Anodic TiO<Subscript>2</Subscript> nanotubes powder and its application in dye-sensitized solar cells

An increasing energy demand and environmental pollution create a pressing need for clean and sustainable energy solutions. TiO₂ semiconductor material is expected to play an important role in helping solve the energy crisis through effective utilization of solar energy based on photovoltaic devices. Dye-sensitized solar cells (DSSCs) are potentially lower cost alternative to inorganic silicon-based photovoltaic cells. In this study, we report on the fabrication of DSSCs from anodic TiO₂ nanotubes (NT) powder, produced by rapid breakdown potentiostatic anodization of Ti foil in 0.1 M HClO₄ electrolyte, as photoanode. TiO₂ NT powders with a typical NT outer diameter of approximately 40 nm, wall thickness of approximately 8–15 nm, and length of about 20–25 μm, have been synthesized. The counter electrode was made by electrodeposition of Pt from an aqueous solution of 5 mM H₂PtCl₆ onto fluorine-doped tin oxide (FTO) glass substrate. The above front-side illuminated DSSCs were compared with back-side illuminated DSSCs fabricated from anodic TiO₂ NTs that were grown on the top of Ti foil as photoanode. The highest cell efficiency was 3.54% under 100 mW/cm² light intensity (1 sun AM 1.5G light, Jsc = 14.3 mA/cm², Voc = 0.544 V, FF = 0.455). To the best of our knowledge, this is the first report on the fabrication of DSSC from anodic TiO₂ NTs powder. The TiO₂/FTO photoanodes were characterized by FE-SEM, XRD, and UV–Visible spectroscopy. The catalytic properties of Pt/FTO counter electrodes have been examined by cyclic voltammetry.     

Hydrothermal growth of large-scale macroporous TiO<Subscript>2</Subscript> nanowires and its application in 3D dye-sensitized solar cells

Large-scale macroporous TiO₂ nanowires (MTN) were directly grown on spiral-shaped titanium wires as photoanodes of dye-sensitized solar cells (DSSCs) via a facile hydrothermal reaction without any seeds, templates, and TiO₂ powder. The MTN thin film was characterized by SEM, XRD and TEM. The studies revealed that the MTN thin film had better mechanical properties and provided an efficient pathway for the diffusion of liquid electrolyte. The efficiency of 0.86% for the 3D DSSC was obtained with a J _sc of 2.30 mA/cm², V _oc of 616 mV, and FF of 0.61. This MNT-based mini 3D DSSC is a promising photovoltaic device for applications in the fields of high-integrated micro-electronic equipment.     

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.     

A simple dye-sensitized solar cell sealing technique using a CO2 laser beam excited by 60 Hz AC discharges

Dye-sensitized solar cells (DSSCs) use two glass substrates (photo electrode and counter electrode) coated with fluorine-doped tin oxide (FTO) to harvest light into the cell and to collect electrons. The space between the photo electrode and the counter electrode are filled with a liquid type electrolyte for electron transfer into the cell. Therefore, an appropriate sealing method is required to prevent the liquid electrolyte leaking out. In this paper, a simple CO₂ laser beam with TEM₀₀ mode excited by a 60 Hz AC discharge was used to seal two glass substrates coated with FTO for the fabrication of DSSCs. The sealing technique improved the durability and stability of the DSSCs. The optimal conditions for the sealing of the DSSCs are related to the pin-hole diameter, the discharge current and the moving velocity of the target. Especially, the CO₂ laser beam is used as a heat source that is precisely controlled by the pin-hole, which plays an important role in adjusting its spot size. From these results, the maximum laser power was found to be 40 W at 18 Torr and 35 mA. In order to achieve the best sealing quality, the following parameters are required: a pin-hole diameter of 4 mm, input voltage of 10.73 kV, discharge current of 9.31 mA, moving velocity of 1 mm/s and distance from the target surface of 26.5 cm. Scanning electron microscope images show that the sealing quality obtained using the CO₂ laser beam is superior to that obtained using a hot press or soldering iron.     

An investigation of DNA-like structured dye-sensitized solar cells

This paper reports a 3D DNA-like structured dye-sensitized solar cell (DSSC) with all-Ti substrates. A self-organized TiO₂ nanotubular arrays layer was directly grown on the photoanode surface by electrochemical anodization. Compared with the traditional flat-type DSSC, the DNA-like DSSC showed superiority of light utilization due to its symmetrical double-helix structure. Different thickness of the nanotubular arrays layers were investigated to find their influence on the cell’s photovoltaic parameters, and the cell with a 15.3 μm layer exhibited the highest P_max, about 0.49 mW. The series–parallel connection characteristics of the DNA-like DSSCs reveal that the total voltage and the total short current equalled the sum of each cell’s in series and in parallel, respectively. It is anticipated that the novel DNA-like structured DSSCs have great application potential in larger modules using integrated circuit.     

Application of polyaniline nanowires electrodeposited on the FTO glass substrate as a counter electrode for low-cost dye-sensitized solar cells

Polyaniline nanowires (PANI NWs) were deposited onto fluorine-doped tin oxide (FTO) glass substrate using the cyclic voltammetric method with aniline monomer precursor in HCl aqueous solution. The secondary oxidation peak plays an important role in polymerization of aniline monomer and the optimization of catalytic activity of PANI-based counter electrodes was achieved by controlling the number of cycles. The photovoltaic performance of the dye-sensitized solar cells (DSSCs) with PANI NWs counter electrodes (CEs) was optimized at 4th cycles, and then following parameters were obtained: J_sc = 17.2 mA cm⁻², V_oc = 0.71 V, FF = 59.3%, and efficiency (η) = 7.24%. While, J_sc = 14.7 mA cm⁻², V_oc = 0.77 V, FF = 70.6%, and efficiency (η) = 7.98% in cells with Pt CEs. The PANI NWs were attractive as an alternative CEs for the low-cost DSSCs instead of Pt.     

Optimization of F-doped SnO2 electrodes for organic photovoltaic devices

Fluorine-doped tin oxide (FTO) thin films have been investigated as an alternative to indium tin oxide anodes in organic photovoltaic devices. The structural, electrical, and optical properties of the FTO films grown by pulsed laser deposition were studied as a function of oxygen deposition pressure. For 400 nm thick FTO films deposited at 300°C and 6.7 Pa of oxygen, an electrical resistivity of 5×10⁻⁴ Ω-cm, sheet resistance of 12.5 Ω/□, average transmittance of 87% in the visible range, and optical band gap of 4.25 eV were obtained. Organic photovoltaic (OPV) cells based on poly(3-hexylthiophene)/[6,6]-phenyl-C₆₁-butyric acid methyl ester bulk heterojunctions were prepared on FTO/glass electrodes and the device performance was investigated as a function of FTO film thickness. OPV cells fabricated on the optimum FTO anodes (∼300–600 nm thick) exhibited power conversion efficiencies of ∼3%, which is comparable to the same device made on commercial ITO/glass electrodes (3.4%).     

Photocatalytic TiO2 thin films deposited on flexible substrates by radio frequency (RF) reactive magnetron sputtering

Titanium dioxide (TiO₂) thin films were deposited on flexible polycarbonate (PC) substrates by radio frequency (RF) reactive magnetron sputtering. The target was metallic titanium, argon was the plasma gas and oxygen was the reactive gas. Taguchi’s method, which uses an L₉ (3⁴) orthogonal array, signal-to-noise ratio and analysis of variance (ANOVA), was employed to study the performance of the deposition process. The effects of the deposition parameters on the structure, morphology and photocatalytic performance of the TiO₂ films were analyzed using scanning electron microscopy (SEM), X-ray diffraction, and UV-vis-NIR spectroscopy. Experiments varied RF power (50, 100, 150 W), deposition time (2, 3, 4 h), O₂/(Ar + O₂) argon/oxygen ratios (40, 60, 80%) and substrate temperatures (room, 80, 120 °C), to optimize the photoinduced decomposition of methylene blue (MB). The experimental results illustrate the effectiveness of this approach.     

Nanostructured ZnO thin films by chemical bath deposition in basic aqueous ammonia solutions for photovoltaic applications

This paper presents further insights and observations of the chemical bath deposition (CBD) of ZnS thin films using an aqueous medium involving Zn-salt, ammonium sulfate, aqueous ammonia, and thioure. Results on physical and chemical properties of the grown layers as a function of ammonia concentration are reported. Physical and chemical properties were analyzed using scanning electron microscopy (SEM), X-ray energy dispersive (EDX), and X-ray diffraction (XRD). Rapid growth of nanostructured ZnO films on fluorine-doped SnO₂ (FTO) glass substrates was developed. ZnO films crystallized in a wurtzite hexagonal structure and with a very small quantity of Zn(OH)₂ and ZnS phases were obtained for the ammonia concentration ranging from 0.75 to 2.0 M. Flower-like and columnar nanostrucured ZnO films were deposited in two ammonia concentration ranges, respectively: one between 0.75 and 1.0 M and the other between 1.4 and 2.0 M. ZnS films were formed with a high ammonia concentration of 3.0 M. The formation mechanisms of ZnO, Zn(OH)₂, and ZnS phases were discussed in the CBD process. The developed technique can be used to directly and rapidly grow nanostructured ZnO film photoanodes. Annealed ZnO nanoflower and columnar nanoparticle films on FTO substrates were used as electrodes to fabricate the dye sensitized solar cells (DSSCs). The DSSC based on ZnO-nanoflower film showed an energy conversion efficiency of 0.84%, which is higher compared to that (0.45%) of the cell being constructed using a photoanode of columnar nanoparticle ZnO film. The results have demonstrated the potential applications of CBD nanostructured ZnO films for photovoltaic cells.     

A comparative study of solution based CIGS thin film growth on different glass substrates

CuIn_xGa_1−xSe_yS_2−y (CIGS) thin films were synthesized on glass substrates by a paste coating of Cu, In, and Ga precursor solution with a three-step heat treatment process: oxidation, sulfurization, and selenization. In particular, morphological changes of CIGS films for each heat treatment step were investigated with respect to the kinds of glass substrates: bare, Mo-coated, and F-doped SnO₂ (FTO) soda-lime glasses. Very high quality CIGS film with large grains and low degree of porosity was obtained on the bare glass substrate. Similar morphology of CIGS film was also acquired on the Mo-coated glass except the formation of an undesired Mo oxide interfacial layer due to the partial oxidation of Mo layer during the first heat treatment under ambient conditions. On the other hand, CIGS film with much smaller grains and higher degree of porosity was gained when FTO glass was used as a substrate, resulting in slight solar to electricity conversion behavior (0.20%). Higher power conversion efficiency (1.32%) was attained by the device with the CIGS film grown on Mo-coated glass in spite of the presence of a Mo oxide impurity layer.     

Effect of fluorine doping on highly transparent conductive spray deposited nanocrystalline tin oxide thin films

The undoped and fluorine doped thin films are synthesized by using cost-effective spray pyrolysis technique. The dependence of optical, structural and electrical properties of SnO₂ films, on the concentration of fluorine is reported. Optical absorption, X-ray diffraction, scanning electron microscope (SEM) and Hall effect studies have been performed on SnO₂:F (FTO) films coated on glass substrates. The film thickness varies from 800 to 1572 nm. X-ray diffraction pattern reveals the presence of cassiterite structure with (2 0 0) preferential orientation for FTO films. The crystallite size varies from 35 to 66 nm. SEM and AFM study reveals the surface of FTO to be made of nanocrystalline particles. The electrical study reveals that the films are degenerate and exhibit n-type electrical conductivity. The 20 wt% F doped film has a minimum resistivity of 3.8 × 10⁻⁴ Ω cm, carrier density of 24.9 × 10²⁰ cm⁻³ and mobility of 6.59 cm² V⁻¹ s⁻¹. The sprayed FTO film having minimum resistance of 3.42 Ω/cm², highest figure of merit of 6.18 × 10⁻² Ω⁻¹ at 550 nm and 96% IR reflectivity suggest, these films are useful as conducting layers in electrochromic and photovoltaic devices and also as the passive counter electrode.     

Effect of 10 MeV electron irradiation on dye-sensitized solar cells

The effect of 10?MeV electrons’ irradiation on dye-sensitized solar cells (DSSCs) has been studied in this paper. J–V characteristics measurements were carried out in order to investigate the degradation of the cells in electron radiation environments. The short-circuit current (J_sc) and maximum power density (P_max) of cells decrease significantly after the electron irradiation. When the irradiation dose increases to 10?kGy, the initial maximum power decreases nearly by 50%. The influences of the electron irradiation on FTO, dye sensitizer and anode were studied to investigate the degradation mechanism of DSSC, respectively. The ultraviolet–visible spectra of FTO show that the absorption peaks of dye decrease, resulting in a decline of the FTO transmittance. According to the X-ray diffraction measurement results, it was found that the particle size of nano-crystalline TiO₂ had changed after the electron irradiation. With the help of SEM, the conglomeration of TiO₂ nano-particles appears after the electron irradiation.     

Dye-sensitized solar cells based on trench structured TiO2 nanotubes in Ti substrate

We have proposed dye-sensitized solar cells (DSSCs) with trench-type TiO₂ nanotube structure to improve the low device efficiency of conventional TiO₂ nanotube DSSCs using Ti substrate. Compared to the conventional standing-type TiO₂ nanotube structure based DSSCs, the trench-type TiO₂ nanotube structure based DSSCs have shown an improvement of device efficiency of approximately 40% due to the large increase of Jsc. In the trench-type TiO₂ nanotube structure, the contact area between the TiO₂ nanotube sidewall and the Ti substrate is significantly increased. This increase of contact area provides more charge transport paths than exist in the conventional standing-type TiO₂ nanotube structure and reduces the electrical resistance between the Ti substrate and the TiO₂ nanotubes. Therefore, the remarkable increase of Jsc is the result of the charge collection efficiency, which is improved due to the increase of contact area between the TiO₂ nanotube sidewall and the Ti substrate in the trench-type TiO₂ nanotube structure. The fabrication of the trench-type TiO₂ nanotube structure is an effective manufacturing process for improving the device efficiency of TiO₂ nanotube based DSSCs using Ti substrate. DSSCs having an 11.9 μm thick trench-type TiO₂ nanotube structure have shown an efficiency of 5.74%.     

Preparation and characterization of F doped SnO2 films and electrochromic properties of FTO/NiO films

The dependence of structural and electrical properties of SnO₂ films, prepared using spray pyrolysis technique, on the concentration of fluorine is reported. X-ray diffraction, FTIR and scanning electron microscope (SEM) studies have been performed on SnO₂:F (FTO) films coated on glass substrates. Measured values of Hall coefficient and resistivity are reported. The 7.5 m% of F doped film had a resistivity of 15 × 10⁻⁴ Ω cm, carrier density of 18.7 × 10¹⁹ cm⁻³ and mobility of 21.86 cm² V⁻¹ S⁻¹. The NiO film was coated on an FTO substrate and its electrochromic (EC) behavior was studied and the results are reported and discussed in this paper.     

The effect of TiCl4-treated TiO2 compact layer on the performance of dye-sensitized solar cell

In order to prevent the charge recombination at the interface between the transparent-conducting oxide (TCO) substrate and electrolyte, a TiO₂ compact layer was deposited on the substrate by hydrolysis of TiCl₄ aqueous solution. Optimum thickness of the compact layer was found to be ∼25 nm, which showed ∼24% increase in the power-conversion efficiency compared with the bare cell. Impedance spectra indicated that the interfacial charge-transfer resistance of TCO/electrolyte interface was increased by more than a factor of three with the TiO₂ compact layer at 0.4 V. Moreover, the electron-carrier lifetime of the 25 nm-deposited cell was improved by a factor of five compared with the bare cell.     

Growth of TiO2 nanosheet-array thin films by quick chemical bath deposition for dye-sensitized solar cells

Rutile TiO₂ nanofilms, which were composed of many nanosheet-array domains with different orientations, were synthesized directly on fluorine-doped SnO₂ conductive glass (FTO) substrates by a chemical deposition method in a short time in this paper. The average thickness of the nanosheets is about 10 nm; the nanosheets in each domain were parallel to each other and perpendicular to the substrate. The size and profile of the domains have a good correspondence to those of the FTO grains of the substrate, indicating a coherent nucleating and epitaxial growing nature of the films. The nanosheets split gradually and finally developed into nanofibers on prolonging the growing time to 20 h. Dye-sensitized solar cells, which were fabricated with the films, present an open-circuit voltage of 0.63 V and a short-circuit current of 7.02 mA/cm², respectively.     

Growth of nanocrystalline TiO2 films by pulsed-laser-induced liquid-deposition method and preliminary applications for dye-sensitized solar cells

A novel technique, the pulsed-laser-induced liquid-deposition (PLLD) method, has been employed to grow nanocrystalline TiO₂ films on fluorine-doped tin-oxide-coated (FTO) glass substrates at room temperature. The PLLD method was implemented by directing a pulsed laser into a liquid precursor and depositing the photosynthesized nanocrystalline TiO₂ on an FTO glass substrate immersed in the liquid precursor. The as-grown nanocrystalline TiO₂ films were found to have a rutile crystal structure and consist of a number of flower-like TiO₂ crystal units arrayed together on the FTO glass substrate. Each of the flower-like TiO₂ crystal units was composed of many nanostructured TiO₂ whiskers, and their building blocks were found to be bundles of TiO₂ nanorods with diameter of about 5 nm. The growth of these TiO₂ nanorods is highly anisotropic, with the preferential growth direction along [001]. As-grown nanocrystalline TiO₂ films were annealed at 450°C in air for 30 min for the applications of dye-sensitized solar cells, and the nanostructured characteristics with good porosity were preserved after annealing. A preliminary dye-sensitized solar cell was built based on the annealed nanocrystalline TiO₂ film. The results suggest that the PLLD method is a promising technique for growing nanocrystalline TiO₂ films for photovoltaic applications.     

Morphological,photovoltaic, and electron transport properties of In2O3-based DSSC with different concentrations of MWCNTs

This study focuses on the influence of loading MWCNTs in In₂O₃-based DSSCs. In₂O₃-MWCNTs were prepared by sol-gel method via spin coating technique and annealed at 450 °C. The structural, morphology, and electrical properties of the photoanodes were characterized by means of XRD, AFM and FESEM, and J-V curve measurement and EIS properties, respectively. Incorporation of MWCNTs in In₂O₃ improved the J _sc and V _oc of the cell. However, excess loading of MWCNTs in In₂O₃ caused a serious aggregation of MWCNTs that increased the recombination rate. Thus, In₂O₃-MWCNTs with 0.3 % of MWCNTs achieved the highest PCE of 1.23 % with large surface area for efficient dye adsorption. Moreover, In₂O₃-MWCNTs_(0.3%) exhibited large D _eff about 25.7 × 10⁻³ cm² s⁻¹ with low recombination effect that increased the PCE. This study suggests an optimum MWCNT incorporation of 0.3 % in the photoanode by sol-gel synthesis method of developing In₂O₃-based nanocomposite.

     

AZO/Ag/AZO multilayer films prepared by DC magnetron sputtering for dye-sensitized solar cell application

Ag films were deposited on Al-doped ZnO (AZO) films and coated with AZO to fabricate AZO/Ag/AZO multilayer films by DC magnetron sputtering on glass substrates without heating of glass substrates. The best multilayer films have low sheet resistance of 19.8 Ω/Sq and average transmittance values of 61% in visible region. It was found that the highest figure of merit (F_TC) is 6.9 × 10⁻⁴ Ω⁻¹. For the dye-sensitized solar cell (DSSC) application, the multilayer films were used as transparent conductive electrode (multilayer films/ZnO + Eosin-Y/LiI + I₂/Pt/FTO). The best DSSC based on the multilayer films showed that open circuit voltage (V_oc) of 0.47 V, short circuit current density (J_sc) of 2.24 mA/cm², fill factor (FF) of 0.58 and incident photon-to-current conversion efficiency (η) of 0.61%. It was shown that the AZO/Ag/AZO multilayer films have potential for application in DSSC.     

Role of sweep direction and substrate work function on resistive switching of titanium-di-oxide [TiO2] nanoparticles

The resistive switching mechanism in titanium-dioxide nanoparticles (TiO₂ NP) is studied using the current-voltage (I–V) measurements. The TiO₂ NP are spin-coated on different substrates like FTO, ITO, Gold, and p-Silicon. The I–V measurements are carried out by changing the initial potential of the substrates to either 0 V (sweep1) or −1 V (sweep2). Resistive switching (RS) was observed only for FTO/TiO₂ NP and ITO/TiO₂NP devices in sweep1 direction. Whereas, in sweep2 direction, no such RS was observed in any of the devices. The detailed I–V analysis infers the Ohmic conduction followed by space charge limited conduction (SCLC) during the RS forming process for FTO/TiO₂ NP and ITO/TiO₂NP devices. The Au and p-Si substrates act as blocking contact for TiO₂ and exhibit Schottky/thermionic emission at lower voltages and SCLC at higher voltages. The TiO₂ NP coated on p-Si substrate exhibits rectifying behaviour with a current ratio of 3 orders of magnitude.