Comparison of the performances of dye-sensitized solar cells based on different TiO2 electrode nanostructures

This article reports on the performances of dye-sensitized solar cells based on three different working electrode structures, i.e., (i) sintered TiO₂ nanoparticles (20–40 nm diameters), (ii) ordered arrays of TiO₂ nanotubules (150 nm external diameters and 80 nm internal diameters), and (iii) ordered arrays of TiO₂ nanorods (150 nm diameters). Even though the highest short-circuit current density was achieved with systems based on TiO₂ nanotubules, the most efficient cells were those based on ordered arrays of TiO₂ nanorods. This is probably due to higher open-circuit photovoltage values attained with TiO₂ nanorods than with TiO₂ nanotubules. The nanorods are thicker than the nanotubules and therefore the injected electrons, stored in the trap states of the inner TiO₂ molecules, are shielded from recombination with holes in the redox electrolyte at open circuit. The high short-circuit photocurrent densities seen in the ordered TiO₂ systems can be explained by the fact that, as opposed to the sintered nanoparticles, the parallel and vertical orientation of the ordered nanostructures provide well-defined electrons percolation paths thus significantly reduce the diffusion distance and time constant.     

Effects of ZnO coating on the performance of TiO2 nanostructured thin films for dye-sensitized solar cells

ZnO-coated TiO₂ (ZTO) thin films were deposited on ITO substrates by a sol–gel method for application as the work electrode for dye-sensitized solar cells (DSSCs). The I–V curve and the incident photon-to-current conversion efficiency (IPCE) value of DSSCs for ZTO thin films were studied and compared with single TiO₂ films. The results show that the short-circuit photocurrent (J _sc) and open-circuit voltage (V _oc) values increased from 3.7 mA/cm² and 0.68 V for the DSSCs with a single TiO₂ film to 4.5 mA/cm² and 0.72 V, respectively, for the DSSCs with a ZTO thin film. It indicated that the DSSCs with a ZTO thin film contributed to provide an inherent energy barrier that suppressed charge recombination significantly. In addition, the higher IPCE value in the ZTO thin film is attributed to the better charge separation by a fast electron transfer process using two semiconductors with different conduction band edges and energy positions.     

Fabrication of a nanoparticle TiO<Subscript>2</Subscript> photoelectrochemical cell utilizing a solid polymeric electrolyte of PAN–PC–LiClO<Subscript>4</Subscript>

A nanoparticle TiO₂ solid-state photoelectrochemical cell utilizing as a solid electrolyte of poly(acrylonitrile)–propylene–carbonate–lithium perchlorate (PAN–PC–LiClO₄) has been fabricated. The performance of the device has been tested in the dark and under illumination of 100-mW cm⁻² light. A nanoparticle TiO₂ film was deposited onto indium tin oxide-covered glass substrate by controlled hydrolysis technique assisted with spin-coating technique. The average grain size for the TiO₂ film is 76 nm. LiClO₄ salt was used as a redox couple. The room temperature conductivity of the electrolyte is 4.2 × 10⁻⁴ S cm⁻¹. A graphite electrode was prepared onto a glass slide by electron beam evaporation technique. The device shows the rectification property in the dark and shows the photovoltaic effect under illumination. The best J _sc and V _oc of the device were 2.82 μA cm⁻² and V _oc of 0.58 V, respectively, obtained at the conductivity of 4.2 × 10⁻⁴ S cm⁻¹ and intensity of 100 mW cm⁻². The J _sc was improved by about three times by introducing nanoparticle TiO₂ and by using a solid electrolyte of PAN–PC–LiClO₄ replacing PVC–PC–LiClO₄ in the device. The current transport mechanism of the cell is also presented in this paper.     

Synthesis and photocatalytic activity of polyaniline–TiO<Subscript>2</Subscript> composites with bionic nanopapilla structure

Polyaniline (PANI)–TiO₂ nanocomposites possessing both nano and microscale structures were prepared through a facile hydrothermal route in the presence of PANI. The nanopapilla particles were characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray analysis, X-ray photoelectron spectra, X-ray diffraction, FTIR spectra, UV–Vis spectroscopy, and N₂ adsorption analysis, etc. The results show that the composites possess both nano and microscale structures. The TiO₂ nanorods are dispersed on PANI with one end fixed to the surface. The photocatalytic properties of the powders were verified by the photodegradation of gaseous acetone under UV (λ = 254 nm) and visible-light irradiation (λ > 400 nm). In fact, the photocatalytic effects exhibited by the composite particles were superior to that of pure TiO₂ and P25 samples. This excellent behavior is attributed to the structural features of PANI–TiO₂ microspheres and the synergistic effect between PANI and TiO₂ which facilitates a larger amount of surface active sites. This in turn causes a faster charge separation and slower charge recombination which results in a more efficient decomposition of gaseous pollutants.     

Explanation of Effect of Added Water on Dye-Sensitized Nanocrystalline TiO2 Solar Cell： Correlation between Performance and Carrier Relaxation Kinetics

Time-resolved mid-IR transient absorption spectroscopy is employed to explore the mechanism of improving the performance of dye-sensitized TiO2 solar cell （DSSC） when a certain amount of H2 0 is added into the electrolyte. The relaxation kinetics of dye-sensitized TiO2 nanocrystalline film and the corresponding DSSC performance are investigated under different conditions. It is found that the interracial charge recombination is retarded and electron injection efficiency is increased in the water vapour and in the electrolyte when D20 is added. The values of open-circuit photovoltage Voc and the short-circuit photocarrent Jsc of the cells are linearly correlated to the product of the two decay time constants. We also observed that Voc well correlates with electron injection efficiency. It provides a preliminary microscopic account for the function of the added water in improving the performance of DSSCs.     

Poly(vinyl chloride)-<Emphasis Type="Italic">graft</Emphasis>-poly(<Emphasis Type="Italic">N</Emphasis>-vinyl caprolactam) graft copolymer: synthesis and use as template for porous TiO<Subscript>2</Subscript> thin films in dye-sensitized solar cells

Poly(N-vinyl caprolactam) (PNVCL) side chains were grafted to a poly(vinyl chloride) (PVC) backbone via atom transfer radical polymerization. The synthesized PVC-g-PNVCL graft copolymer was templated for the preparation of porous TiO₂ thin films, which involved a sol–gel reaction and calcination process. The interaction of the carbonyl groups in the PVC-g-PNVCL with the titania was revealed by FT-IR spectroscopy. X-ray diffraction and transmission electron microscopy analysis showed the formation of porous TiO₂ thin films with the anatase phase. A series of porous TiO₂ thin films with different pore sizes and porosities was prepared by varying the solution compositions and were used as photoelectrodes in dye-sensitized solar cells (DSSC) with a polymer electrolyte. The DSSC performed best when using the TiO₂ film with higher porosity, lower interfacial resistance, and longer electron life time. The highest energy conversion efficiency, photovoltage (V _oc), photocurrent density (J _sc), and fill factor (FF) were 1.2%, 0.68 V, 3.2 mA/cm², and 0.57 at 100 mW/cm², respectively, for the quasi-solid state DSSC with a 730-nm-thick TiO₂ film.     

Effect of built-in electric field in photovoltaic InAs quantum dot embedded GaAs solar cell

In this paper, three p–i–n GaAs solar cells were grown and characterized, one with InAs quantum dot (QD) layers embedded in the depletion region (sample A), one with QD layers embedded in the n ⁻ base region (B), and the third without QDs (control sample C). QD-embedded solar cells (samples A and B) show broad photoluminescence spectra due to QD multi-level emissions but have lower open-circuit voltages V _oc and lower photovoltaic (PV) efficiencies than sample C. On the other hand, the short-circuit current density J _sc in sample A is increased while it is decreased in sample B. Theoretical analysis shows that in sample B where the built-in electric field in QDs is zero, electrons tend to occupy QDs and strong potential variations exist around QDs which deteriorate the electron mobility in the n ⁻ base region so that J _sc in sample B is decreased. Hole trapping and electron–hole recombination in QDs are also enhanced in sample B, resulting in a reduced V _oc and thus a worse PV effect. In sample A, a strong built-in field exists in QD layers, which facilitates photo-carrier extraction from QDs and thus J _sc is increased. However, QDs in the depletion region in sample A act also as recombination-generation centers so that the dark saturated current density is drastically increased, which reduces V _oc and the total PV effect. In conclusion, a nonzero built-in electric field around QDs is vital for using QDs to increase the PV effect in conventional p–i–n GaAs solar cells.     

Effects of preannealing temperature of ZnO thin films on the performance of dye-sensitized solar cells

The preferred (002) orientation zinc oxide (ZnO) nanocrystalline thin films have been deposited on FTO-coated glass substrates by sol–gel spin-coating technology and rapid thermal annealing for use in dye-sensitized solar cells (DSSC). The effects of preannealing temperature (100 and 300°C) on the microstructure, morphology and optical properties of ZnO thin films were studied. The ZnO thin films were characterized by X-ray diffraction (XRD), scanning electron microscopic (SEM) and Brunauer–Emmett–Teller (BET) analysis. The photoelectric performance of DSSC was studied by I–V curve and the incident photon-to-current conversion efficiency (IPCE), respectively. From the results, the intensities of (002) peaks of ZnO thin films increases with increasing preannealing temperature from 100°C to 300°C. The increase in pore size and surface area of ZnO films crystallized at the increased preannealing temperature contributed to the improvement on the absorption of N3 dye onto the films, the short-circuit photocurrent (J _sc) and open-circuit voltage (V _oc) of DSSC. The higher efficiency (η) of 2.5% with J _sc and V _oc of 8.2 mA/cm² and 0.64 V, respectively, was obtained by the ZnO film preannealed at 300°C.     

Photoelectric properties of ZnO: In nanorods/SiO2/Si heterostructure assembled in aqueous solution

In-doped zinc oxide (ZnO:In) nanorods were grown onto SiO₂/n-Si substrate without catalyst in aqueous solution. The ZnO:In nanorods/SiO₂/n-Si heterostructure photovoltaic device was prepared. The structural and photoelectric properties of the as-grown ZnO:In nanorods were analyzed. ZnO:In nanorods had a strong and broad UV surface photovoltage response in the range of 300–400 nm, and the bands were identified. The photoelectric conversion properties of ZnO:In nanorods/SiO₂/n-Si heterostructure were investigated. ZnO:In/SiO₂/n-Si heterostructure showed a wide range photocurrent spectral response with high intensity in the UV and visible region. The rectifying behavior of this heterostructure was observed. Moreover, the device had a low turn-on voltage and a high breakdown voltage. Current–voltage characteristic was studied for the heterostructure, and the open-circuit voltage and short-circuit current were obtained. PACS 73.40.Lq; 85.35.Be; 81.16.Dn     

A new one-step synthesis method for coating multi-walled carbon nanotubes with iron oxide nanorods

A facile solution-chemical method has been developed to be capable of covering a multiwalled carbon nanotube (MWNTs) with iron oxide nanorods without using any bridging species. MWNTs in this composite were decorated randomly by α-Fe₂O₃ nanorods with diameters in the range of 3–5 nm and lengths of 15–30 nm. The formation route to anchor α-Fe₂O₃ nanorods onto MWNTs was proposed as the intercalation and adsorption of iron ions onto the wall of MWNTs, followed by the nucleation and growth of α-Fe₂O₃ nanorods. α-Fe₂O₃/MWNTs nanocomposites show specific high Brunauer–Emmett–Teller surface areas. The photocatalytic activity experiment indicated that the prepared α-Fe₂O₃/MWNTs nanocomposites exhibited a higher photocatalytic activity for the photocatalytic decolorization of rhodamine B aqueous solution under the visible-light illumination than the single phase α-Fe₂O₃ samples. This methodology made the synthesis of MWNTs-nanorods composites possible and may be further extended to prepare more complicated nanocomposites based on MWNTs for technological applications.     

Structure and magnetic properties of Zn<Subscript>0.9</Subscript>Co<Subscript>0.1</Subscript>O nanorods synthesized by a simple sol–gel method using metal acetylacetonate and poly(vinyl alcohol)

Room-temperature ferromagnetism was observed in Zn_0.9Co_0.1O nanorods with diameters and lengths of ∼100–200 nm and ∼200–1000 nm, respectively. Nanorods were synthesized by a simple sol–gel method using metal acetylacetonate powders of Zn and Co and poly(vinyl alcohol) gel. The XRD, FT-IR and SAED analyses indicated that the nanorods calcined at 873–1073 K have the pure ZnO wurtzite structure without any significant change in the structure affected by Co substitution. Optical absorption measurements showed absorption bands indicating the presence of Co²⁺ in substitution of Zn²⁺. The specific magnetization of the nanorods appeared to increase with a decrease in the lattice constant c of the wurtzite unit cell with the highest value being at 873 K calcination temperature. This magnetic behavior is similar to that of Zn_0.9Co_0.1O nanoparticles prepared by polymerizable precursor method. We suggest that this behavior might be related to hexagonal c-axis being favorable direction of magnetization in Co-doped ZnO and the 873 K (energy of 75 meV) being close to the exciton/donor binding energy of ZnO.     

Facile synthesis and visible-light photocatalytic activity of bismuth titanate nanorods

Highly crystalline bismuth titanate (Bi₁₂TiO₂₀, BiT) nanorods, as visible-light photocatalysts were prepared by a template-free hydrothermal process. The as-prepared BiT nanorods fabricated in high yields by simply manipulating pH values in the absence of any capping agent, were characterized by a number of techniques, such as XRD, SEM, TEM, HRTEM, BET, and UV–Vis spectrum. In this case, hydroxide ions seem to play a pivotal role in controlling the formation of seeds and the growth of the BiT nanorods. Based on the structural analysis of nanocrystals obtained at different pH values, we proposed a plausible mechanism to account for the formation of the tunable morphologies. Most importantly, the BiT nanorods with good stability exhibited higher photocatalytic activities in the degradation of Rhodamine B under visible light irradiation (λ ≥ 420 nm) than the commercial P25 TiO₂ and bulk BiT powders, demonstrating that Bi₁₂TiO₂₀ is a promising candidate as a visible-light photocatalyst.     

Theoretical analysis on the limitations of the open-circuit voltage of a hydrogenated amorphous silicon p-i-n solar cell

We have made theoretical studies on the limitation of the open-circuit voltageV _oc of a hydrogenated amorphous silicon (a-Si:H) p-i-n type solar cell. The effects of the tail states in the a-Si:H i layer and of the interface recombination are discussed in detail. The opencircuit voltage increases when the distribution of the tail states is sharp and/or the capture cross sections of these states are small. This is because the recombination rate of photogenerated carriers and/or the density of space charge due to trapped carriers in these states become low in these conditions. These effects of the tail states on the value ofV _oc become pronounced when the built-in potential of the p-i-n junction is high. The decrease in the effective recombination velocity of carriers at the p/i and n/i interfaces results in an increase ofV _oc. This increase becomes remarkable when the effects of the tail states on the value ofV _oc are small. Both the sharp distribution of tail states and the small value of the interface recombination velocity are necessary to increase considerably the value ofV _oc. We show the conditions of the material parameters necessary to obtain an open-circuit voltage of 1.0 V.     

Ascent of open-circuit voltage on diamond-like carbon photovoltaic cell by infrared heating-assisted pulsed-laser deposition

Phosphorus-doped diamond-like carbon (DLC) films were deposited on quartz and p-type silicon (p-Si) substrates by pulsed-laser deposition. Open-circuit voltage (V _oc) and short-circuit density (I _sc/cm²) from a heating process converted from one type of electrode to another and the two types of electrode pattern are shown by the V–I characteristics. The first heating process was by a ceramic heater, and the other was by an infrared heater. We adopted two electrode patterns, from a bipectinate electrode and a plot pattern electrode, to measure electric photovoltaic characteristics. We were able to upgrade V _oc and I _sc/cm² to 35∼45 mV, and 0.24 μA/cm², respectively, under infrared heating. V _oc by the plot pattern electrode was over 2 V under infrared heating and ceramic heating did not match this on deposition by the PLD method.     

a-Si/SiN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> multilayered light absorber for solar cell

40 alternate a-Si/SiN _x multilayer are incorporated as an absorber layer in a p–i–n solar cell. The device is fabricated using hot-wire chemical vapor deposition (HWCVD) technique. The structure of the multilayer film is examined by high resolution transmission electron microscopy (HR-TEM) which shows distinct formation of alternate a-Si and SiN _x layers. The a-Si and SiN _x layers have thickness of ~3.5 and 4 nm, respectively. The photoluminescence (PL) of multilayer film shows bandgap energy of ~2.52 eV, is larger than that of the c-Si and a-Si. Dark and illuminated current–voltage (I–V) characterization of the ML films shows that these ML are photosensitive. In the present work, it is seen that the p–i–n structure with i-layer as ML quantum well (QW) structures show photovoltaic effect with relatively high open-circuit voltage (V _OC). The increment of bandgap energy in PL and high V _OC of the device is attributed to the quantum confinement effect (QCE).     

TiO<Subscript>2</Subscript> Nanorod Arrays Sensitized with CdS Quantum Dots for Solar Cell Applications: Effects of Rod Geometry on Photoelectrochemical Performance

CdS quantum dot (QD) sensitized TiO₂ nanorod array (NRA) film electrodes with different rod geometries were fabricated via a solvothermal route followed by a sequentialchemical bath deposition (S-CBD) process. By controlling the solution growth conditions, the rod geometries, especially the tip structures, of the TiO₂ NRAs were tuned. The results indicated that the vertically aligned hierarchical NRAs possessed conically shaped tip geometry, which was favorable for film electrodes due to the reduced reflectance, enhanced light harvesting, fast charge-carrier separation and transfer, suppression of carrier recombination, sufficient electrolyte penetration and subsequent efficient QD assembly. CdS QD sensitized TiO₂ NRA film electrodes with tapered tips exhibited an enhanced photoelectrochemical (PEC) performance, a photocurrent intensity of 5.13 mA/cm² at a potential of 0 V vs. saturated calomel electrode, an open-circuit potential of −0.68 V vs. saturated calomel electrode and an incident photon to current conversion efficiency (IPCE) of 22% in the visible-light region from 400 to 500 nm. The effects of rod geometry on the optical absorption, reflectance, hydrophilic properties and PEC performance of bare TiO₂ and CdS QD sensitized TiO₂ NRA film electrodes were investigated. The mechanism of charge-carrier generation and transfer in these CdS QD sensitized solar cells based on vertically aligned TiO₂ nanorods is discussed.     

Electro-optical characterization and analysis of CuPc-based solar cells with high photovoltage

Organic solar cells using the CuPc and PTCBI semiconductor layers were studied. A high open circuit voltage of 1.15 V was obtained in a device with ITO/PEDOT:PSS/CuPc (15 nm)/PTCBI (7 nm)/Al structure. Results were interpreted in terms of a modified CuPc-Al Schottky diode for the thin PTCBI case and a CuPc-PTCBI heterojunction for the thick PTCBI case. Also, the formation of a thin aluminum oxide layer under the aluminum electrode was postulated. This layer has a beneficial aspect wherein shunting losses are reduced and a high photovoltage is enabled. However, it adds greatly to the series resistance to a point where the short circuit current density is reduced. CuPc Schottky diodes with an ITO/PEDOT:PSS/CuPc/Al structure yielded a high V _oc of 900 mV for a CuPc layer of thickness 140 nm. The V _oc increased with increase in CuPc layer thickness.     

Biotemplate fabrication of SnO<Subscript>2</Subscript> nanotubular materials by a sonochemical method for gas sensors

A sonochemical method is developed to fabricate SnO₂ nanotubular materials from biological substances (here, it is cotton). The cotton fibers in SnCl₂ solution were first treated with ultrasonic waves in air, followed by calcinations to give nanotubular materials that faithfully retain the initial cotton morphology. The microstructure and morphology of the obtained SnO₂ nanotubules were characterized by the combination of field-emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), X-ray diffraction (XRD), and N₂ adsorption/desorption measurements. The thermal behavior and crystalline properties were examined in the temperature range of 450–700 °C. The nanocrystals composing of SnO₂ nanotubules were estimated about 8.5, 13.2, and 14.2 nm corresponding to calcination temperatures of 450, 550, and 700 °C, respectively. The sensor performance of biomorphic SnO₂ nanotubules calcined at 700 °C was investigated in the atmosphere of ethanol, formaldehyde, carbinol, carbon monoxide, hydrogen, ammonia, and acetone, respectively, which exhibited a good selectivity for acetone at a working temperature of 350 °C. The sensitivity to 20 ppm acetone, S, was 6.4 at 350 °C with rapid response and recovery (around 10–9 s). These behaviors were well explained in relation to the morphology of the nanotubules thus produced.     

Electrochemical properties of TiO2 nanoparticle/nanorod composite photoanode for dye-sensitized solar cells

A unique composite of TiO₂ nanoparticles (NPs) and nanorods (NRs) has been used to fabricate a photoelectrode for developing dye-sensitized solar cells (DSSCs) with higher sensitivity. The TiO₂ nanorods were synthesized using a mechanical process, in which electrospun TiO₂ nanofibers was grinded in a controlled way to obtain uniform size distribution. The characteristics of electron transport, recombination lifetime and charge collection were investigated by intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS). Photoelectrodes prepared with the composites of NRs and NPs showed significant improvements in electron transportation compared to only NP photoelectrodes, which would enhance the photovoltaic performance of DSSCs. IMPS and IMVS measurements show that fast electron transport and slightly decreased recombination lifetime resulted in the improvement of efficiency. The highest energy conversion efficiency obtained from the photoelectrodes fabricated with the as-prepared rutile TiO₂ nanofibers at 5 wt% NR content was up to 6.1% under AM1.5G solar illumination. The results demonstrate that the composite nanostructure can take advantage of both the fast electron transport of the nanorods and the high surface area of the nanoparticles.     

The electrical characteristics of MBE n-Hg1–xCdxTe (x?=?0.29–0.31) MIS structures with sharp inhomogeneities in composition

The effect of regions with periodic sharp 48–54 nm thick inhomogeneities in composition on the electrophysical characteristics of MIS structures based on graded-gap n-Hg_1–x Cd _x Te (x = 0.29–0.31) grown by molecular-beam epitaxy is studied. It is found that major electro-physical and photo-electrical characteristics are qualitatively similar for MIS structures based on n-Hg_1–x Cd _x Te with sharp inhomogeneities in composition (barriers) and without “barriers”. It is shown that the electrical characteristics are mostly affected by the “barrier regions” located close to the insulator – semiconductor interface. This effect is manifested in an increase of the effective dielectric thickness, which can be due to the fact that the regions of enhanced composition form potential barriers for electrons, and in a decrease in the relaxation time of non-equilibrium carriers due to recombination at the boundaries of the regions with sharp changes in composition.