Double-layer TiO2 nanotube arrays by two-step anodization: Used in back and front-side illuminated dye-sensitized solar cells

Double-layer TiO₂ nanotube arrays were fabricated by a two-step anodization process on Ti foils. The first TiO₂ nanotube layer was annealed after anodization and then exposed to the second anodization to grow the second TiO₂ nanotube layer beneath it. The crystallized upper layer acts as a protective layer against chemical etching of the lower layer tubes top by electrolyte that leads to growing of thick layers with open-top-tubes beneath the upper one. The effect of different anodization parameters on the final geometry of the nanotubes, grown beneath the protective layer was investigated. The upper TiO₂ layer was detached as an intact membrane at the end of the two-step anodization process and used in front-side illuminated dye-sensitized solar cells (DSSCs) with high conversion efficiency up to 8.66%. Also, the remained TiO₂ nanotubes on the substrate with different diameters were used in the back-side illuminted DSSCs.     

Effect of seed layer on the growth of rutile TiO2 nanorod arrays and their performance in dye-sensitized solar cells

In order to improve the performance of TiO₂ photoanode-based dye sensitized solar cells (DSSCs), rutile TiO₂ nanorod arrays (NRAs) were grown on SnO₂:F (FTO) conductive glass coated with TiO₂ seed layer by a hydrothermal method. The TiO₂ seed layer was obtained by spin-coating titanium tetraisopropoxide (TTIP) isopropanol solution with concentration in the range of 0~0.075 M. Then the effect of the thin TiO₂ seed layer on the crystal structure and surface morphology of TiO₂ NRAs and the photoelectric conversion properties of the corresponding DSSCs were investigated. It is found that TiO₂ NRAs are vertically oriented, about 1.7 μm long and the average diameter is about 35 nm for the samples derived from TTIP in the range of 0.005~0.05 M, which are more uniform and better separated from each other than those without TiO₂ seed layer (average diameter 35~85 nm). The photoelectric conversion efficiency of DSSCs based on TiO₂ NRAs with TiO₂ seed layer is larger than that without TiO₂ seed layer. Typically, the energy efficiency of DSSCs obtained from the seed solution of 0.025 M TTIP is 1.47%, about 1.8 times greater than that without TiO₂ seed layer. The performance improvement is attributed to the thinner, denser and better oriented NRAs grown on seeded-FTO substrate absorbing more dye and suppressing charge recombination at the FTO substrate/electrolyte interface.     

Study on the thermal stability of Ga-doped ZnO thin film: A transparent conductive layer for dye-sensitized TiO2 nanoparticles based solar cells

Generally, optoelectronic devices are fabricated at a high temperature. So the stability of properties for transparent conductive oxide (TCO) films at such a high temperature must be excellent. In the paper, we investigated the thermal stability of Ga-doped ZnO (GZO) transparent conductive films which were heated in air at a high temperature up to 500 °C for 30 min. After heating in air at 500 °C for 30 min, the lowest sheet resistance value for the GZO film grown at 300 °C increased from 5.5 Ω/sq to 8.3 Ω/sq, which is lower than 10 Ω/sq. The average transmittance in the visible light of all the GZO films is over 90%, and the highest transmittance is as high as 96%, which is not influenced by heating. However, the transmittance in the near-infrared (NIR) region for the GZO film grown at 350 °C increases significantly after heating. And the grain size of the GZO film grown at 350 °C after annealing at 500 °C for 30 min is the biggest. Then dye-sensitized TiO2 NPs based solar cells were fabricated on the GZO film grown at 350 °C (which exhibits the highest transmittance in NIR region after heating at 500 °C for 30 min) and 300 °C (which exhibits the lowest sheet resistance after heating at 500 °C for 30 min). The dye-sensitized solar cell (DSSC) fabricated on the GZO film grown at 350 °C exhibits superior conversion efficiency. Therefore, transparent conductive glass applying in DSSCs must have a low sheet resistance, a high transmittance in the ultraviolet–visible–infrared region and an excellent surface microstructure.     

In situ preparation of hierarchically structured dual-layer TiO2 films by E-spray method for efficient dye-sensitized solar cells

Hierarchically-structured mesoporous TiO₂ films are prepared by the electrospray (E-spray) method. The microstructures of TiO₂ films can be feasibly tuned as spheres or nanocrystalline-mixed spheres, rendering in situ preparation of TiO₂ dual-layer. With these dual-layer TiO₂ films as photoanode and N719 as sensitizer, the dye-sensitized solar cell achieves a power conversion efficiency (PCE) of 8.96%, which is among the best of N719 devices so far, and constituting up to 19% improvement relative to single-layer TiO₂ photoanode based devices. To disclose the mechanism for the improvement, corresponding samples are prepared and investigated by scanning electron microscopy, electrochemical impedance spectroscopy, diffuse reflectance spectra. It was found that the dual-layer photoanode can simultaneously incorporate high dye loading and low charge transfer resistance, leading to high short current density and thus high PCE. Different to other reported dual-layer photoanodes, which often need two or more preparing procedures, only one step is needed in this work. To our best knowledge, it is the first time to employ only one step to in situ prepare photoanodes with dual-layer structures, which greatly simplifies the experimental processes.     

Enhanced short circuit current density of dye-sensitized solar cells aided by Sr,V co-doped TiO2 particles

This study comes up with a straightforward method for preparing uniform electrodes containing Sr,V co-doped TiO₂ particles for dye-sensitized solar cells (DSCs) applications. The spherical particles with the average diameter around 2.5 µm are assembled from small nanoparticles with the average grain size of 60 nm. X-ray diffraction (XRD) reveals that the introduction of dopants not only inhibits the growth of rutile phase, but also results in smaller primary crystallites, improving the surface area and dye adsorption ability of the electrodes. X-ray photoelectron spectroscopy (XPS) showed that Sr²⁺ and V⁵⁺ ions are well incorporated into the titania crystal lattice without forming specific Strontium and Vanadium compositions. UV–visible spectra show that the co-doped TiO₂ films have lower band gap energy than that of undoped-TiO₂, extending the absorption of TiO₂ into visible region. Isolated energy levels in band structure of TiO₂ as well as local lattice distortions due to dopants introduction are the parameters enhanced the short circuit current density of the cells. The TiO₂ DSC co-doped with 0.075 at% Sr and 1.5 at% V (i.e., S7V15 cell) had the highest circuit current density and power conversion efficiency of 18.57 and 7.76%, respectively, as a result of less recombination, which is demonstrated by electrochemical impedance spectroscopy (EIS).     

Rutherford Backscattering Spectrometry Analysis of Self-Formed Ti-Rich Interface Layer Growth in Cu(Ti)/Low-<Emphasis Type="Italic">k</Emphasis> Samples

A new fabrication technique to prepare ultrathin barrier layers for nanoscale Cu wires was proposed in our previous studies. Ti-rich layers formed at Cu(Ti)/dielectric layer interfaces consisted of crystalline TiC or TiSi and amorphous Ti oxides. The primary control factor for the Ti-rich interface layer composition was C concentration in the dielectric layers rather than the formation enthalpy of the Ti compounds. To investigate Ti-rich interface layer growth in Cu(Ti)/dielectric layer samples annealed in ultrahigh vacuum, Rutherford backscattering spectrometry (RBS) was employed in the present study. Ti peaks were obtained only at the interfaces for all samples. Molar amounts of Ti atoms segregated to the interfaces (n) were estimated from Ti peak areas. Log n values were proportional to log t values. Slopes were similar for all samples, suggesting similar growth mechanisms. The activation energy (E) for Ti atoms reacting with the dielectric layers containing carbon (except SiO₂) tended to decrease with decreasing C concentration (decreasing k), while those for the SiO₂ layers were much higher. Reaction rate coefficients [Z · exp(−E/RT)] were insensitive to C concentration in the dielectric layers. These factors lead to the conclusion that growth of the Ti-rich interface layers is controlled by chemical reactions, represented by the Z and E values, of the Ti atoms with the dielectric layers, although there are a few diffusion processes possible.     

The effect of ethylene glycol/citric acid molar ratio in the initial precursor of TiO2 nanoparticle paste synthesized by a polymerizable complex method on the photovoltaic properties of dye-sensitized solar cells

A polymerizable complex method, also known as a Pechini method, was employed to synthesize titanium-sol (Ti-sol) as a matrix for TiO₂ nanoparticle paste, suitable for fabrication of semiconducting mesoporous TiO₂ layer as a photoanode of dye-sensitized solar cells (DSSCs). The purpose of the present work was to investigate the effect of ethylene glycol (EG)/citric acid (CA) molar ratio (Z), in the initial Ti-sol precursor, on the photovoltaic properties of DSSCs. From viscosity (µ) measurement and Fourier transform infrared (FTIR) spectrum of Ti-sols it was revealed that the amount of polyester in the sol decreases with increasing Z. The higher polyester content in the Ti-sols with lower Z ratios led to their higher surface tension (γ) and as a result the higher contact angle (α). The low wettability of fluorine doped tin oxide (FTO) coated glass with Ti-sol was the main reason of micro-cracking of TiO₂ layers after sintering. This effect was significant for lower Z ratios. Micro-cracks increase the back electron–hole recombination rate. Also, at higher Z ratio, the back electron–hole recombination rate increased, which was due to the lower Ti⁴⁺ ions in the Ti-sol precursor and poor interconnection between TiO₂ nanoparticles. Therefore, the maximum short circuit current density (I_sc) and the maximum conversion efficiency (η) were obtained for Z=4. Fill factor (FF) decreased with increasing Z. But, open circuit voltage (V_oc) was nearly independent of Z.     

Improved performance of nanoporous TiO2 film in dye-sensitized solar cells via ZrCl4 and TiCl4 surface co-modifications

In this study, nanoporous TiO₂ films were modified by a dip-coating process using a mixture aqueous solution of ZrCl₄ and TiCl₄ followed by calcination to prepare a photoanode for dye-sensitized solar cells. Compared with the control film modified with 0.04 mol L⁻¹ TiCl₄, the power conversion efficiency of the TiO₂ film modified with a mixed solution of 0.05 mol L⁻¹ ZrCl₄ and 0.04 mol L⁻¹ TiCl₄, was 18.67% higher because of the improved short circuit current (J_sc) and open circuit voltage (V_oc). The improvement in J_sc was due to the suppression of charge recombination, which was demonstrated by a series of measurements, including electrochemical impedance spectroscopy, monochromatic incident photon-to-electron conversion efficiency spectroscopy, and the open-circuit voltage decay technique. The Mott-Schottky measurement results indicated that the negative shift of a flat band led to the increased V_oc.     

Structural characterization of GaAs<Subscript>1−x</Subscript>Bi<Subscript>x</Subscript> alloy by rutherford backscattering spectrometry combined with the channeling technique

Rutherford backscattering spectrometry (RBS) combined with the channeling technique has been applied to a GaAs_1−xBi_x epilayer to investigate concentration and lattice location of Bi atoms and crystalline quality of the epilayer. The metastable GaAs_1−xBi_x alloy layer was grown on a GaAs substrate at a temperature as low as 365°C. The GaBi mole fraction obtained was 2.6 ± 0.2%. Angular scans for [100] and [111] crystal directions reveal that the incorporated Bi atoms exactly occupy substitutional sites in the GaAs crystal lattice. Crystal perfection of the GaAs_1−xBi_x metastable alloy is fairly good in spite of the low growth temperature.     

Boosting the Efficiency of Perovskite Solar Cells with CsBr‐Modified Mesoporous TiO2 Beads as Electron‐Selective Contact

Rapid extraction of photogenerated charge carriers is essential to achieve high efficiencies with perovskite solar cells (PSCs). Here, a new mesoscopic architecture as electron‐selective contact for PSCs featuring 40 nm sized TiO₂ beads endowed with mesopores of a few nanometer diameters is introduced. The bimodal pore distribution inherent to these films produces a very large contact area of 200 m² g^?1 whose access by the perovskite light absorber is facilitated by the interstitial voids between the particles. Modification of the TiO₂ surface by CsBr further strengthens its interaction with the perovskite. As a result, photogenerated electrons are extracted rapidly producing a very high fill factor of close to 80% a V_OC of 1.14 V and a PCE up to 21% with negligible hysteresis.     

Solar Cells by Design: Photoelectrochemistry of TiO2 Nanorod Arrays Decorated with CdSe

One‐dimensional (1D) nanostructures of TiO₂ are grown directly on transparent, conductive glass substrate using hydrothermal/solvothermal methods. When employed as a photoanode in photoelectrochemical cells, the vertically aligned TiO₂ nanorod array exhibits slower charge recombination at electrolyte interface as compared to mesoscopic TiO₂ particulate film. Electrochemical deposition of CdSe onto TiO₂ nanorod array is carried out to extend absorption into visible light region. The role of CdSe‐sensitized, 1D rutile TiO₂ architecture in the solar cell design is discussed.     

Effect of bath temperature on the properties of CuInxGa1-x Se2 thin films grown by the electrodeposition technique

Electrodeposition is a promising and low cost method to synthesize CulnxGa1-xSe2 (CIGS)thin films as an absorber layer for solar cells. The effect of bath temperature on the properties of CIGS thin films was investigated in this paper. CIGS films of 1 μm thickness were electrodeposited potentiostatically from aqueous solution, containing trisodium citrate as a complexing agent, on Mo/glass substrate under a voltage of-0.75 V, and bath temperatures were varied from 20 to 60 ℃. The effects of bath temperature on the properties of CIGS thin films were characterized by X-ray diffraction (XRD) and scanning electron microscopy. XRD revealed the presence of the CuIn0.7Ga0.3Se2 phase, the optimal phase for application in solar cells. The grain dimensions and crystallizability increase along with the increase of the bath temperature, and the films become stacked and homogeneous. There were few changes in surface morphology and the composition of the films.     

阴极修饰对染料敏化TiO2太阳能电池性能的改进

通过对染料敏化TiO2纳米晶太阳能电池中阴极进行修饰来提高电池的光电性能。结果表明:在阴极表面镀上具有催化性能的白金、镍或石墨均可提高电池的光电转化效率(IPCE)、短路电流、开路电压和填充因子等性能。其中白金修饰阴极后,电池的性能较好,IPCE从7.59%升至48.32%,短路电流从0.91 mA升至7.23 mA,开路电压从478 mV升至571 mV以及填充因子从0.09升至0.47。并给出用UV—3100型紫外可见分光光度计测定染料RuL2(SCN)2溶液的吸收光谱。     

Performance and Stability Enhancement of Dye‐Sensitized and Perovskite Solar Cells by Al Doping of TiO2

Reversible photo‐induced performance deterioration is observed in mesoporous TiO₂‐containing devices in an inert environment. This phenomenon is correlated with the activation of deep trap sites due to astoichiometry of the metal oxide. Interestingly, in air, these defects can be passivated by oxygen adsorption. These results show that the doping of TiO₂ with aluminium has a striking impact upon the density of sub‐gap states and enhances the conductivity by orders of magnitude. Dye‐sensitized and perovskite solar cells employing Al‐doped TiO₂ have increased device efficiencies and significantly enhanced operational device stability in inert atmospheres. This performance and stability enhancement is attributed to the substitutional incorporation of Al in the anatase lattice, “permanently” passivating electronic trap sites in the bulk and at the surface of the TiO₂.     

Pechini法制备TiO_2薄膜及其在染料敏化太阳电池中的应用

用Pechini法在FTO导电玻璃上制备不同厚度的TiO2薄膜,并组装成染料敏化太阳能电池。XRD结果表明,在450℃退火1h得到了主相为锐钛矿的TiO2。SEM结果表明,TiO2薄膜表面疏松多孔,粒径均匀,厚度在6~15μm。紫外-可见光谱分析表明,TiO2薄膜染料的吸附量随薄膜厚度的增加而增加。光电性能研究表明,在0.005W/cm2的弱光照下,膜1(厚6μm)和膜2(厚15μm)光阳极的光电转换效率分别为6.85%和11.83%;在0.1 W/cm2的模拟标准太阳光照下,膜1和膜2光阳极的光电转换效率分别为1.72%和2.39%。     

聚乙二醇共水热合成TiO2纳米晶多孔薄膜

以钛酸丁酯为原料,在水热过程中加入聚乙二醇(分子量2 000)合成TiO2纳米晶,并制备多孔薄膜用于染料敏化太阳能电池(DSSCs)。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、台阶仪、紫外-可见分光光度计(UV-vis)对纳米晶粒的晶体结构、薄膜的表面形貌、厚度和光学吸收性能以及电池的光电能量转换性能随聚乙二醇的加入量变化的规律进行了探索。结果表明,聚乙二醇的加入抑制了锐钛矿相TiO2晶粒的生长,诱导了金红石相的形成。当聚乙二醇的加入量为TiO2质量的5%时性能达到最佳,采用单层多孔薄膜以及不添加四-叔丁基吡啶的电解质组装的电池获得了2.86%的光电能量转换效率。     

Significant improvement of photocurrent in dye-sensitized solar cells by incorporation thiophene into electrolyte as an inexpensive and efficient additive

For the first time, thiophene as an efficient additive is applied in electrolyte of dye-sensitized solar cells (DSSCs). In the cell based on 2-cyano-3-(4-(diphenylamino)phenyl)acrylic acid (TPA) sensitizer, addition of 1 M thiophene to the electrolyte (instead of 4-tert-butylpyridine (TBP)) increases significantly photocurrent density (J_sc) from 4.62 to 7.80 mA cm⁻². Consequently, overall conversion efficiency (η) enhances from 2.17% to 3.18% with a 46% improvement. For DSSC based on 2-cyano-3-(2′-(5′,10′,15′,20′-tetraphenylporphyrinato zinc(II))yl)acrylic acid (Zn-1) with modified electrolyte, J_sc increases from 4.18 to 8.23 mA cm⁻² and η improves from 1.46% to 1.96% that shows an enhancement of 34% in η. Intensity modulated photocurrent spectroscopy (IMPS) indicates the faster electron transfer in the DSSC based on thiophene additive compared to the standard device. Also, the higher electron diffusion coefficient (D_n) of the DSSC with modified electrolyte shows the thiophene additive facilitates the electron transfer. Based on cyclic voltammetry (CV) and UV–vis data, thiophene forms a molecular complex with iodine molecule in the electrolyte solution that has a remarkable effect on the redox couple oxidation–reduction reactions which improves J_sc. A significant improvement in J_sc with a small decrease in V_oc and thereby an increase in η are observed from addition thiophene.     

Improving the performance of Sb2Se3 thin film solar cells over 4% by controlled addition of oxygen during film deposition

Sb₂Se₃ has attracted great research interest very recently as a promising absorber material for thin film photovoltaics due to its suitable bandgap, high absorption coefficient, and non‐toxic, low cost, and earth abundant nature. In this work, a significant efficiency improvement to 4.8% of superstrate cadmium sulfide (CdS)/Sb₂Se₃ solar cells is obtained by the controlled addition of oxygen during thermal evaporation of Sb₂Se₃ films. Systematic materials and device physics characterization reveal that oxygen addition during Sb₂Se₃ film evaporation significantly improves the CdS/Sb₂Se₃ heterojunction quality through effective passivation of interfacial defect states, resulting in a substantial enhancement in device circuit voltage and short circuit current density. The 4.8% device is the highest efficiency thus far reported for Sb₂Se₃ thin film solar cells. Copyright © 2015 John Wiley & Sons, Ltd.     

Template‐Directed Liquid ALD Growth of TiO2 Nanotube Arrays: Properties and Potential in Photovoltaic Devices

Dense and well‐aligned arrays of TiO₂ nanotubes extending from various substrates are successfully fabricated via a new liquid‐phase atomic layer deposition (LALD) in nanoporous anodic alumina (AAO) templates followed by alumina dissolution. The facile and versatile process circumvents the need for vacuum conditions critical in traditional gas‐phase ALD and yet confers ALD‐like deposition rates of 1.6–2.2 Å cycle^?1, rendering smooth conformal nanotube walls that surpass those achievable by sol–gel and Ti‐anodizing techniques. The nanotube dimensions can be tuned, with most robust structures being 150–400 nm tall, 60–70 nm in diameter with 5–20 nm thick walls. The viability of TiO₂ nanotube arrays deposited on indium tin oxide (ITO)–glass electrodes for application in model hybrid poly(3‐hexylthiophene) (P3HT):TiO₂ solar cells is studied. The results achieved provide platforms and research directions for further advancements.     

Large‐scale Synthesis of Urchin‐like Mesoporous TiO2 Hollow Spheres by Targeted Etching and Their Photoelectrochemical Properties

A versatile targeted etching strategy is developed for the large‐scale synthesis of urchin‐like mesoporous TiO₂ hollow spheres (UMTHS) with tunable particle size. Its key feature is the use of a low‐temperature hydrothermal reaction of surface‐fluorinated, amorphous, hydrous TiO₂ solid spheres (AHTSS) under the protection of a polyvinylpyrrolidone (PVP) coating. With the confinement of PVP and water penetration, the highly porous AHTSS are selectively etched and hollowed by fluoride without destroying their spherical morphology. Meanwhile TiO₂ hydrates are gradually crystallized and their growth is preferentially along anatase (101) planes, reconstructing an urchin‐like shell consisting of numerous radially arranged single‐crystal anatase nanothorns. Complex hollow structures, such as core–shell and yolk–shell structures, can also be easily synthesized via additional protection of the interior by pre‐filling AHTSS with polyethylene glycol (PEG). The hollowing transformation is elucidated by the synergetic effect of etching, PVP coating, low hydrothermal reaction temperature, and the unique microstructure of AHTSS. The synthesized UMTHS with a large surface area of up to 128.6 m² g^‐1 show excellent light‐harvesting properties and present superior performances in photocatalytic removal of gaseous nitric oxide (NO) and photoelectrochemical solar energy conversion as photoanodes for dye‐sensitized mesoscopic solar cells.