Hui-Ping Wu

Enhanced photovoltaic performance with co-sensitization of porphyrin and an organic dye in dye-sensitized solar cells

We designed a stepwise approach for co-sensitization of a zinc porphyrin sensitizer (LD12) with a spirally configured organic dye (CD5) for dye-sensitized solar cells. The co-sensitized LD12 + CD5 device showed significantly enhanced VOC and JSC relative to its individual single-dye sensitized devices. Upon optimization, the device made of the LD12 + CD5 system yielded JSC/mA cm−2 = 16.7, VOC/V = 0.74, FF = 0.73 and η = 9.0%; this performance is superior to that of either individual device made from LD12 (η = 7.5%) and CD5 (η = 5.7%) under the same conditions of fabrication. To understand the effects of the potential shift and charge recombination on the cell performance, we measured charge-extraction (CE) and intensity-modulated photovoltage spectra (IMVS). Upon sensitization with each dye, the TiO2 potentials are similar, but co-sensitization causes the potential to shift down (cathodic shift). Charge recombination was significantly retarded for the co-sensitized system relative to each individual dye-sensitized system, to account for the enhanced VOC for the former relative to the latter. A test of stability indicates a systematic trend between the LD12 + CD5 and LD12 devices; the performance of the co-sensitized device degraded only ∼15% and remained stable during the period of 500–1000 h near 295 K.

Molecular engineering of cocktail co-sensitization for efficient panchromatic porphyrin-sensitized solar cells

Co-sensitization of two or more dyes with complementary absorption spectra on a semiconductor film is an effective approach to enhance the performance of a dye-sensitized solar cell (DSSC). Porphyrin sensitizer YD2-oC8 showed outstanding photovoltaic performance co-sensitized with an organic dye to cover the entire visible spectral region, 400–700 nm. To promote the light-harvesting capability beyond 700 nm, a porphyrin dimer (YDD6) was synthesized for a co-sensitized system. We report a systematic approach for engineering of molecular co-sensitization of TiO2 films in a cocktail solution containing YD2-oC8, an organic dye (CD4) and YDD6 in a specific molar ratio to optimize the photovoltaic performance of the device. The resulting device showed panchromatic spectral features in the IPCE action spectrum in the region 400–700 nm attaining efficiencies of 75–80%; the spectrum is extended to the near-IR region attaining 40–45% in 700–800 nm region, giving JSC/mA cm−2 = 19.28, VOC/mV = 753, FF = 0.719, and η = 10.4% under standard AM 1.5 G one-sun irradiation. This performance is superior to what is obtained from the individual single-dye devices and the two-dye co-sensitized systems. The shifts of TiO2 potential upon dye uptake and the kinetics of charge recombination were examined through measurements of the charge extraction (CE) and intensity-modulated photovoltage spectroscopy (IMVS), respectively. Five co-sensitized systems were investigated to demonstrate that suppression of dye aggregation of YDD6 in the co-sensitized film is a key factor to further improve the device performance.

Design and characterization of alkoxy-wrapped push-pull porphyrins for dye-sensitized solar cells

Three alkoxy-wrapped push-pull porphyrins were designed and synthesized for dye-sensitized solar cell (DSSC) applications. Spectral, electrochemical, photovoltaic and electrochemical impedance spectroscopy properties of these porphyrin sensitizers were well investigated to provide evidence for the molecular design.

Size-controlled anatase titania single crystals with octahedron-like morphology for dye-sensitized solar cells.

A simple hydrothermal method with titanium tetraisopropoxide (TTIP) as a precursor and triethanolamine (TEOA) as a chelating agent enabled growth in the presence of a base (diethylamine, DEA) of anatase titania nanocrystals (HD1-HD5) of controlled size. DEA played a key role to expedite this growth, for which a biphasic crystal growth mechanism is proposed. The produced single crystals of titania show octahedron-like morphology with sizes in a broad range of 30-400 nm; a typical, extra large, octahedral single crystal (HD5) of length 410 nm and width 260 nm was obtained after repeating a sequential hydrothermal treatment using HD3 and then HD4 as a seed crystal. The nanocrystals of size ~30 nm (HD1) and ~300 nm (HD5) served as active layer and scattering layer, respectively, to fabricate N719-sensitized solar cells. These HD devices showed greater V(OC) than devices of conventional nanoparticle (NP) type; the overall device performance of HD attained an efficiency of 10.2% power conversion at a total film thickness of 28 μm, which is superior to that of a NP-based reference device (η = 9.6%) optimized at a total film thickness of 18-20 μm. According to results obtained from transient photoelectric and charge extraction measurements, this superior performance of HD devices relative to their NP counterparts is due to the more rapid electron transport and greater TiO(2) potential.

Fabrication of long TiO2 nanotube arrays in a short time using a hybrid anodic method for highly efficient dye-sensitized solar cells

We report a simple hybrid anodic method, with initial potentiostatic anodization followed by galvanostatic anodization, to grow much longer titania nanotube (TNT) arrays in a much shorter anodization period (t). The length of the TNT arrays (L) depends linearly on t and is controlled by the electric current; the growth rates are 5.3, 10.7 and 20.3 μm h−1 for current densities 3.7, 5.6 and 7.5 mA cm−2, respectively. The produced TNT films of L = 15–57 μm sensitized with N719 dye were fabricated into devices for photovoltaic characterization. The NT-DSSC devices show systematically improved cell performance depending on L, reflecting the excellent intrinsic light-scattering property of the NT-DSSC devices to harvest increased sunlight with long TNT arrays. The great effective surface area inside TNT arrays has been shown to significantly increase the dye loading, which might help to enhance the cell performance of the device with co-sensitizing of different dyes for improved efficiency of light harvesting in the future. The best performance of the NT-DSSC device was achieved at L ∼ 30 μm with a spacer of similar thickness, giving JSC = 14.63 mA cm−2, VOC = 0.741 V, FF = 0.70, and η = 7.6%, which is unprecedented for a back-illumination DSSC.

Detachment and transfer of ordered TiO2 nanotube arrays for front-illuminated dye-sensitized solar cells

We report a method of detachment and transfer of one-dimensional TiO2 nanotube (NT) arrays to fabricate dye-sensitized solar cells (DSSCs) with illumination from the front side. The ordered NT arrays (tube length 20 μm) were detached from the NT–Ti substrate, as annealed, by means of a second anodization at 20 V for 4 h and then transferred, inverted, onto a transparent substrate of conducting oxide (TCO) with an interface of TiO2 nanoparticles of thickness ∼2 μm. Dry etching of the NT surface in a highly dense plasma reactor under BCl3/Cl2 for 90 s opened previously closed ends of the tubes. The inverted (bottom-up) NT–TCO substrate was fabricated into a DSSC device that shows a cell performance (η = 6.24%) significantly improved over those of a front-illuminated counterpart with an upright (face-up) structure (η = 4.84%) and of a conventional back-illuminated device (η = 4.61%). Electrochemical impedance spectra (EIS) of the devices under one-sun irradiation were measured to rationalize the cell performances that are consistent with the corresponding interfacial impedances between the NT arrays and the electrode for collection of electrons.

Characterisation of electron transport and charge recombination using temporally resolved and frequency-domain techniques for dye-sensitised solar cells

We review systematically the kinetic characterisation of electron transport and charge recombination in dye-sensitised solar cells (DSSC) using both temporally resolved and frequency-domain techniques. For the temporally resolved approach, charge extraction (CE), transient-photocurrent decay (TCD) and transient-photovoltage decay (TVD) methods are introduced in detail; for the frequency-domain approach, techniques involving electrochemical impedance spectroscopy (EIS), intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS) are presented in detail. The TCD and TVD data are obtained under short-circuit and open-circuit conditions, respectively, and the electron diffusion coefficients and electron lifetimes are extracted from fitting the decay curves accordingly; the IMPS/IMVS results are the counterparts of the TCD/TVD results in the frequency domain. Even though the EIS results are readily acquired, an accurate interpretation of the data requires an appropriate model to determine the internal features of the device. This review provides an account of each technique about its operating principle, experimental setup and data analysis. As case studies for each technique, examples are given to rationalise the observed potential shift, decay coefficients of electron transport and of charge recombination in relation to the corresponding photovoltaic performance of the device.

High-Performance Large-Scale Flexible Dye-Sensitized Solar Cells Based on Anodic TiO2 Nanotube Arrays

A simple strategy to fabricate flexible dye-sensitized solar cells involves the use of photoanodes based on TiO2 nanotube (TNT) arrays with rear illumination. The TNT films (tube length ∼35 μm) were produced via anodization, and sensitized with N719 dye for photovoltaic characterization. Pt counter electrodes of two types were used: a conventional FTO/glass substrate for a device of rigid type and an ITO/PEN substrate for a device of flexible type. These DSSC devices were fabricated into either a single-cell structure (active area 3.6×0.5 cm2) or a parallel module containing three single cells (total active area 5.4 cm2). The flexible devices exhibit remarkable performance with efficiencies η=5.40% (single cell) and 4.77% (parallel module) of power conversion, which outperformed their rigid counterparts with η=4.87% (single cell) and 4.50% (parallel model) under standard one-sun irradiation. The flexible device had a greater efficiency of conversion of incident photons to current and a broader spectral range than the rigid device; a thinner electrolyte layer for the flexible device than for the rigid device is a key factor to improve the light-harvesting ability for the TNT-DSSC device with rear illumination. Measurements of electrochemical impedance spectra show excellent catalytic activity and superior diffusion characteristics for the flexible device. This technique thus provides a new option to construct flexible photovoltaic devices with large-scale, light-weight, and cost-effective advantages for imminent applications in consumer electronics.

Panchromatic co-sensitization of porphyrin-sensitized solar cells to harvest near-infrared light beyond 900 nm

We designed a dimeric porphyrin dye (LDD1) based on an efficient push–pull zinc porphyrin (LD14) with extended π-conjugation through coupling of two zinc porphine cores via an acetylene bridge at the meso position of the porphyrin to extend the absorption spectrum effectively into the near infrared region. The effect of dye aggregation among porphyrin molecules was significantly suppressed when the LDD1 and LD14 dyes were co-sensitized on a nanocrystalline TiO2 film in a dye-sensitized photovoltaic system. The light-harvesting ability of the device exhibits a panchromatic feature covering a broad spectral region from 400 nm to 900 nm, which results in a short-circuit current density of 21.3 mA cm−2 and a power conversion efficiency of 10.4% in an iodine-based solar cell.

Design and Characterization of Heteroleptic Ruthenium Complexes Containing Benzimidazole Ligands for Dye-Sensitized Solar Cells: The Effect of Fluorine Substituents on Photovoltaic Performance.

We designed heteroleptic ruthenium complexes (RD12-RD15) containing fluoro-substituted benzimidazole ligands for dye-sensitized solar cells (DSSCs). These dyes were synthesized according to a typical one-pot procedure with the corresponding ancillary ligands produced in two simple steps; they were prepared into DSSC devices according to the same conditions of fabrication. The eventual devices show a systematic trend of increasing VOC and decreasing JSC with fluorine atoms of increasing number substituted on the ligand. The charge-extraction results show that upward shifts of the TiO2 potential occurred when the fluoro-substituted dyes were sensitized on TiO2 with a systematic trend of shift N719 > RD15 (with 5 F) > RD12 (with 2 F) >RD5 (no F); the intensity-modulated photovoltage spectra indicate that those fluoro substituents retard charge recombination with the electron lifetimes (τR) in the order RD15 > RD12 > RD5 > N719, consistent with the variation of VOC for the systems.