The effects of hydrothermal temperature and thickness of TiO2 film on the performance of a dye-sensitized solar cell

The effects of hydrothermal temperature on the preparation of TiO₂ colloids, and their film thickness on fluorine-doped tin oxide (FTO) glass, toward the performance of a dye-sensitized solar cell (DSSC) were investigated. Pore diameter and surface area of the TiO₂ are of paramount importance in determining the cell efficiency. With the increase of hydrothermal temperature, the pore diameter increases linearly; however, the surface area shows the reverse effect. It is found that the DSSC assembled with the TiO₂ films prepared under the hydrothermal temperature of 240 °C, and the film thickness larger than 10 μm gives optimal performance. The effect of film thickness of TiO₂ on the performance of the DSSC can be explained by the relative size of reactive species diffusing into the thin film and the lifetime of injected electrons. Electrochemical impedance spectroscopy (EIS) was also used to analyze the resistance of the cell, developed as a result of the change in the thickness of the TiO₂ thin film. The at-rest stability for over 200 days was monitored and the results show that the solar energy conversion efficiency was found to decrease from 5.0% of initial value to 3.0% at the end.     

On the photophysical and electrochemical studies of dye-sensitized solar cells with the new dye CYC-B1

In this study, the photoelectrochemical characteristics of a ruthenium photosensitizer with an alkyl bithiophene group, designated as CYC-B1, are studied. The effect of mesoporous TiO₂ film thickness on the photovoltaic performance of CYC-B1 and N3 dye-sensitized solar cells was investigated. The performance of the dye-sensitized nanocrystalline TiO₂ solar cells (DSSC) fabricated using CYC-B1 dye-anchored TiO₂ photoelectrode showed a convincing enhancement in cell efficiency when the TiO₂ film thickness was increased from 3 μm (eff.=5.41%) to 6 μm (eff.=7.19%). The efficiency of the CYC-B1-sensitized DSSC was maximum at 6 μm of the TiO₂ film thickness, reached its limiting value and remained constant up to 53 μm, although a similar trend was also observed for N3 dye-sensitized DSSC, however, the maximum efficiency achieved was only at 27 μm thickness (eff.=6.75%). As expected, the photocurrent density generated in the DSSC modified by CYC-B1 dye is larger than that from N3 dye. The effect of guanidinium thiocyanate (GuSCN) (additive) addition to the electrolyte on the photovoltaic performance of DSSCs based on CYC-B1 was also investigated. Furthermore, the electrochemical impedance spectroscopy (EIS) technique and photo-transient laser method have been employed to analyze the charge transfer resistances (R_ct) and the lifetime of the injected electrons on the TiO₂ containing different thicknesses.     

Photovoltage enhancement of dye sensitised solar cells by using ZnO modified TiO2 electrode

Abstract

A ZnO modified TiO₂ (ZnO/TiO₂) film was prepared by immersing TiO₂ electrodes in Zn(Ac)₂ aqueous solution. The open circuit voltage of a dye sensitised solar cell (DSSC) with the ZnO/TiO2 film electrode has a dramatic enhancement, compared to the DSSC with the TiO₂ film electrode. However, the short circuit current density of the DSSC with the ZnO/TiO₂ film electrode is lower than that with TiO₂ electrode. The film electrodes were characterised by SEM, EDX and UV-vis, and the photoelectric performance of DSSCs were measured. The photovoltage enhancement is attributed to the formation of a flat-band potential energy barrier by ZnO at TiO₂/electrolyte interface. The decline of the photocurrent with ZnO/TiO₂ film electrode is due to poor dye absorption on larger particles of ZnO.     

Influence of electrolyte on the photovoltaic performance of a dye-sensitized TiO2 solar cell based on a Ru(II) terpyridyl complex photosensitizer

We have investigated the influence of electrolyte composition on the photovoltaic performance of a dye-sensitized nanocrystalline TiO₂ solar cell (DSSC) based on a Ru(II) terpyridyl complex photosensitizer (the black dye). We have also spectroscopically investigated the interaction between the electrolyte components and the adsorbed dye. The absorption peaks attributed to the metal-to-ligand charge transfer transitions of the black dye in solution and adsorbed on a TiO₂ film, were red-shifted in the presence of Li cations, which led to an expansion of the spectral response of the solar cell toward the near-IR region. The photovoltaic performance of the DSSC based on the black dye depended remarkably on the electrolyte composition. We developed a novel efficient organic liquid electrolyte containing an imidazolium iodide such as 1,2-dimethyl-3-n-propylimidazolium iodide or 1-ethyl-3-methylimidazolium iodide (EMImI) for a DSSC based on the black dye. A high solar energy-to-electricity conversion efficiency of 9.2% (J_sc=19.0 mA cm⁻², V_oc=0.67 V, and FF=0.72) was attained under AM 1.5 irradiation (100 mW cm⁻²) using a novel electrolyte consisting of 1.5 M EMImI, 0.05 M iodine, and acetonitrile as a solvent with an antireflection film.     

Solid-state dye-sensitized solar cell with p-type NiO as a hole collector

A solid-state dye-sensitized solar cells (DSSC) comprising of p-type NiO thin layer on TiO₂ was fabricated in which the dye is adsorbed on the p-type oxide and the thin NiO layer acts as a hole collector as well as a barrier for charge recombination. DSSC with NiO-coated TiO₂ electrodes with Ru-dye delivers I_sc=0.15 mA and V_oc=480 mV. It was shown that the p-type oxide materials could be successfully used to construct DSSC and the plausible charge transfer mechanism is discussed.     

Effect of TiO2 photo-electrode growth condition on dye-sensitised solar cells

Titanium dioxide- (TiO₂) based photo-electrode for dye-sensitised solar cells (DSSCs) use is fabricated with the electro-phoretic deposition (EPD) technique on indium-tin-oxide (ITO). TiO₂ films were synthesised at different EPD biases ranging from 70 to 110 V. We correlate the morphological and optical properties of formed films to the electrical characteristics of fabricated DSSCs. In addition, by neglecting the tunnelling and the tunnelling-assisted thermo-ionic currents with respect to the pure thermo-ionic current at the ITO/TiO₂ interface, we evaluate the high potential barrier, e?_B. Investigation of the electrical properties of the formed DSSCs shows a best result when the TiO₂ film is elaborated at 100 V. Furthermore, by taking into account the high band energy of 0.6 eV at an aluminium-based counter electrode/electrolyte interface, we deduce that aluminium reduces drastically the short-circuit current of the DSSC.     

Optimization of paste formulation for TiO2 nanoparticles with wide range of size distribution for its application in dye sensitized solar cells

Dye sensitized solar cell (DSSC) can be an economically viable and technically simpler alternate to the silicon based solar cells. Films of nanocrystalline titanium dioxide (TiO₂) are considered as the most suitable photoelectrode for DSSC. For this study, TiO₂ powder of anatase phase, synthesized in acidic environment was used. The average diameter of the nanoparticles was ～20 nm and BET surface area was 64.68 m²/g. Different TiO₂ pastes were prepared by varying the proportion of TiO₂ powder, α-terpineol, and ethyl cellulose (EC) in their composition. The TiO₂ paste was cast on fluorine doped tin oxide (FTO) coated glass surface using doctor blade to prepare photoelectrode of TiO₂ film. Composition of the paste ingredients was optimized by comparing the conversion efficiencies of the DSSCs fabricated with the photoelectrode of thickness ～18 μm. The outcome of this study can be crucial for the preparation of reliable TiO₂ paste in a simple way for its application in DSSC.     

Influences of different TiO2 morphologies and solvents on the photovoltaic performance of dye-sensitized solar cells

The effects of TiO₂ photoelectrode's surface morphology and different solvents on the photovoltaic performance of dye-sensitized solar cells (DSSCs) were studied. By successive coating of TiO₂ suspension, composed of low and high molecular weight poly(ethylene)glycol (PEG) as a binder, double layered TiO₂ photoelectrodes with four different structures were obtained. Among the DSSCs with different TiO₂ electrodes, DSSC with P2P1 electrode (P2 and P1 correspond to PEG molecular weights of 20,000 and 200,000, respectively) showed higher performance under identical film thickness at a constant irradiation of 100 mW cm⁻², which may be correlated with large pore size and high surface area of the corresponding TiO₂ electrode. This was confirmed by electrochemical impedance spectroscopy (EIS) analysis of the DSSC and the transient photovoltage measurement of electrons in the TiO₂ electrode. Among the different solvents investigated here, the DSSC containing acetonitrile showed high conversion efficiency and the order of performance of the DSSCs with different solvents were AN > MPN > PC > GBL > DMA > DMF > DMSO. Better correlation was observed between the donor number of solvents and photoelectrochemical parameters of the DSSCs containing different solvents rather than the measured viscosity and dielectric constant of solvents. The reasons for the low performance of the DSSCs containing DMA, DMSO and DMF, respectively, were due to the negative shift of TiO₂ conduction band and the desorption of dye molecules from the TiO₂ photoelectrode by those solvents.     

Theoretical modeling of TiO2/TCO interfacial effect on dye-sensitized solar cell performance

A theoretical model based on an integration of both Schottky barrier model and electron diffusion differential model was developed to determine the TiO₂/TCO interfacial effect on the current–voltage (J–V) characteristics of a dye-sensitized solar cell (DSSC). The thermionic-emission theory was appropriately applied to describe the electron transfer at the TiO₂/TCO interface. A parametric analysis was conducted to study how the photoelectric outputs varied with multiple independent variables, such as Schottky barrier height (φ_b) and temperature. It was found that the variation of the maximum DSSC power output (P_max) was insignificant when φ_b varied at a low value; however, an increase in φ_b exceeding a critical value caused an apparent decrease in the maximum DSSC power output. The theoretical results were quantitatively compared and agreed very well with published theoretical results. The experimental data from literature were found to agree well with the present theoretical results, qualitatively validating the present model. The theoretical model can be applied to facilitate selection of suitable TCO material in DSSC design to avoid the adverse TiO₂/TCO interfacial effect.     

Plastic dye-sensitized photo-supercapacitor using electrophoretic deposition and compression methods

A plastic photo-rechargeable capacitor is studied using a three-electrode configuration, separating a flexible dye-sensitized solar cell (DSSC) and a supercapacitor by sharing a common Pt electrode. The thick and uniform TiO₂ film is formed by using commercially available TiO₂ nanocrystals, which are treated in an isopropyl alcohol without surfactant by the electrophoretic deposition (EPD) to deposit the mesoporous TiO₂ photoanode film with good adherence onto the plastic substrate. Afterward, a static mechanical compression technique as the post-treatment is employed to the electrophoretic deposited film in order to enhance the particles connection. In addition, a supercapacitor using PEDOT (poly(3,4-ethylenedioxythiophene)), which is potentiostatically electropolymerized to form a thick film, is fabricated to store the energy. The flexible DSSC part is fabricated with a TiO₂ film of 10.9 μm thickness and it can provide photoelectric conversion efficiency up to 4.37% under 1 sun illumination. The photocapacitor is made with such a flexible DSSC and a supercapacitor with ca. 0.5 mm thick PEDOT film, which provides a specific capacitance of 0.52 F cm⁻².     

Hydrogen treated TiO2 nanoparticles onto FTO glass as photoanode for dye-sensitized solar cells with remarkably enhanced performance

Hydrogen treatment is a facile and efficient approach for the enhancement in the functioning of TiO₂ nanoparticles for dye-sensitized solar cells (DSSC). In this work, TiO₂ nanoparticles have been synthesized in the hydrogen environment followed by the deposition onto FTO glass substrates with various film thickness as photoanodes for DSSC. The synthesized hydrogen treated TiO₂ nanoparticles based photoanodes have showed significantly improved photocurrent in the resulting fabricated devices. SEM and TEM analyses have confirmed the particle size and morphology of TiO₂ nanoparticles at various magnifications. The crystalline structure and phase identification were studied by XRD analysis and Raman spectroscopic measurements. The UV–Vis spectroscopy analysis was carried out to find the response of samples for ultraviolet and visible light. The current-voltage measurements have confirmed the improvement of photocurrent that is principally due to improved photo-activity of hydrogen treated TiO₂ nanoparticles. Moreover, hydrogen treated TiO₂ nanoparticles-based photoanode with the film thickness of 11.65 μm has remarkably enhanced power conversion efficiency of 6.05% in DSSCs. The ability of highly photoactive hydrogen treated TiO₂ nanoparticles will provide the new openings in different fields that include photo-electrochemical water splitting and in many other applications.     

Low-temperature oxygen plasma treatment of TiO2 film for enhanced performance of dye-sensitized solar cells

The effects of low-temperature O₂ plasma treatment of a TiO₂ film are studied with the objective of improving the performance of dye-sensitized solar cells (DSSCs). X-ray photoelectron spectra (XPS) reveal that the ratio of titanium dioxide to titanium sub-oxides is increased in the O₂ plasma-treated TiO₂ film, compared with that of the untreated TiO₂ film. This increase suggests that the oxygen vacancies in the film are effectively reduced. The near-edge X-ray absorption fine structure (NEXAFS) spectra results agree with the XPS result. It is proposed that there is a correlation between the shifts of the peaks in the NEXAFS spectra and the adsorption of N719 dye on the TiO₂ particles. A DSSC having an O₂ plasma-treated, 4 μm thick TiO₂ film electrode renders a short-circuit photocurrent of 7.59 mA cm⁻², compared with 6.53 mA cm⁻² for a reference cell with an untreated TiO₂ electrode of the same thickness. As a result of these changes, the solar-to-electricity conversion efficiency of the O₂ plasma-treated cell is found to be 4.0% as compared with 3.5% for the untreated cell. This improvement in the performance is rationalized on the basis of increased N719 dye adsorption on to the TiO₂, due to the reduction in the number of oxygen vacancies caused by the oxygen plasma treatment.     

Anchorage of N3 dye-linked polyacrylic acid to TiO2/electrolyte interface for improvement in the performance of a dye-sensitized solar cell

A synthetic route was developed to link N3 dye to polyacrylic acid (PAA) using ethylenediamine (en) as the linker. The resulting complex, PAA–en–N3, was then coated onto a TiO₂ film. The modified TiO₂ film electrode (hereafter PAA–en–N3/TiO₂), when used as the photoanode in a dye-sensitized solar cell (DSSC), exhibited enhanced solar energy conversion efficiency compared with that of the usual DSSC with the N3/TiO₂ film electrode. The increase in efficiency was attributed to the increased open-circuit voltage (V_oc) and short-circuit photocurrent (J_sc). The increase in V_oc was attributed to the formation of a hydrophobic PAA–en–N3 layer on the TiO₂/electrolyte interface, while the increase in J_sc was attributed to the additional dye acquired by the TiO₂ film from the PAA–en–N3 complex.     

Columnar rutile TiO2 based dye-sensitized solar cells by radio-frequency magnetron sputtering

Columnar-structured rutile TiO₂ film with a thickness of 1.4 μm is prepared using the radio-frequency (RF) magnetron sputtering technique, for application in dye-sensitized solar cells (DSSCs). Pure rutile TiO₂ films are fabricated by controlling the substrate temperature during sputtering and using a substrate with a rough surface morphology. Successive substrate heating to 623 K induces the growth of a rutile TiO₂ film that has a specific direction in the (1 1 0) plane, which results in a decrease in the average grain size. This causes in an increase of dye uptake and thereby contributes to enhancement of the photocurrent in the DSSC.     

CTAB facilitated spherical rutile TiO2 particles and their advantage in a dye-sensitized solar cell

Spherical rutile TiO₂ particles (14–20 nm) and their corresponding well-defined round clusters (500–600 nm) were obtained by using a cationic surfactant cetyltrimethylammonium bromide (CTAB). The surfactant was employed in two stages, i.e., in the hydrolysis of TiCl₄ and then in the precipitation of the corresponding Ti(IV) polymers at approximately 46 °C. On the other hand, without CTAB in the hydrolyzing solution, irregular clusters consisting of typical ellipsoidal TiO₂ particles were produced. The advantage of such spherical rutile TiO₂ particles and clusters was examined in terms of photovoltaic characteristics of a dye-sensitized solar cell (DSSC). Significantly higher overall solar energy conversion efficiency was obtained for a DSSC using the film of these spherical rutile TiO₂ particles, compared with that of a cell using a TiO₂ film of ellipsoidal particles. A mechanism for the formation of these spherical rutile particles and clusters is proposed.     

Dye-sensitized solar cells based on anatase TiO2 hollow spheres/carbon nanotube composite films

Dye-sensitized solar cells (DSSCs) based on anatase TiO₂ hollow spheres (TiO2HS)/multi-walled carbon nanotubes (CNT) nanocomposite films are prepared by a directly mechanical mixing and doctor blade method. The prepared samples are characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV-vis absorption spectroscopy and N₂ adsorption-desorption isotherms. The photoelectric conversion performances of the DSSCs based on TiO2HS/CNT composite film electrodes are also compared with commercial-grade Degussa P25 TiO₂ nanoparticles (P25)/CNT composite solar cells at the same film thickness. The results indicate that the photoelectric conversion efficiencies (η) of the TiO2HS/CNT composite DSSCs are dependent on CNT loading in the electrodes. A small amount of CNT clearly enhances DSSC efficiency, while excessive CNT loading significantly lowers their performance. The former is because CNT enhance the transport of electrons from the films to FTO substrates. The latter is due to high CNT loading shielding the visible light from being adsorbed by dyes.     

Algal buffer layers for enhancing the efficiency of anthocyanins extracted from rose petals for natural dye‐sensitized solar cell (DSSC)

Natural dye‐sensitized solar cells (DSSCs) are becoming promising candidates for replacing synthetic dyes. Anthocyanins, a flavonoid pigment which is responsible for the coloration in fruits and flowers, have shown productive results in employing them as natural dye for DSSC. But unfortunately, they exhibit low efficiency compared with synthetic dyes. Probing the reasons for the low efficiency of anthocyanin paves way for finding solution to increase the efficiency. This paper lists the important factors that are responsible for anthocyanin instability in DSSC. As a remedial measure, this paper introduces two buffer layer made of algal byproducts—sodium alginate and Spirulina. Rutile phase TiO₂ nanorods prepared by hydrothermal method were used as photoelectrode and are subsequently characterized by X ray diffraction, transmission electron microscopy, and optical studies. The use of sodium alginate above the photoelectrode has proved to improve the dye concentration in the film by introducing more hydroxyl groups on the surface of TiO₂. Anthocyanins extracted from rose petals using citric acid as solvent were used as dye for DSSC. Prior to the sensitization process with anthocyanin dye, the TiO₂ film (with sodium alginate) was sensitized with Spirulina. The chlorophylls, xanthophylls, phycocyanins, and amino acids present in Spirulina assist the anthocyanins to bond with TiO₂ efficiently. This helps in enhancing the efficiency of anthocyanins of rose dye from 0.99% to 1.47%.     

Tailor and functionalize TiO2 compact layer by acid treatment for high performance dye-sensitized solar cell and its enhancement mechanism

Surface tailoring and functionalization of an annealed TiO₂ compact layer by H₂SO₄ acid was performed to improve the dye-sensitized solar cell (DSSC) performance. Compared to untreated counterpart, the acid-treated compact layer possesses a rougher surface and more hydroxyl groups, which result in increased surface area and enhanced adherence of the compact layer with the mesoporous TiO₂ film by Ti–O–Ti bonds formed by a followed heating process. Impedance measurement was further used to investigate the enhancement mechanism, indicating the acid post treatment of the TiO₂ compact layer reduces the ohmic bulk resistivity while effectively suppressing charge recombination at FTO/electrolyte interface. In DSSCs with untreated TiO₂ compact layer, a significantly increased series resistivity is very likely to be the rate determining factor to limit the charge separation process. Thus, an optimal post acid treatment could reduce the resistivity for high charge transport, resulting in larger short-circuit current for further improvement of power conversion efficiency from 6.60% in DSSC with untreated compact layer to 7.21% in DSSC with acid-treated compact layer. This work also provides fundamental insight of the compact layer for DSSC performance improvement.     

A study on the electron transport properties of TiO2 electrodes in dye-sensitized solar cells

The influences of annealing temperature and different poly (ethylene glycol) (PEG) contents in nano-crystalline TiO₂ electrodes with and without N3 dye on the electron transfer in a dye-sensitized solar cell (DSSC) were investigated. It is found that the power conversion efficiency increases with the increase in annealing temperature and becomes saturated at 400–500 °C, and further increase lowers the performance which is consistent with the enhancement of the crystalline TiO₂ particles observed in X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) images. Electrochemical impedance spectroscopy (EIS) also confirms this behavior. These results have been further verified by studying the electron lifetimes (τ_e) and electron diffusion coefficients (D_e) of a bare TiO₂ and a dye-sensitized TiO₂ film using a pulsed laser spectrometer. It is noted that both the electron lifetime and the electron diffusion coefficient increase with the increase in annealing temperature. However, the evolution of rutile TiO₂ begins beyond 600 °C and this lowers the dye absorbance and the electron diffusion coefficients of TiO₂ electrodes. A similar study was made by varying the content of the PEG in the TiO₂ films. It is found that with the increase in the PEG content, a decrease in the electron lifetimes and a little hike in the electron diffusion coefficients are noted, where the cell performance remains almost the same. In addition, the dye adsorption decreases the electron lifetime and increases the electron diffusion coefficient of the TiO₂ films regardless of the PEG content and the annealing temperature.     

Reduced graphene oxide–titania nanocomposite‐modified photoanode for efficient dye‐sensitized solar cells

We report the successful application of reduced graphene oxide–titania (rGO–TiO₂) nanocomposite as an efficient photoanode for dye‐sensitized solar cell (DSSC). The DSSC assembled with the rGO–TiO₂‐modified photoanode demonstrated an enhanced solar to electrical energy conversion efficiency of 4.74% compared with the photoanode of DSSC composed with unmodified TiO₂ (2.19%) under full sunlight illumination (100 mW/cm², AM 1.5G) as a result of the better charge collection efficiency of rGO, which reduced the back electron transfer process. Influence of the rGO content on the overall efficiency was also investigated, and the optimal rGO content for TiO₂ was 0.5 mg. Further, the modification of rGO–TiO₂ on the compact layer TiO₂ surface led to an increase in efficiency to 5.83%. The superior charge collection and enhanced solar energy conversion efficiency of the rGO–TiO₂ nanocomposite makes it to be used as a promising alternative to conventional photoanode‐based DSSCs. Copyright © 2015 John Wiley & Sons, Ltd.