Size dependent photodegradation of CdS particles deposited onto TiO2 mesoporous films by SILAR method

The properties of CdS nanoparticles incorporated onto mesoporous TiO2 films by a successive ionic layer adsorption and reaction (SILAR) method were investigated by Raman spectroscopy, UV-visible spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). High resolution TEM indicated that the synthesized CdS particles were hexagonal phase and the particle sizes were less than 5 nm when SILAR cycles were fewer than 9. Quantum size effect was found with the CdS sensitized TiO2 films prepared with up to 9 SILAR cycles. The band gap of CdS nanoparticles decreased from 2.65 eV to 2.37 eV with the increase of the SILAR cycles from 1 to 11. The investigation of the stability of the CdS/TiO2 films in air under illumination (440.6 µW/cm2) showed that the photodegradation rate was up to 85% per day for the sample prepared with 3 SILAR cycles. XPS analysis indicated that the photodegradation was due to the oxidation of CdS, leading to the transformation from sulphide to sulphate (CdSO4). Furthermore, the degradation rate was strongly dependent upon the particle size of CdS. Smaller particles showed faster degradation rate. The size-dependent photo-induced oxidization was rationalized with the variation of size-dependent distribution of surface atoms of CdS particles. Molecular Dynamics (MD) simulation has indicated that the surface sulphide anion of a large CdS particle such as CdS made with 11 cycles (CdS11, particle size = 5.6 nm) accounts for 9.6% of the material whereas this value is increased to 19.2% for (CdS3) based smaller particles (particle size: 2.7 nm). Nevertheless, CdS nanoparticles coated with ZnS material showed a significantly enhanced stability under illumination in air. A nearly 100% protection of CdS from photon induced oxidation with a ZnS coating layer prepared using four SILAR cycles, suggesting the formation of a nearly complete coating layer on the CdS nanoparticles.

Development of SnS quantum dot solar cells by SILAR method

SnS quantum dot solar cell is fabricated by Successive Ionic Layer Adsorption and Reaction (SILAR) method. SnS layer is optimized by different SILAR cycles of deposition. The particle size increased with the increase in number of SILAR cycles. Cu2S coated FTO is used as counter electrode against the conventional Platinum electrode. On comparison with a cell having a counter electrodeelectrolyte combination of Platinum-Iodine, Cu2S-polysulfide combination is found to improve both the short circuit current and fill factor of the solar cell. A maximum efficiency of 0.54% is obtained with an open circuit voltage of 311 mV and short circuit current density of 4.86 mA/cm. (C) 2014 Elsevier Ltd. All rights reserved.

改进的SILAR法制备ZnO薄膜及其表征

A modified solution method, successive ionic layer adsorption and reaction(SILAR), was applied to prepare transparent zinc oxide(ZnO) film on glass substrate at (125±5) ℃ in mixed ion precursor solution. The surface morphology and crystallizations of films were analyzed by field emission scanning microscopy(FESEM) and X-ray diffraction(XRD), respectively. The optical properties of the films were studied by ultraviolet visible(UV-Vis)spectroscopy. The results show that the obtained samples are polycrystallin...中文文摘：采用一种改进的液相成膜技术——连续离子层吸附与反应(SILAR)法,用锌氨络离子[Zn(NH3)4]2+溶液作为独立的前驱体溶液,以载玻片为衬底,在(125±5)℃的温度下沉积出致密、透明的ZnO薄膜。分别用冷场发射型扫描电镜(FESEM)和X射线衍射(XRD)分析了薄膜样品的表面形貌和结晶状态,用紫外-可见分光光度计(UV-Vis spectroscopy)研究了薄膜样品的发光性能。结果表明:获得样品为六角纤锌矿结构的多晶薄膜材料沿[002]方向择优生长;样品表面均匀、致密,厚度约为550nm;在可见光波段具有高的透射率(>80%)。

改进的SILAR法制备ZnO薄膜及其表征

采用一种改进的液相成膜技术——连续离子层吸附与反应(SILAR)法,用锌氨络离子[Zn(NH3)4]2+溶液作为独立的前驱体溶液,以载玻片为衬底,在(125±5)℃的温度下沉积出致密、透明的ZnO薄膜。分别用冷场发射型扫描电镜(FESEM)和X射线衍射(XRD)分析了薄膜样品的表面形貌和结晶状态,用紫外-可见分光光度计(UV-Vis spectroscopy)研究了薄膜样品的发光性能。结果表明:获得样品为六角纤锌矿结构的多晶薄膜材料沿[002]方向择优生长;样品表面均匀、致密,厚度约为550nm;在可见光波段具有高的透射率(>80%)。

Interplay Between Structure, Stoichiometry, and Electron Transfer Dynamics in SILAR-based Quantum Dot-Sensitized Oxides

We quantify the rate and efficiency of picosecond electron transfer (ET) from PbS nanocrystals, grown by successive ionic layer adsorption and reaction (SILAR), into a mesoporous SnO2 support. Successive SILAR deposition steps allow for stoichiometry- and size-variation of the QDs, characterized using transmission electron microscopy. Whereas for sulfur-rich (p-type) QD surfaces substantial electron trapping at the QD surface occurs, for lead-rich (n-type) QD surfaces, the QD trapping channel is suppressed and the ET efficiency is boosted. The ET efficiency increase achieved by lead-rich QD surfaces is found to be QD-size dependent, increasing linearly with QD surface area. On the other hand, ET rates are found to be independent of both QD size and surface stoichiometry, suggesting that the donor–acceptor energetics (constituting the driving force for ET) are fixed due to Fermi level pinning at the QD/oxide interface. Implications of our results for QD-sensitized solar cell design are discussed.

High efficiency quantum dot-sensitised solar cells by material science and device architecture

This thesis studied cadmium sulfide and cadmium selenide quantum dots and their performance as light absorbers in quantum dot-sensitised solar cells. This research has made contributions to the understanding of size dependent photodegradation, passivation and particle growth mechanism of cadmium sulfide quantum dots using SILAR method and the role of ZnSe shell coatings on solar cell performance improvement.

Enhanced electron lifetime of CdSe/CdS quantum dot (QD) sensitized solar cells using ZnSe core–shell structure with efficient regeneration of quantum Ddots

Research on development of efficient passivation materials for high performance and stable quantum dot sensitized solar cells (QDSCs) is highly important. While ZnS is one of the most widely used passivation material in QDSCs, an alternative material based on ZnSe which was deposited on CdS/CdSe/TiO2 photoanode to form a semi-core/shell structure has been found to be more efficient in terms of reducing electron recombination in QDSCs in this work. It has been found that the solar cell efficiency was improved from 1.86% for ZnSe0 (without coating) to 3.99% using 2 layers of ZnSe coating (ZnSe2) deposited by successive ionic layer adsorption and reaction (SILAR) method. The short circuit current density (Jsc) increased nearly 1-fold (from 7.25 mA/cm2 to13.4 mA/cm2), and the open circuit voltage (Voc) was enhanced by 100 mV using ZnSe2 passivation layer compared to ZnSe0. Studies on the light harvesting efficiency (ηLHE) and the absorbed photon-to-current conversion efficiency (APCE) have revealed that the ZnSe coating layer caused the enhanced ηLHE at wavelength beyond 500 nm and a significant increase of the APCE over the spectrum 400−550 nm. A nearly 100% APCE was obtained with ZnSe2, indicating the excellent charge injection and collection process in the device. The investigation on charge transport and recombination of the device has indicated that the enhanced electron collection efficiency and reduced electron recombination should be responsible for the improved Jsc and Voc of the QDSCs. The effective electron lifetime of the device with ZnSe2 was nearly 6 times higher than ZnSe0 while the electron diffusion coefficient was largely unaffected by the coating. Study on the regeneration of QDs after photoinduced excitation has indicated that the hole transport from QDs to the reduced species (S2−) in electrolyte was very efficient even when the QDs were coated with a thick ZnSe shell (three layers). For comparison, ZnS coated CdS/CdSe sensitized solar cell with optimum shell thickness was also fabricated, which generated a lower energy conversion efficiency (η = 3.43%) than the ZnSe based QDSC counterpart due to a lower Voc and FF. This study suggests that ZnSe may be a more efficient passivation layer than ZnS, which is attributed to the type II energy band alignment of the core (CdS/CdSe quantum dots) and passivation shell (ZnSe) structure, leading to more efficient electron−hole separation and slower electron recombination.

Improved photovoltaic performance of CdSe/CdS/PbS quantum dot sensitized ZnO nanorod array solar cell

Single crystalline zinc oxide (ZnO) nanorod array has been used for the fabrication of CdSe/CdS/PbS/ZnO quantum dot sensitized solar cell (QDSSC). The ZnO nanorod array photoanodes are sensitized with consecutive layer of PbS, CdS and CdSe quantum dots by employing simple successive ion layer adsorption and reaction (SILAR) and chemical bath deposition (CBD) techniques. The performances of the QDSSCs are examined in detail using polysulfide electrolyte with copper sulfide (CuS) counter electrode. The combination of two successive layers of PbS with CdSe/CdS/ZnO shows an improved short circuit current density (12.223 mA cm(-2)) with a maximum power to conversion efficiency of 2.352% under 1 sun illumination. This enhancement is mainly attributed due to the better light harvesting ability of the PbS quantum dots and make large accumulation of photo-injected electrons in the conduction band of ZnO, and CdSe/CdS layers lower the recombination of photo-injected electrons with the electrolyte, these are well evidenced with the photovoltaic studies and electrochemical impedance spectroscopy. (C) 2013 Elsevier B.V. All rights reserved.

Cadmium Sulfide Nanocrystal Sensitized Vertically Aligned Titanium Dioxide Rods for Large Area Image Sensors on 3-D Substrates

We discuss here a semiconductors assembly comprising of titanium dioxide (TiO2) rods sensitized by cadmium sulfide (CdS) nanocrystals for potential applications in large area electronics on three dimensional (3-D) substrates. Vertically aligned TiO2 rods are grown on a substrate using a 150 degrees C process flow and then sensitized with CdS by SILAR method at room temperature. This structure forms an effective photoconductor as the photo-generated electrons are rapidly removed from the CdS via the TiO2 thereby permitting a hole rich CdS. Current-voltage characteristics are measured and models illustrate space charge limited photo-current as the mechanism of charge transport at moderate voltage bias. The stable assembly and high speed are achieved. The frequency response with a loading of 10 pF and 9 M Omega shows a half power frequency of 100 Hz. (C) 2015 The Electrochemical Society. All rights reserved.

Non-Destructive Evaluation of Ion-Implanted Semiconductor Thin Films Using Photothermal Deflections Spectroscopy

Materials and equipment which fail to achieve the design requirements or projected life due to undetected defects may require expensive repair or early replacement. Such defects may also be the cause of unsafe conditions or catastrophic unexpected failure, and will lead to loss of revenue due to plant shutdown. Non-Destructive Evaluation (NDE) / Non Destructive Testing (NDT) is used for the examination of materials and components without changing or destroying their usefulness. NDT can be applied to each stage of a system’s construction, to monitor the integrity of the system or structure throughout its life.

Carbon nanostructure based electrodes for high efficiency dye sensitized solar cell

Synthesis and functionalization of large-area graphene and its structural, electrical and electrochemical properties has been investigated. First, the graphene films, grown by thermal chemical vapor deposition (CVD), contain three to five atomic layers of graphene, as confirmed by Raman spectroscopy and high-resolution transmission electron microscopy. Furthermore, the graphene film is treated with CF4 reactive-ion plasma to dope fluorine ions into graphene lattice as confirmed by X-ray photoelectron spectroscopy (XPS) and UV-photoemission spectroscopy (UPS). Electrochemical characterization reveals that the catalytic activity of graphene for iodine reduction enhanced with increasing plasma treatment time, which is attributed to increase in catalytic sites of graphene for charge transfer. The fluorinated graphene is characterized as a counter-electrode (CE) in a dye-sensitized solar cell (DSSC) which shows ~ 2.56% photon to electron conversion efficiency with ~11 mAcm−2 current density. Second, the large scale graphene film is covalently functionalized with HNO3 for high efficiency electro-catalytic electrode for DSSC. The XPS and UPS confirm the covalent attachment of C-OH, C(O)OH and NO3- moieties with carbon atoms through sp2-sp3 hybridization and Fermi level shift of graphene occurs under different doping concentrations, respectively. Finally, CoS-implanted graphene (G-CoS) film was prepared using CVD followed by SILAR method. The G-CoS electro-catalytic electrodes are characterized in a DSSC CE and is found to be highly electro-catalytic towards iodine reduction with low charge transfer resistance (Rct ~5.05 Ωcm 2) and high exchange current density (J0~2.50 mAcm -2). The improved performance compared to the pristine graphene is attributed to the increased number of active catalytic sites of G-CoS and highly conducting path of graphene. We also studied the synthesis and characterization of graphene-carbon nanotube (CNT) hybrid film consisting of graphene supported by vertical CNTs on a Si substrate. The hybrid film is inverted and transferred to flexible substrates for its application in flexible electronics, demonstrating a distinguishable variation of electrical conductivity for both tension and compression. Furthermore, both turn-on field and total emission current was found to depend strongly on the bending radius of the film and were found to vary in ranges of 0.8 - 3.1 V/μm and 4.2 - 0.4 mA, respectively.

Fabrication and characterization of a nanostructured TiO2/In2S3-Sb2S3/CuSCN extremely thin absorber (eta) solar cell

CuSCN extremely thin absorber solar cell. Nanostructured TiO2 deposited by screen printing on an ITO substrate was used as an n-type electrode. An ∼80 nm extremely thin layer of the system In2S3-Sb2S3 deposited by successive ionic layer adsorption and a reaction (silar) method was used as an absorber. The voids were filled with p-type CuSCN and the entire assembly was completed with a gold contact. The solar cell fabricated with this heterostructure showed an energy conversion efficiency of 4.9%, which is a promising result in the development of low cost and simple fabrication of solar cells.

Arquiteturas do trigo: espaços de silagem no Alentejo, do século XIX à atualidade

O presente trabalho de investigação apresenta um estudo sistemático da expressão arquitetónica que teve na região do Alentejo a implantação agro-industrial da cultura do trigo, em especial, durante a "Campanha do Trigo", iniciada em 1929 e prosseguida durante o Estado Novo, até 1969. Para tanto, procede ao mapeamento dos elementos edificados, em ligação com os processos de produção, silagem e moagem industrial do trigo, bem como ao seu transporte, estabelecendo uma análise comparativa com outras regiões e países, com o intuito de revelar o impacto destes equipamentos nos diversos territórios e paisagens. Assim, procura-se compreender as relações que se estabeleceram entre a forma arquitetónica do silo (cujo desenho resulta fundamentalmente de uma resposta programática intrinsecamente ligada à sua função primordial - armazenamento do cereal) e os lugares, onde se implantaram e com os quais se procuraram articular, e as paisagens, com as quais perspetivaram dialogar. Para tal, procede-se a descrição do estado atual de cada exemplar das denominadas "arquiteturas do trigo", com o objetivo de gerar, num primeiro nível, o entendimento de cada caso em particular e, posteriormente, estabelecer, por efeito de comparação, um confronto, quer entre os diferentes contextos em que se inserem, quer entre as suas caraterísticas formais, de modo a tirar ilações que possibilitem problematizar o seu uso futuro, equacionando diferentes perspetivas de atuação sobre o edificado. Finalmente procura-se introduzir uma discussão segundo diferentes orientações e posicionamentos, de modo a invocar perspetivas de atuação sobre os silos, que se adequem a cada situação específica, a cada contexto e a cada lugar. É no confronto entre as abordagens enunciadas, que se evidencia, mais do que a pertinência, a emergência social e cultural de uma ação diligente, quer ao nível particular de cada peça silar, quer do sistema, do qual era parte integrante a linha de caminho de ferro, que através do seu traçado permitia interligar todas as peças silares e garantir o seu funcionamento a escala industrial; ABSTRACT: This research presents a systematic study of architectural expression of wheat crop agro-industrial development, in particular the "Wheat Campaign", started in 1929 and continue during the "New State", until 1969. We first proceed to map the built elements related to production processes, silage and wheat industrial grinding, as well as the ways of transportation, establishing a comparative analysis with other countries and regions, in order to reveal the impact of these objects in various territories and landscapes. We seek to understand the relationships between the architectural form of the silo (whose design is mainly a result of an intrinsically programmatic response linked to its primary function - cereal storage) and the places where they are implemented and the landscapes which they sought to communicate and articulate. Secondly, we describe the current status of each copy of the "wheat architectures" in Alentejo, with the main objective of attain, at first, the understanding of each particular case and, then, to establish a connection between the different contexts in which they operate and their formal characteristics, in order to conceive and discuss their future use, equating different perspectives of action in the buildings. Finally seeks to introduce a discussion according to different orientations and positions in order to invoke prospects for action on the grain elevators that are appropriate to each specific situation, every context and every place. It is the clash between the stated approaches, which shows more than the relevance, it shows social and cultural emergence of a diligent action on the particular level of each grain elevator on the system, which was an integral part of the railway, which through its tracing allowed to interconnect all grain elevators and assure its operation on an industrial scale