CdS and PbS quantum dots co-sensitized TiO2 nanorod arrays with improved performance for solar cells application

In this paper, we report a novel CdS and PbS quantum dots (QDs) co-sensitized TiO₂ nanorod arrays photoelectrode for quantum dots sensitized solar cells (QDSSCs). TiO₂ film consisting of free-standing single crystal nanorods with several microns high and 90–100 nm in diameter were deposited on a conducting glass (SnO₂:FTO) substrate by hydrothermal method. Then CdS/PbS QDs were deposited in turn on TiO₂ nanorods by facile SILAR technique. The FTO/TiO₂/CdS/PbS, used as photoelectrode in QDSSCs, produced a light to electric power conversion efficiency (Eff) of 2.0% under AM 1.5 illumination (100% sun), which shows the best power conversion efficiency compared with single CdS or PbS sensitized QDSSCs. One dimension TiO₂ nanorod provides continuous charge carrier transport pathways without dead ends. The stepwise structure of the band edges favored the electron injection and the hole-recovery for both CdS and PbS layers in photoelectrode, which may gave a high electric power conversion efficiency. The facile preparation and low cost nature of the proposed method and structure make it has a bright application prospects in photovoltaic areas in the future.     

TiO2 Coating for SnO2:F Films Produced by Filtered Cathodic Arc Evaporation for Improved Resistance to H+ Radical Exposure

Titanium dioxide thin films were deposited by filtered cathodic arc evaporation (FCAE) from a Ti target in an oxygen atmosphere onto (a) fluorine-doped tin oxide substrates SnO₂:F (FTO) and (b) glass microscope slides. The growth rate calculated from film thickness profilometry measurements was found to be approximately 0.8?nm/s. The films were highly transparent to visible light. x-Ray photoemission spectroscopy analysis of the Ti 2p electron binding- energy shift confirmed the presence of a TiO₂ stoichiometric compound. The results for the root-mean-square (RMS) surface roughness of the films deposited onto FTO substrates evaluated by atomic force microscopy suggested nanostructured film surfaces. When exposed to hydrogen plasma, TiO₂ films revealed insignificant changes in the optical spectra. The initial sheet resistance of the SnO₂:F layer was 14?Ω/sq. The deposition of the top TiO₂ layer (45?nm thick) over the FTO electrode resulted in an increase of the sheet resistance of 2?Ω/sq. In addition, the sheet resistance of the double-layer FTO/TiO₂ transparent conductive oxide (TCO) electrode increased by 1?Ω/sq as a result of H⁺ plasma exposure. Regardless of the TiO₂ film’s low conductivity, a thin protective layer could be coated onto FTO films (presumably 15?nm thick) due to their high transparency, offering high resistance to aggressive H⁺ plasma conditions. In this paper we show that ～50-nm-thick TiO₂ coating on FTO films provides sufficient protection against deterioration of transparency and conductivity due to hydrogen radical exposure.     

Effect of CdS layers on opto-electrical properties of chemically prepared ZnS/CdS/TiO2 photoanodes

In the present work, CdS nanoparticles as a sensitizer were grown on the spin coated nanoporous TiO₂ film by repeated cycles of a Successive Ionic Layer Adsorption and Reaction (SILAR) method. ZnS layer was coated on the CdS/TiO₂ anodes to act as a protection layer on CdS. The crystallite size of CdS nanocrystals is calculated to be 3 nm from XRD spectra. The optical band gap of the film determined from transmittance spectra decreases from 3.46 to 2.15 eV with the increase in the number of CdS SILAR cycles. SEM and TEM analysis depict the enabled penetration of CdS (1 1 1) nanoparticles into the nanoporous TiO₂ (1 0 1) structure. EDX study confirms the presence of all the elements (Ti, Cd, S, Zn and O) found on the photoanode. The attachment of cubic structured CdS on anatase phase of TiO₂ in the photoanode is verified using Raman spectra. Photoluminescence (PL) study shows that the emission peak corresponding to TiO₂ has been slightly blueshifted due to the interaction of CdS nanoparticles in TiO₂ nanoporous structures. The electrical measurement shows that the dark and light illuminated resistivity of the preferred photoanode is 7.91 and 5.65 Ω cm respectively.     

Femtosecond laser deposition of TiO2 nanoparticle-assembled films with embedded CdS nanoparticles

Based on the normal pulsed laser ablation method,femtosecond pulsed laser deposition（fs-PLD）is adopted in vacuum for the production of TiO2nanoparticle-assembled films.We study the morphology and electronic characteristics of TiO2nanoparticle-assembled films deposited at different oxygen background gas pressures from high vacuum（~10-4Pa）to 100 Pa and different deposition time.Our results show that TiO2nanoparticle-assembled films obtained in high vacuum present both a mixture with rutile phase and anatase phase and a pure rutile phase.At the same time,there are more mesoporous structures in the film after annealing,which is beneficial for the enhancement of photocatalytic activity.In water splitting experiment,part of the TiO2nanoparticle-assembled films embedded with a small mass fraction of CdS nanoparticles（~5%）present an interesting photocurrent enhancement with a maximum value of~0.2mA/cm2under a solar simulator.     

Photosensitization of TiO2 Nanostructures with CdS Quantum Dots: Particulate versus Tubular Support Architectures

TiO₂ nanotube arrays and particulate films are modified with CdS quantum dots with an aim to tune the response of the photoelectrochemical cell in the visible region. The method of successive ionic layer adsorption and reaction facilitates size control of CdS quantum dots. These CdS nanocrystals, upon excitation with visible light, inject electrons into the TiO₂ nanotubes and particles and thus enable their use as photosensitive electrodes. Maximum incident photon to charge carrier efficiency (IPCE) values of 55% and 26% are observed for CdS sensitized TiO₂ nanotube and nanoparticulate architectures respectively. The nearly doubling of IPCE observed with the TiO₂ nanotube architecture is attributed to the increased efficiency of charge separation and transport of electrons.     

Photoelectrochemical characteristics of TiO2 nanorod arrays grown on fluorine doped tin oxide substrates by the facile seeding layer assisted hydrothermal method

TiO2 nanorod arrays (NRAs) were prepared on fluorine doped tin oxide (FTO) substrates by a facile two-step hydrothermal method. The nanorods were selectively grown on the FTO regions which were covered with TiO2 seeding layer. It took 5 h to obtain the compact arrays with the nanorod length of ~2 μm and diameter of ~50 nm. The photoelectrochemical (PEC) properties of TiO2 NRAs are also investigated. It is demonstrated that the TiO2 NRAs indicate the good photoelectric conversion ability with an efficiency of 0.22% at a full-wavelength irradiation. A photocurrent density of 0.21 mA/cm2 is observed at 0.7 V versus the saturated calomel electrode (SCE). More evidences suggest that the charge transferring resistance is lowered at an irradiation, while the flat-band potential (Vfb) is shifted towards the positive side.     

Enhanced photocatalytic performance of platinized CdS/TiO2 by optimizing calcination temperature of TiO2 nanotubes

TiO₂ nanotubes were prepared by hydrothermal treatment of TiO₂ powder in NaOH aqueous solution and then calcined at various temperatures. The post-calcination treated TiO₂ nanotubes were decorated with CdS by wetness impregnation and subsequently sulfurization to fabricate CdS/TiO₂ composites. The photocatalytic performance of CdS/TiO₂ composites toward hydrogen production from water splitting was investigated. The results show that the calcination temperature of TiO₂ nanotubes has a significant effect on the photocatalytic performance of CdS/TiO₂. With the increase of calcination temperature from 300 to 500 °C, the crystallinity of TiO₂ nanotubes is increased resulting in the enhanced photocatalytic performance of CdS/TiO₂. When the calcination temperature is higher than 500 °C, TiO₂ nanotubes gradually transform into nanorods and finally completely collapse, which leads to the decrease of photocatalytic performance of CdS/TiO₂. The CdS/TiO₂ composite with TiO₂ nanotubes calcined at 500 °C exhibits the highest hydrogen evolution rate, which could be attributed to its 1 D nanotubular structure and good crystallinity.     

Fabrication of CdS nanowires on TiO2 nanorods for solar cell application

A composition of CdS nanoparticles and nanowires were deposited on TiO₂ nanorods by successive ionic layer adsorption and reaction method grown on Ti substrate. CdS/TiO₂/Ti device were used as photoanode in solar cell. Efficiency, short circuit current, and open circuit voltage were measured. Also, electron life time in each Fermi level and order of recombination were obtained by open circuit voltage decay and short circuit photocurrent interrupt voltage; respectively. Our results showed that there is an optimum composition of CdS nanoparticles and nanowires which improves solar cell properties of this type of cell.     

PbS and CdS Quantum Dot‐Sensitized Solid‐State Solar Cells: “Old Concepts,New Results”

Lead sulfide (PbS) and cadmium sulfide (CdS) quantum dots (QDs) are prepared over mesoporous TiO₂ films by a successive ionic layer adsorption and reaction (SILAR) process. These QDs are exploited as a sensitizer in solid‐state solar cells with 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) as a hole conductor. High‐resolution transmission electron microscopy (TEM) images reveal that PbS QDs of around 3 nm in size are distributed homogeneously over the TiO₂ surface and are well separated from each other if prepared under common SILAR deposition conditions. The pore size of the TiO₂ films and the deposition medium are found to be very critical in determining the overall performance of the solid‐state QD cells. By incorporating promising inorganic QDs (PbS) and an organic hole conductor spiro‐OMeTAD into the solid‐state cells, it is possible to attain an efficiency of over 1% for PbS‐sensitized solid‐state cells after some optimizations. The optimized deposition cycle of the SILAR process for PbS QDs has also been confirmed by transient spectroscopic studies on the hole generation of spiro‐OMeTAD. In addition, it is established that the PbS QD layer plays a role in mediating the interfacial recombination between the spiro‐OMeTAD⁺ cation and the TiO₂ conduction band electron, and that the lifetime of these species can change by around 2 orders of magnitude by varying the number of SILAR cycles used. When a near infrared (NIR)‐absorbing zinc carboxyphthalocyanine dye (TT1) is added on top of the PbS‐sensitized electrode to obtain a panchromatic response, two signals from each component are observed, which results in an improved efficiency. In particular, when a CdS‐sensitized electrode is first prepared, and then co‐sensitized with a squarine dye (SQ1), the resulting color change is clearly an addition of each component and the overall efficiencies are also added in a more synergistic way than those in PbS/TT1‐modified cells because of favorable charge‐transfer energetics.     

A novel CdCl2 treatment for glass/SnO2/CBD-CdS/CdTe solar cell

Residual CdCl₂ in chemical bath deposited (CBD) CdS layer was utilized to observe grain growth in CdTe layer for glass/SnO₂/CBD-CdS/CdTe structures. The above as-deposited composite films were subjected to rapid thermal annealing (RTA) for observing grain growth and subsequent cell fabrication. The films were characterized by studying their microstructural and compositional properties. Interfacial mixing behavior was studied by secondary ion mass spectroscopy (SIMS) measurements which showed a slight interfacial diffusion of the CdS layer into the CdTe layer. Performance of a photovoltaic (PV) cell structure with non-optimized thickness of the CdTe and CdS layers obtained by this technique was studied. Carrier life time was obtained from V_oc decay measurement. Photoinduced charge separation observed in this glass/SnO₂/CBD–CdS/CdTe structure was associated with an increase in the dielectric constant and a decrease in the device resistance.     

Hematite Photoanodes: Synergetic Enhancement of Light Harvesting and Charge Management by Sandwiched with Fe2TiO5/Fe2O3/Pt Structures

Efficient charge separation and transport as well as high light absorption are key factors that determine the efficiency of photoelectrochemical (PEC) water splitting devices. Here, a PEC device consisting of a hematite nanoporous film deposited on Pt nanopillars, followed by the decoration with an Fe₂TiO₅ passivation layer, is designed and fabricated. This structure can largely improve the light absorption in the composite materials, and significantly enhance the water oxidation performance of hematite photoanodes. The Fe₂TiO₅ thin shell and Pt underlayer significantly improve the interfacial charge transfer while minimizing the hole‐migration length in Fe₂O₃ photoanodes, leading to a drastically increased photocurrent density. Specially, the Fe₂TiO₅/Fe₂O₃/Pt photoanode yields an excellent photoresponse for PEC water splitting reactions with 1.0 and 2.4 mA cm^?2 obtained at 1.23 and 1.6 V_RHE under AM 1.5G illumination in 1 m KOH. The resulting photocurrents are 2.5 times enhanced compared to a pristine Fe₂O₃ photoanode of the same geometry. These results demonstrate a synergistic charge transfer effect of Fe₂TiO₅ and Pt layers on hematite for the improvement of PEC water oxidation.     

Enhancing current density of perovskite solar cells using TiO2-ZrO2 composite scaffold layer

A novel scaffold layer composed of TiO₂-ZrO₂ composite was fabricated for perovskite solar cell. Compared with pure TiO₂ nanoparticles (NPs), the relatively larger ZrO₂ NPs could increase film roughness and enhance light-scattering effect in TiO₂-ZrO₂ composite films. The device exhibited outstanding power conversion efficiency (PCE) of 11.41%. The morphology and aggregation of particles, three-dimensional roughness, as well as the ingredient and micro-structure of FTO/compact TiO₂/TiO₂-ZrO₂ was investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscope (AFM), energy dispersive spectrometer (EDS), and X-ray diffraction (XRD), respectively. Moreover, the optical property of TiO₂-ZrO₂ films for visible light was characterized by UV–visible absorption spectroscopy (UV–vis), and its influence on quantum yield of the device was further demonstrated by incident photon-to-electron conversion efficiency (IPCE). Owing to the inert oxide, the short-circuit current density of perovskite solar cell using TiO₂-ZrO₂ composition as scaffold layer increased by 21% compared to the one employing pure TiO₂ mesoporous film.     

Contact wetting angle as a characterization technique for processing CdTe/CdS solar cells

The feasibility of measuring contact wetting angles to characterize processing induced changes to thin film semiconductors in CdTe/CdS solar cells is evaluated. The contact angles of water and formamide are used to determine the polar and dispersive surface energies of the thin films using two analysis methods. Changes in surface energies resulting from processing are correlated to changes in surface chemistry and structure detected by glancing incidence X‐ray diffraction (GIXRD), X‐ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Surface energies are evaluated for sputtered In₂O₃:SnO₂, chemical surface‐deposited CdS, and physical vapor‐deposited (PVD) CdTe thin films under as‐deposited and treated conditions. Treatments include thermal anneal in air, argon, and CdCl₂ ambient as well as surface etching. Indium tin oxide (ITO) and CdS films exhibit increased polar surface energy corresponding to enhanced crystallization of surfaces resulting from processing and increasing CdS growth temperature. Native oxidation of PVD CdTe (111)‐oriented film surfaces occurs rapidly and is readily detected by changes in contact angle. Surface energies of PVD (111)‐oriented CdTe stored under various humidities prior to processing are energetically similar due to native oxidation. The polar energy of CdTe surfaces is affected by the addition or removal of crystalline surface oxides during film processing. Copyright © 2006 John Wiley & Sons, Ltd.     

The influence of substrate temperature on RF sputtered CdS thin films and CdS/p-Si heterojunctions

Cadmium sulfide (CdS) thin films were deposited onto soda lime glasses and p-Si semiconductors at various substrate temperatures (40, 150 and 275 °C) by radio frequency (RF) sputtering technique. The effect of substrate temperature on morphological, structural and optical properties of CdS thin films were analyzed by means of atomic force microscopy (AFM), x-ray diffraction (XRD) and uv–vis spectrum data. The results showed that the average roughness (R_a) of thin films increased from 2.0 to 4.0 nm and all films had hexagonal wurtzite structure. The optical band gaps of CdS thin films varied between 2.46–2.43 eV. Characteristic parameters of CdS/p-Si heterojunctions including ideality factor, barrier height, series resistance and rectification ratio were measured. It was seen that both ideality factor and barrier height values of the heterojunctions increase with the increase substrate temperature. It was attributed to increase in inhomogenity of the thin films. Furthermore, the photoelectrical parameters of CdS/p-Si heterojunctions were studied.     

High Performance PbS Colloidal Quantum Dot Solar Cells by Employing Solution‐Processed CdS Thin Films from a Single‐Source Precursor as the Electron Transport Layer

CdS thin films are a promising electron transport layer in PbS colloidal quantum dot (CQD) photovoltaic devices. Some traditional deposition techniques, such as chemical bath deposition and RF (radio frequency) magnetron sputtering, have been employed to fabricate CdS films and CdS/PbS CQD heterojunction photovoltaic devices. However, their power conversion efficiencies (PCEs) are moderate compared with ZnO/PbS and TiO₂/PbS heterojunction CQD solar cells. Here, efficiencies have been improved substantially by employing solution‐processed CdS thin films from a single‐source precursor. The CdS film is deposited by a straightforward spin‐coating and annealing process, which is a simple, low‐cost, and high‐material‐usage fabrication process compared to chemical bath deposition and RF magnetron sputtering. The best CdS/PbS CQD heterojunction solar cell is fabricated using an optimized deposition and air‐annealing process achieved over 8% PCE, demonstrating the great potential of CdS thin films fabricated by the single‐source precursor for PbS CQDs solar cells.     

Metal–Organic Framework Derived Co3O4/TiO2/Si Heterostructured Nanorod Array Photoanodes for Efficient Photoelectrochemical Water Oxidation

A novel hierarchical structured photoanode based on metal–organic frameworks (MOFs)‐derived porous Co₃O₄‐modified TiO₂ nanorod array grown on Si (MOFs‐derived Co₃O₄/TiO₂/Si) is developed as photoanode for efficiently photoelectrochemical (PEC) water oxidation. The ternary Co₃O₄/TiO₂/Si heterojunction displays enhanced carrier separation performance and electron injection efficiency. In the ternary system, an abnormal type‐II heterojunction between TiO₂ and Si is introduced, because the conduction band and valence band position of Si are higher than those of TiO₂, the photogenerated electrons from TiO₂ will rapidly recombine with the photogenerated holes from Si, thus leading to an efficient separation of photogenerated electrons from Si/holes from TiO₂ at the TiO₂/Si interface, greatly improving the separation efficiency of photogenerated hole within TiO₂ and enhances the photogenerated electron injection efficiency in Si. While the MOFs‐derived Co₃O₄ obviously improves the optical‐response performance and surface water oxidation kinetics due to the large specific surface area and porous channel structure. Compared with MOFs‐derived Co₃O₄/TiO₂/FTO photoanode, the synergistic function in the MOFs‐derived Co₃O₄/TiO₂/Si NR photoanode brings greatly enhanced photoconversion efficiency of 0.54% (1.04 V vs reversible hydrogen electrode) and photocurrent density of 2.71 mA cm^?2 in alkaline electrolyte. This work provides promising methods for constructing high‐performance PEC water splitting photoanode based on MOFs‐derived materials.     

Binder-free MWCNT/TiO2 multilayer nanocomposite as an efficient thin interfacial layer for photoanode of dye sensitized solar cell

Multiwalled carbon nanotube/TiO₂ multilayer nanocomposite was successfully deposited on the fluorine-doped tin oxide (FTO) glass via layer-by-layer assembly technique to modify interfacial contact between the FTO surface and nanocrystalline TiO₂ layer as well as carbon nanotube/TiO₂ contacts in photoanode of dye sensitized solar cell. Using this approach, binder-free interfacial thin film was developed with nonagglomerated, well-dispersed MWCNTs on FTO and into TiO₂ matrix and with maximum covering of TiO₂ nanoparticles on MWCNTs. Introduction of MWCNTs/TiO₂ interfacial layer into the TiO₂ photoanode increased short circuit current density (J_sc) from 11.90 to 17.25 mA/cm² and open circuit voltage (V_oc) from 730 mV to 755 mV, whereas there was no notable change in the fill factor (FF). Consequently, power conversion efficiency (η) was enhanced from 5.32% to 7.53%, yielding a 41.5% enhancement. The results suggest that our simple strategy can integrate reduction of back electron reaction at FTO/TiO₂ interface with the effective charge transport ability of carbon nanotubes and possessing high surface area for efficient dye loading.     

Chlorine-doped CdS thin films from CdCl<Subscript>2</Subscript>-mixed CdS powder

The CdS:Cl thin films have been prepared using thermally evaporated, CdCl₂-mixed CdS powder at 200°C substrate temperature. The percentage of CdCl₂ in the mixture varied from 0% to 0.20%. The electrical properties and the grain size of the deposited films were investigated. The results show that light doping, resistivity, carrier concentration, and mobility follow Seto’s model for polycrystalline material. However, with heavy doping, these properties undergo a saturation trend. The saturation behavior can be understood in terms of the rapid formation of the A-center complexes in the films. The deposited films were annealed at 250°C and 300°C. The resistivity of pure and lightly doped CdS films increased with annealing temperature, whereas carrier concentration and mobility in these films decreased. However, for the higher doping concentrations, the resistivity decreased, whereas carrier concentration and mobility showed improvement. These changes in electrical properties of the deposited films with annealing and doping concentration are attributed to a reduction in the lattice defect sites in CdS upon annealing. The experimental results are interpreted in terms of a modified version of Seto’s model for polycrystalline materials.     

Phase‐Modulated Band Alignment in CdS Nanorod/SnSx Nanosheet Hierarchical Heterojunctions toward Efficient Water Splitting

CdS is a promising visible light response photoanode of photoelectrochemical (PEC) water splitting, but it remains a great challenge for practical application, due to the photohole‐induced self‐corrosion, and sulfide/sulfite ions as hole scavengers are always necessary for stable solar hydrogen generation. Herein, a CdS/SnS_x nanorods/nanosheets hierarchical heterostructure with novel phase‐engineered band alignment is rationally designed via a two‐step solution reaction route for PEC water splitting. In the Na₂SO₄ aqueous electrolyte without any hole scavengers, compared with the pristine CdS, the CdS/SnS_x photoanode achieves a remarkably enhanced photocurrent density of 1.59 mA cm^?2 and a considerable stability at bias potential 1.23 V versus reversible hydrogen electrode (RHE) under simulated sunlight. It is proposed that the deposited SnS_x nanosheets not only act as protective layers to restrain the photocorrosion of CdS, but also facilitate the charge separation in CdS by the virtue of the Type II heterojunction formed between CdS and SnS_x.     

溶液PH值对CdS薄膜结构特性的影响

采用化学水浴沉积(CBD)工艺在玻璃衬底上制 备CdS薄膜,研究溶液PH值对CdS 薄膜结构特性的影响。薄膜的厚度、组份、晶相结构和表观形貌分别由台阶仪、X射线荧光 光谱(XRF)、X射线衍射(XRD)和场发射扫描电子显微镜(FESEM)来表征。溶液的 PH值为11.26、 11.37和11.48时,CdS薄膜的晶相以六方相为主,薄膜的厚度先增大后减小; PH值为11.62、11.66时,薄膜的晶相以立方相为主,薄 膜的厚度进一步减小。同时,随着溶液PH值 增大,CdS薄膜的晶格常数也逐渐增大。两种晶相的CdS薄膜缓冲层与CIGS薄膜分别构成异 质 对形成异质结时的晶格失配分别为32.297%和1.419%,界面态密度分别为2.792×10¹⁴和8.507×10¹²,因此高效CIGS薄 膜太阳电池更需要立方相的CdS薄膜。