Influence of TiO2/electrode interface on electron transport properties in back contact dye-sensitized solar cells

The influence of the TiO₂/electrode interface was investigated on electron transport properties at the interface and in TiO₂ porous film in back contact dye-sensitized solar cells. Analysis of dye-sensitized solar cells (DSCs) with Ti and TCO indicated that electron transport properties at TiO₂/Ti and TiO₂/TCO interfaces are similar despite the former's lack of a ‘built-in potential’. The dependence of short circuit current density on TiO₂ thickness indicated that TiO₂ electron transport is not affected by ‘built-in potential’ or electrode structure. Electron transport thus appears similar in back contact dye-sensitized solar cells and DSCs. A back contact dye-sensitized solar cell fabricated with a Ti electrode and optimum TiO₂ porous film showed a conversion efficiency of 7.8% with a metal mask under an air mass of 1.5 sunlight.     

Fabrication of dye-sensitized solar cells by transplanting highly ordered TiO2 nanotube arrays

Highly ordered TiO₂ nanotube arrays fabricated by anodization are very attractive to dye-sensitized solar cells (DSCs) due to their superior charge percolation and slower charge recombination. However, the efficiency of TiO₂-nanotube-based DSCs is 6.89%, which is still lower than that of TiO₂-nanoparticle-based DSCs. We have suggested the transplanting the highly ordered TiO₂ nanotube arrays to FTO glass to improve the performance of TiO₂-nanotube-based DSCs. DSCs based on transplanted TiO₂ nanotube arrays and TiO₂ nanoparticles were fabricated by same process and materials to exclude the unexpected factors. In TiO₂ thickness of ca. 15 μm, the efficiency of 2.91% in front-side illuminated DSCs based on TiO₂ nanotube arrays was higher than those in back-side illuminated DSCs based on TiO₂ nanotube arrays and in front-side illuminated DSCs based on TiO₂ nanoparticle. Front-side illuminated DSCs based on TiO₂ nanotube arrays having various thicknesses were successfully fabricated. The efficiency in DSCs having 20.0 μm thick TiO₂ nanotube arrays was improved to 5.36% by TiCl₄ treatment.     

TiO2 films obtained by microwave-activated chemical-bath deposition used to improve TiO2-conducting glass contact

In traditional solar cells, metal-semiconductor contacts used to extract photogenerated carriers are very important. In dye-sensitized solar cells (DSSC) not much attention has been given to contact between the TiO₂ and the transparent conducting glass (TCO), which is used instead of a metal contact to extract electrons. TiO₂ layers obtained by microwave-activated chemical-bath deposition (MW-CBD) are proposed to improve TiO₂ contact to conducting glass. Spectra of incident photon to current conversion efficiency (IPCE) are obtained for two-photoelectrode TiO₂ photoelectrochemical cells. IPCE spectra show higher values when TiO₂ double layer photoelectrodes are used. In these, the first layer or contacting layer is made by MW-CBD. Best results are obtained for double layer photoelectrodes on FTO (SnO₂:F) as conducting oxide substrate. Modeling of IPCE spectra reveals the importance of electrical contact and electron extraction rate at the TiO₂/TCO interface.     

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.     

TiO2/ZnO/TiO2 sandwich multi‐layer films as a hole‐blocking layer for efficient perovskite solar cells

A continuous and compact hole‐blocking layer is crucial to prevent photocurrent recombination at the photoanode/electrode interface of high‐performance mesostructure perovskite‐based solar cells. Novel TiO₂/ZnO/TiO₂ sandwich multi‐layer compact film prepared as hole‐blocking layer for perovskite solar cell. Herein, TiO₂, ZnO, and TiO₂ layers were successfully deposited by spin‐coating onto FTO glass substrate in sequence. The fill factor and power conversion efficiency of the perovskite solar cell are remarkably improved by the employment of a TiO₂/ZnO/TiO₂ sandwich compact layer. Perovskite solar cell based on TiO₂/ZnO/TiO₂ sandwich film has been observed to exhibit maximum incident‐photon‐to‐current conversion efficiency in the visible region (400–780 nm) and reach a power conversion efficiency of 12.8% under AM1.5G illumination. Copyright © 2016 John Wiley & Sons, Ltd.     

Growth of anatase and rutile TiO2@Sb:SnO2 heterostructures and their application in photoelectrochemical water splitting

We report three-dimensional (3D) nanostructures based on shape- and phase-controlled TiO₂ coated transparent conducting oxide (TCO) nanowire array. Core-shell and branched nanostructures were obtained using an aqueous chemical bath deposition (CBD) method at room temperature. Adjusting the pH of a TiCl₄ solution is a key factor that determines the morphology of the nanostructure. Spherical TiO₂ anatase covered a Sb-doped SnO₂ (ATO) nanowire when pH was maintained at a high level. In contrast, branched nanostructures with TiO₂ rutile nanorods were synthesized by keeping a TiCl₄ solution going down to a low pH. Nanorods were grown epitaxially along the [001] direction on ATO nanowires. Morphological and structural analysis indicates that phases and shapes of the 3D hybrid nanostructure are determined by the pH of the solution and the reaction time. A two-fold higher photoconversion efficiency of rutile TiO₂ rod@ATO was obtained under simulated solar illumination compared to that of the anatase TiO₂ nanoshell@ATO. These 3D hybrid nanostructures can offer (i) a large surface area and efficient charge transport in the TiO₂ nanostructure, and (ii) an effective charge collection path through one-dimensional TCO, which is promising for various areas, including photoelectrochemical water splitting, as well as for application in electronic and photonic nanodevices.     

The effect of a blocking layer on the photovoltaic performance in CdS quantum-dot-sensitized solar cells

In order to reduce the surface recombination at the interface between the fluorine-doped tin oxide (FTO) substrate and the polysulfide electrolyte in CdS quantum-dot-sensitized solar cells (QDSCs), compact TiO₂ is deposited on the FTO electrode by sputtering. The TiO₂-coated CdS-sensitized solar cell exhibits enhanced power-conversion efficiency (0.52%) compared with a bare CdS-sensitized solar cell (0.23%). Charge-transfer kinetics are analyzed by impedance spectroscopy, open-circuit decay, and cyclic voltammetry. The TiO₂ layer deposited on the FTO substrate acts as a blocking layer, which plays a significant role in reducing the electron back transfer from the FTO to the polysulfide electrolyte. Interestingly, with respect to the incident photon-to-current conversion efficiency (IPCE) data, asymmetric enhancement is observed from the sample with a thicker blocking layer. This is because CdS quantum dots absorb ultraviolet light completely with the TiO₂ layer because of the high extinction coefficient of the CdS quantum dots compared with dye molecules.     

Impact of Zn1-xMgxO:Al transparent electrode for buffer-less Cu(In,Ga)Se2 solar cells

Buffer layers such as CdS and ZnS are used in high efficiency Cu(In,Ga)Se₂ (CIGS) thin film solar cells. Eliminating buffer layer is attractive to realize low-cost thin film solar cells by reducing fabrication process. However, the elimination of the buffer layers leads to shunting due to the interface recombination between transparent conductive oxide (TCO) and CIGS layers. To reduce the interface recombination, the control of conduction band offset (CBO) is effective. In this study, we fabricated Zn_1−xMg_xO:Al (ZMO:Al) as the TCO for the CBO control. ZMO:Al was prepared by co-sputtering of ZnO:Al₂O₃ (ZnO:Al) and MgO:Al₂O₃ targets. ZMO:Al shows high transmittance in visible region and the band gap energy widen with the addition of Mg to ZnO:Al. Buffer-less CIGS solar cells with an Al/NiCr/TCO/CIGS/Mo/soda-lime glass structure using ZMO:Al and ZnO:Al were fabricated. For comparison, ZnO/CdS buffered cell was also fabricated. Current density-voltage characteristics of the devices showed the cell with ZMO:Al film achieved higher efficiency compared to the buffer-less cell with ZnO:Al. This result suggested that the control of CBO is important to reduce interface recombination between TCO layer and CIGS absorber.     

The effect of pre-thermal treatment of TiO2 nano-particles on the performances of dye-sensitized solar cells

We have demonstrated the effect of pre-thermal treatment of TiO₂ nano-particles on the performances of dye-sensitized solar cells (DSCs) by using high specific surface area and anatase only TiO₂ nano-particles (ca. 340 m²/g, Sachtleben Chemie GmgH, represented as HK). TiO₂ particles and thin films were characterized with X-ray diffraction, FT-IR, UV–Vis diffuse reflectance spectroscopy and FE-SEM. The photoelectrochemical properties of the thin films and the performances of DSCs were measured by photocurrent densities, AC impedance spectra and photocurrent–voltage curves. Before coating the raw TiO₂ of HK (HK-raw) on transparent conducting oxide (TCO) glass for DSC fabrication, pre-thermal treatment of HK-raw by calcining at 450 °C (HK-450) was an essential step to achieve the optimum properties in terms of morphological feature, crystallinity, specific surface area and photocurrent density. HK-450 film showed the high adsorption of dye, high photocurrent density and low interface resistance between TiO₂ and TCO glass, R_TiO2/TCO and TiO₂ and redox electrolyte, R_CT, resulting in the superior photovoltaic performance on the DSC fabricated with HK-450 and Eosin Y (or ruthenium 535 bis-TBA) at AM 1.5: open-circuit voltage of 0.62 V (0.77 V), short-circuit current of 3.03 mA/cm² (22.80 mA/cm²), fill factor of 0.57 (0.44) and overall conversion efficiency of 1.06%, (7.52%). Accordingly, the optimization between the morphological feature, specific surface area and photocurrent density of TiO₂ substrate is promising to accomplish the improved overall conversion efficiency of DSC.     

Doubled layered ITO/SnO2 conducting glass for substrate of dye-sensitized solar cells

The effects of indium tin oxide (ITO) and ITO/SnO₂ conducting substrates on photovoltaic properties of dye-sensitized solar cells (DSCs) using nanocrystalline TiO₂ were studied. The decrease in fill factor of the DSCs was correlated to the increase in resistance of conducting substrate. The heat stability of ITO conducting glass was improved by depositing SnO₂ on ITO layer. The efficiency of the cells using double layered ITO/SnO₂ substrate remarkably increased comparing with that of the cells using ITO substrates. It is worth mentioning that increasing in sintering time, which enhanced the electronic contact between substrate and TiO₂, also modified the cell performance of MP-TiO₂ cells. Our experimental finding suggests that 3000 Å ITO substrate, which was covered by 1000 Å SnO₂ layer, exhibited the best properties for the DSCs.     

Formation of single-crystalline rutile TiO2 splitting microspheres for dye-sensitized solar cells

The morphological evolution of specimen taken out after the different duration in TiCl₃ solution was investigated by field emission scanning electron microscopy (FE-SEM). The rutile TiO₂ splitting microspheres may be formed by the splitting crystal growth mechanism through the multistep process. The microsphere composed of the 20 nm width nanorods was in the range of 1.5–2.5 μm in the diameter. The dye-sensitized solar cell (DSC) based on the microspheres received 3.57% conversion efficiency under simulated AM 1.5 (100 mW/cm²) solar illumination, which exhibited remarkably higher charge collection efficiency and light scattering compared to that of P25. Electrochemical impedance spectroscopy (EIS) measurement revealed that impedance resistance at the surface of single-crystalline rutile TiO₂ splitting microspheres was 6 times larger than that of P25 nanoparticles, indicating electron recombination was significantly retarded.     

Development of high efficiency p-i-n amorphous silicon solar cells with the p-μc-Si:H/p-a-SiC:H double window layer

A structure is developed to help improve the TCO/p contact and efficiency of the solar cell. A p-i-n amorphous silicon (a-Si:H) solar cell with high-conversion efficiency is presented via use of a double p-type window layer composed of microcrystalline silicon and amorphous silicon carbide. The best efficiency is obtained for a glass/textured TCO/p-μc-Si:H/p-a-SiC:H/buffer/i-a-Si:H/n-μc-Si:H/GZO/Ag structure. Using a SnO₂/GZO bi-layer and a p-type hydrogenated microcrystalline silicon (p-μc-Si:H) layer between the TCO/p-a-SiC:H interface improves the photovoltaic performance due to reduction of the surface potential barrier. Layer thickness, B₂H₆/SiH₄ ratio and hydrogen dilution ratio of the p-μc-Si:H layer are studied experimentally. It is clearly shown that the double window layer can improve solar cell efficiency. An initial conversion efficiency of 10.63% is achieved for the a-Si:H solar cell.     

Investigation on the energy conversion of dye-sensitized solar cells based on TiO<Subscript>2</Subscript> core/shell using metal oxide as a barrier layer

Photo-electrochemical solar cells based on a core-shell structure including ZnO shell and TiO₂ cove, have been fabricated with ruthenium bipyridyl complex (N719) as the sensitizer. Compared with the pure anatase TiO₂, the ZnO-covered TiO₂ film possesses outstanding ability to transport electrons with an overall power conversion efficiency of 3.72. Elctrochemical study shows that surface modification of TiO₂ film with ZnO can increase the concentration of free electrons in the conduction band of TiO₂. This remit implies that the charge recombination is reduced in process of electron transport through the TiO₂ porous film, which can decrease the photocurrent loss and hence improve Dye-Sensitized solar ceils (DSSCs) efficiency. This result indicates that optimization of TiO₂ porous network fabrication condition is efficient, for the improvement of TiO₂ based DSSC’s performances.     

The superiority of Ti plate as the substrate of dye-sensitized solar cells

The photovoltaic properties of dye-sensitized solar cells (DSCs) based on several types of substrates, FTO, Ti and stainless steel, were investigated. The sheet resistances of the substrates were correlated to the photovoltaic properties. The efficiency of the DSC using Ti substrate was higher than that of the DSCs using stainless steel and FTO. For the large-size DSCs based on FTO, the metal track is an important component to retain the decrease in cell performance due to the relatively high sheet resistance of FTO. To minimize the internal resistance of DSCs, the Ti sheet was used as a support of nano-crystalline TiO₂ due to the low sheet resistance. Although the IPCE of DSCs based on Ti substrate was lower than that of DSCs based on FTO in the range from 400 to 500 nm, the DSC based on Ti substrate showed the higher IPCE in red region due to the light reflecting on Ti substrate. The efficiency of 3.2% for the DSC based on Ti substrate was obtained with a Jsc , Voc 0.75 V, and FF 0.610. This result shows that the Ti plate has superiority for producing the large DSCs without metal track and reduces the cost of DSCs.     

High-efficiency inverted polymer solar cells with solution-processed metal oxides

The selection of carrier transporting layer in polymer solar cells is an important issue because the nature and direction of carrier transport can be manipulated by inserting different functional layers in the device structure. In this work, we report a very efficient inverted polymer solar cell (PSC) system based on regioregular poly(3-hexylthiophene) and a n-type acceptor, bis-indene[C₆₀]. With a pair of metal oxides and the insertion of TiO₂ nanorods electron collecting layer between the ZnO thin film and the active layer, the device efficiency can be greatly improved. The contact area between the active layer and the electron collecting layer, as well as the thickness of active layer, can be increased with the incorporation of TiO₂ nanorods. As a result, photocurrent can be enhanced due to more absorption of light and more charge separation interface. In addition, the larger contact area and the crystalline TiO₂ nanorods provide a more efficient transporting route for the carriers to the cathode. The most efficient device demonstrated shows a high power conversion efficiency of 5.6% with the inverted structure.     

Performance of superstrate multijunction amorphous silicon-based solar cells using optical layers for current management

The performance of multijunction amorphous silicon-based thin film solar cells has been reported using thin layers of TiO₂ and SiO_x acting as refractive index matching optical layers for different interfaces of the superstrate device structure. Improvement of short-circuit current from the sub-cells of a-Si/μc-Si cells is demonstrated with TiO₂ as anti-reflection layer at TCO/Si interface and SiO_x as intermediate-reflector layer between two sub-cells. An initial efficiency of 11.8% is achieved by applying both the TiO₂ and SiO_x optical layers in a-Si/μc-Si solar cell.     

Selective conditions for the fabrication of a flexible dye-sensitized solar cell with Ti/TiO2 photoanode

The effects of four factors, i.e., (i) sputter-deposition time of platinum (Pt) film, (ii) sintering temperature of TiO₂-coated Ti foil (Ti/TiO₂), (iii) thickness of Ti foil, and (iv) concentration of iodine are reported for the photovoltaic performance of a back-illuminated flexible dye-sensitized solar cell (DSSC) with Ti foil substrate for the TiO₂ layer. Optimization of these four factors yields a solar-to-electricity conversion efficiency (η) of 5.95%. Transmittance spectra, cyclic voltammetry (CV), electrochemical impedance spectra (EIS), X-ray diffraction (XRD), scanning electron micrographs (SEM), and laser-induced photovoltage transient technique are used to substantiate the explanations.     

Dye-sensitized solar cells based on a single layer deposition of TiO2 from a new formulation paste and their photovoltaic performance

A new strategy for enhancing the efficiency and reducing the production cost of TiO₂ solar cells by design of a new formulated TiO₂ paste with tailored crystal structure and morphology is reported. The conventional three- or four-fold layer deposition process was eliminated and replaced by a single layer deposition of TiO₂ compound. Different TiO₂ pastes with various crystal structures, morphologies and crystallite sizes were prepared by an aqueous particulate sol–gel process. Based on simultaneous differential thermal (SDT) analysis the minimum annealing temperature to obtain organic-free TiO₂ paste was determined at 400 °C, being one of the lowest crystallization temperatures of TiO₂ photoanode electrodes for solar cell application. Photovoltaic measurements showed that TiO₂ solar cell with pure anatase crystal structure had higher power conversion efficiency (PCE) than that made of pure rutile-TiO₂. However, the PCE of solar cells depends on the anatase to rutile weight ratio, reaching a maximum at a specific value due to the synergic effect between anatase and rutile TiO₂ nanoparticles. Moreover, it was found that the PCE of solar cells made of crystalline TiO₂ powders was much higher, increasing in the range 32–84% depending on anatase to rutile weight ratio, than that of prepared by amorphous powders. TiO₂ solar cell with the morphology of mixtures of nanoparticles and microparticles had higher PCE than the solar cell with the same phase composition containing TiO₂ nanoparticles due to the role of TiO₂ microparticles as light scattering particles. The presented strategy would open up new insight into fabrication and structural design of low-cost TiO₂ solar cells with high power conversion efficiency.     

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.