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.     

The effect of ZnO-coating on the performance of a dye-sensitized solar cell

This study investigates the effect of a ZnO-coated TiO₂ working electrode on the power conversion efficiency of a dye-sensitized solar cell (DSSC). This electrode was designed and fabricated by dipping the TiO₂ electrode with the TiCl₄ treatment in a solution of zinc acetate dehydrate [Zn(CH₃COO)₂·2H₂O] and ethanol. The effects of the concentration of Zn(CH₃COO)₂·2H₂O and the duration of dipping on the band gap of a working electrode and the power conversion efficiency of a DSSC were also examined. The band gap of the working electrode increases to 3.75 eV [TiO₂ electrode dipped in 0.05 M Zn(CH₃COO)₂·2H₂O) for 3 min] from 3.22 eV (TiO₂ electrode). Interestingly, the power conversion efficiency of the DSSC with a Zn-coated TiO₂ electrode (6.7%) substantially exceeds that of the conventional DSSC with a TiO₂ electrode (5.9%), and it may be originated from an increased energy barrier between ZnO and TiO₂ that reduces the electron recombination rate.     

A quasi solid-state dye-sensitized solar cell containing binary ionic liquid and polyaniline-loaded carbon black

A quasi solid-state dye-sensitized solar cell (DSSC) is fabricated using 1-propyl-3-methylimidazolium iodide (PMII) and polyaniline-loaded carbon black (PACB) as the composite electrolyte. The electrolyte without added iodine is sandwiched between TiO₂ working electrode and platinum counter electrode (CE). A power conversion efficiency (η) of 5.81% is achieved with this type of cell. With the addition of 1-ethyl-3-methylimidazolium thiocyanate (EMISCN), a low-viscosity ionic liquid (IL), the cell with the binary ionic liquid (bi-IL) renders an efficiency of 6.15%, the best for any quasi solid-state DSSC without the addition of iodine. To fabricate a low cost DSSC using the bi-IL, the platinum layer of the counter electrode is replaced with a polymer layer, 3,3-diethyl-3,4-dihydro-2H-thieno-[3,4-b][1,4] dioxepine (PProdot-Et₂) through electrodeposition, and the corresponding DSSC shows an efficiency of 5.27%. At-rest stability of the quasi solid-state DSSC with bi-IL is compared with that of a liquid electrolyte DSSC at room temperature; the power conversion efficiency of the former shows a decrease of hardly 3% after 1000 h, while that of the latter shows a decrease of about 30%. The quasi solid-state cell shows unfailing durability at 70 °C.     

Newly designed dye-sensitized solar cells fabricated with double-layered TiO2 (bottom layer)/Bx–TiO2 (top layer) combined electrodes for improved photocurrent

An unusual double-layered TiO₂ (bottom layer)/B_x–TiO₂ (top layer) combined electrode array was investigated to improve the photocurrent in dye-sensitized solar cells (DSSCs). A positive semiconductor, B_x–TiO₂, with nanometer-sized B (1.0, 5.0, and 10.0 mol%)-incorporated TiO₂ prepared using a solvothermal method, was utilized as the working electrode material by coating onto the second level above the TiO₂ electrode. The photocurrent and photovoltaic efficiency of the TiO₂ (bottom)/B_x–TiO₂ (top)-DSSC were 20.5% and 17.3% greater, respectively, than that of the double-layers of anatase TiO₂–DSSC in the photocurrent–voltage (I–V) curve of the optimal electrode. This result was attributed to their energy levels of reduction (LUMO)/oxidation (HOMO) as determined by cyclic voltammetry (CV). As the LUMO level of B_x–TiO₂ was located at a slightly higher level than that of pure anatase TiO₂, the electrons donated from the dye were easily transferred to the surface of the TiO₂ electrode without electron loss. Moreover, the recombination was also much slower in the TiO₂ (bottom)/B_x–TiO₂ (top)-based DSSCs than in the double-layered pure TiO₂ DSSC.     

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.     

Thickness effect of RF sputtered TiO2 passivating layer on the performance of dye-sensitized solar cells

We report on the characteristics of a TiO₂ passivating layer grown by radio frequency (RF) magnetron sputtering on F-doped SnO₂ (FTO) electrodes as a function of its thickness. The optical transparency, surface roughness and passivation properties of the TiO₂ layer passivating the FTO electrode depend on the thickness of the TiO₂ passivating layer. In addition, it was found that the power conversion efficiency of the dye-sensitized solar cells (DSSCs) is critically dependent on the thickness of RF sputtered TiO₂ layer inserted between FTO electrode and nanoporous TiO₂ layer. The DSSC fabricated on 50 nm thick TiO₂ passivating FTO electrode showed the maximum power conversion efficiency of 4.42% due to effective prevention of the electron transfer to electrolyte. This indicates that the thickness optimization of the TiO₂ passivating layer is one of the important parameter to obtain high performance DSSCs.     

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.     

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.     

Improved performance of a dye-sensitized solar cell using a TiO2/ZnO/Eosin Y electrode

TiO₂/ZnO/Eosin Y structure films were prepared by a one-step cathodic electrodeposition method and used as a photoanode in a dye-sensitized solar cell (DSSC). Using this TiO₂/ZnO/Eosin Y electrode in DSSC, the degradation of the cell with time was reduced and I_SC, V_OC and fill factor values were increased. The use of a thin ZnO layer, permitted the formation of an energy barrier at the electrode/electrolyte interface, thus reducing recombination rate and improving cell performance. In addition, the adsorbed dye molecules prepared by one-step cathodic electrodeposition with ZnO were very stable compared with that prepared by conventional immersing method, as evidenced by UV/vis absorption spectroscopy measurements.     

Highly efficient dye-sensitized solar cell prepared by electrophoretic deposition method: the effect of TiO<Subscript>2</Subscript> films thickness on the performance of cells

In this work, nanocrystalline P25 TiO₂ films with different thicknesses were deposited on FTO coated glass substrates by an electrophoretic deposition technique (EPD) and applied as the work electrode for dye-sensitized solar cells (DSSC) using cis-bis(isothiocyanato)(2,2'-bipyridyl-4,4'-dicarboxylato)(4,4'di-nonyl-2'-bipyridyl) ruthenium(II) (Z907, Dyesol) as sensitizing dye.The results showed that the increasing the thickness of TiO₂ films lead to increase the adsorption of the dye on the TiO₂ layers which in turns improved the short-circuit photocurrent (J_sc) and open-circuit voltage (V_oc), respectively. Furthermore, it was found that the effects of the surface states on the recombination of the photo-injected electrons (electron–hole pairs) in the TiO₂ films strongly depend on theTiO₂ electrode annealing temperature. Finally, a DSSC with a 32.82 μm thickness for TiO₂ film annealed at 600°C produced the highest conversion efficiency with an incident solar energy of 100 mW/cm² (η = 8.23%, J_sc = 15.98, V_oc = 0.73, FF = 0.7).     

Influence of scattering layers on efficiency of dye-sensitized solar cells

Thin titaniumdioxide (TiO₂) semiconductor layer with different scattering layers was investigated in dye-sensitized solar cells (DSSC). Since the cost of the photoactive dye in the DSSC is relatively high, it is reasonable to assume that the price of the dye could be one of the decisive factors in determining the price of the DSSC modules. Use of a thin layer of nanocrystalline TiO₂ would imply reduction in the amount of dye coverage, however, lower amount of dye in the thin films would imply fewer electron generation upon illumination. Thus, it becomes necessary to include a light scattering layer such that the lower photon conversion due to thin layer could be compensated. In the present study up to 80% increase in current density was observed due to inclusion of scattering layers. Reflectance and transmittance measurements were employed in order to study the optical properties of these scattering layers. The scattering layers, which are considered here, are TiO₂-Rutile, zirconiumdioxide (ZrO₂), and layers consisting of these two in various proportions. With a 4 μm thin titanium dioxide semiconductor layer as photo electrode and an additional light scattering layer (consisting of TiO₂-Rutile and ZrO₂ in a ratio of 1:3), efficiencies of 6.8% were achieved.     

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.     

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.     

Synthesis of TiO2 submicro-rings and their application in dye-sensitized solar cell

In this paper, novel TiO₂ submicro-rings were synthesized via potentiostatic anodization of titanium powder coated on transparent conducting oxide glass. The TiO₂ submicro-rings film was characterized by SEM, XPS and 3D optical profiling. Accordingly, a possible growth mechanism of submicro-rings was discussed. The TiO₂ submicro-rings based dye-sensitized solar cell (DSSC) with the film thickness of ca. 3.1 μm was assembled and a conversion efficiency of 1.36% was achieved under AM 1.5 illumination. The photoelectron transport properties of TiO₂ submicro-rings based DSSC were also discussed according to the electron impedance spectroscopy.     

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.     

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.     

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.     

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.     

Synthesis of TiO2 nanoparticles at low hydrothermal temperature and its performance for DSSC sensitized using natural dye extracted from Melastoma malabathricum L. seeds

Efficiency of a dye‐sensitized solar cell (DSSC) device depends on its semiconductor layer and the sensitizing dye to absorb the light. This work seeks to obtain the best solvent for the natural dye extraction from Melastoma malabathricum L. seeds. The extracted dye is used as sensitizer on TiO₂ nanoparticles produced via hydrothermal but optimized at relatively low temperature. Infrared characterization of the extracted dyes showed differences in functional groups using different solvents, whereas ultraviolet visible examination of the dyes showed differences in intensity along the spectrum ranges of 600 to 400 nm with maximum absorption around 550 to 500 nm. Thermal analysis revealed that the natural dye should be stable around room temperature. Analysis on the synthesized TiO₂ nanoparticles showed that the average crystallite size reported in the previous work is consistent with crystallite sizes observed in the transmission electron microscope images. Photoactivity examination showed that the DSSC sensitized using natural dye extracted with ethanol containing 20% distilled water on TiO₂ synthesized at 150°C has an efficiency of 5.7%, whereas the one on commercial TiO₂ P25 Degussa has an efficiency of 3.0%. The DSSC device sensitized using commercial dye on TiO₂ synthesized at 150°C has an efficiency of 4.4%, whereas the one on TiO₂ P25 Degussa has an efficiency of 4.0%. This result is promising for further development of the DSSC device using TiO₂ nanoparticles synthesized at low hydrothermal temperature and sensitized with the natural dye.     

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.