb0.05)S:CdCl2,Gd

Results of XRD, optical absorption spectra, photoconductivity, photovoltaic effect and photoluminescence are reported for (Cd_0.95–Pb_0.05)S:CdCl₂,Gd films prepared by chemical deposition technique at 60 °C and room temperature (RT). The XRD studies show prominent diffraction lines of CdS and PbS. Optical absorption spectra show direct bandgap nature with decreasing value due to addition of PbS. The saturated photocurrent (I_pc) to dark current (I_dc) ratios 10⁷ are found in films prepared at 60 °C and 10⁴ in films prepared at RT. Photoluminescence is found to be brighter in films prepared at RT. Photovoltaic efficiency 5% has been observed in such films.     

基于微接触印刷法的PbS微图案的制备

以聚二甲基硅氧(PDMS)弹性体为印模,十八烷基三氯硅烷(OTS)为"墨水",采用微接触印刷法分别在平整的玻璃基片表面和弯曲的玻璃棒表面进行印刷操作,将印刷后的基片浸入到PbS化学浴液中沉积得到微图案化的PbS薄膜.交叉印刷和光学显微观察结果表明,所沉积的PbS微图案边界清晰规整,并且PbS会选择性沉积在基片表面没有被OTS覆盖的区域.     

Cubic PbS thin films on TCO glass substrate by galvanic technique

We report an electrochemical deposition of PbS thin films on SnO₂:F coated Transparent Conducting Oxide (TCO) glass substrates from a solution of EDTA, Pb(OAc)₂ and Na₂S₂O₃. A Pb strip acted as a sacrificial anode, while the TCO glass was the cathode. No external bias was applied. The deposition of PbS thin films was pH sensitive and a pH around 3 was found to be optimum for film deposition. The deposition was carried out at 80 °C, with stirring of the solution. X-ray diffraction studies revealed that the PbS films were of cubic phase. Scanning electron microscope image analysis showed a highly compact surface morphology. IR spectrum yielded an energy band gap around 0.4 eV. A.C. current–voltage (I–V) measurements were carried out using gold as one of the contacts. It was found that the PbS film formed an ohmic contact when the other electrode was also gold, however, a Schottky junction resulted, when the second contact was TCO.     

Comparative studies on structural, optoelectronic and electrical properties of SILAR grown PbS thin films from acidic, neutral and alkaline cationic reaction bath

Thin films of Lead sulphide (PbS) were grown on soda lime glass substrate by Successive Ionic Layer Adsorption and Reaction method from acidic, neutral and alkaline cationic precursor reaction bath by keeping the pH of the anionic precursor invariant. The structural and morphological aspects of the as prepared samples were investigated using XRD and SEM results. The as-prepared samples were polycrystalline with nanometer sized grains and identified as galena type cubic structure. The values of average crystallite size were found to be in the range 22–30?nm. The SEM micrographs show variations in morphology. Optical studies revealed the existence of both direct and indirect band gap with values in the range of 1.65–1.98 and 0.61–0.90?eV respectively. The room temperature conductivity of the PbS thin films were in the range 1.19?×?10^?8–5.92?×?10^?8?Ω?cm^?1. The optical band gap energy has inverse relation with grain size and electrical conductivity is closely related to structural parameters like grain size, crystallinity and micro strain. The estimated lattice parameter, grain size, optical band gaps, solid state and electrical properties were correlated with pH of the cationic solution. In this work, we establish that the pH of the cationic precursor media has colossal effect on the structural, morphological, optoelectronic, solid-state and electrical properties of PbS thin films.     

Structural analysis of chemically deposited nanocrystalline PbS films

Nanocrystalline PbS films are deposited on glass substrates by chemical bath deposition technique at room temperature. The structural parameters of PbS nanoparticles are studied by X-ray line profile analysis using Williamson-Hall and modified Williamson-Hall plot. The values of average crystallite sizes are found to vary from 12 to 18 nm having very high dislocation density of the order of 10¹⁷ m⁻².     

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.     

Preparation of lead iodide films by iodination of chemically deposited lead sulphide films

A method of preparation of PbI₂ films by iodination of chemically deposited PbS films is described. The X-ray characterization of these films show that they are poly-crystalline in nature and the crystallites are preferentially oriented with c-axis perpendicular to the plane of the substrates. The analysis of the diffuse reflectance measurements performed on material scraped off the substrates yielded a forbidden energy gap of 2.34 eV in conformation with the results of pure PbI₂ powder. The transmittance spectra of these films, in the wavelength range 400 to 600 nm, revealed a characteristic strong absorption edge at about 510 nm and a hump at about 490 nm. On the basis of the changes in conductance of PbS film during iodine treatment a mechanism of iodination has been proposed.