Wangchao Chen

Mesoporous TiO2 Yolk-Shell Microspheres for Dye-sensitized Solar Cells with a High Efficiency Exceeding 11%.

Yolk-shell TiO2 microspheres were synthesized via a one-pot template-free solvothermal method building on the aldol condensation reaction of acetylacetone. This unique structure shows superior light scattering ability resulting in power conversion efficiency as high as 11%. This work provided a new synthesis system for TiO2 microspheres from solid to hollow and a novel material platform for high performance solar cells.

One-Pot Synthesis of Mesoporous TiO2 Micropheres and Its Application for High-Efficiency Dye-Sensitized Solar Cells

TiO2 microspheres are of great interest for a great deal of applications, especially in the solar cell field. Because of their unique microstructure and light-scattering effect, TiO2 microsphere-based solar cells often exhibit superior photovoltaic performance. Hence, exploring new suitable TiO2 microspheres for high-efficiency solar cells is essential. In this work, we demonstrate a facile one-pot solvothermal approach for synthesis of TiO2 microspheres using acetone as solvent. The as-prepared TiO2 microspheres are composed of densely interconnected nanocrystals and possess a high specific surface area up to 138.47 m(2) g(-1). As the photoanode, the TiO2 microsphere-based DSSC gives higher dye loading and light adsorption ability as well as longer electron lifetime, resulting in higher short-circuit current value and superior power conversion efficiency (PCE) compared with Dyesol 18 nm TiO2 nanoparticle paste. Finally, the TiO2 microsphere-based DSSC were optimized by adding a TiO2 nanocrystal underlayer and TiCl4 post-treatment, giving a high PCE of 10.32%.

Superior Light-Harvesting Heteroleptic Ruthenium(II) Complexes with Electron-Donating Antennas for High Performance Dye-Sensitized Solar Cells

Three heteroleptic polypyridyl ruthenium complexes, RC-41, RC-42, and RC-43, with efficient electron-donating antennas in the ancillary ligands were designed, synthesized, and characterized as sensitizers for dye-sensitized solar cell. All the RC dye sensitizers showed remarkable light-harvesting capacity and broadened absorption range. Significantly, RC-43 obtained the lower energy metal-ligand charge transfer (MLCT) band peaked at 557 nm with a high molar extinction coefficient of 27 400 M(-1) cm(-1). In conjunction with TiO2 photoanode of submicrospheres and iodide-based electrolytes, the DSSCs sensitizing with the RC sensitizers, achieved impressively high short-circuit current density (19.04 mA cm(-2) for RC-41, 19.83 mA cm(-2) for RC-42, and 20.21 mA cm(-2) for RC-43) and power conversion efficiency (10.07% for RC-41, 10.52% for RC-42, and 10.78% for RC-43). The superior performances of RC dye sensitizers were attributed to the enhanced light-harvesting capacity and incident-photon-to-current efficiency (IPCE) caused by the introduction of electron-donating antennas in the ancillary ligands. The interfacial charge recombination/regeneration kinetics and electron lifetime were further evaluated by the electrochemical impedance spectroscopy (EIS) and transient absorption spectroscopy (TAS). These data decisively revealed the dependences on the photovoltaic performance of ruthenium sensitizers incorporating electron-donating antennas.

Tetraphenylmethane-Arylamine Hole-Transporting Materials for Perovskite Solar Cells

A new class of hole-transporting materials (HTM) containing tetraphenylmethane (TPM) core have been developed. After thermal, charge carrier mobility, and contact angle tests, it was found that TPA-TPM (TPA: arylamine derivates side group) showed higher glass-transition temperature and larger water-contact angle than spiro-OMeTAD with comparable hole mobility. Photoluminescence and impedance spectroscopy studies indicate that TPA-TPMs hole-extraction ability is comparable to that of spiro-OMeTAD. SEM and AFM results suggest that TPA-TPM has a smooth surface. When TPA-TPM is used in mesoscopic perovskite solar cells, power conversion efficiency comparable to that of spiro-OMeTAD is achieved. Notably, the perovskite solar cells employing TPA-TPM show better long-term stability than that of spiro-OMeTAD. Moreover, TPA-TPM can be prepared from relatively inexpensive raw materials with a facile synthetic route. The results demonstrate that TPM-arylamines are a new class of HTMs for efficient and stable perovskite solar cells.

Solvothermal Synthesis of Hierarchical TiO2 Microstructures with High Crystallinity and Superior Light Scattering for High-Performance Dye-Sensitized Solar Cells

In this article, hierarchical TiO2 microstructures (HM-TiO2) were synthesized by a simple solvothermal method adopting tetra-n-butyl titanate as the titanium source in a mixed solvent composed of N,N-dimethylformamide and acetic acid. Due to the high crystallinity and superior light-scattering ability, the resultant HM-TiO2 are advantageous as photoanodes for dye-sensitized solar cells. When assembled to the entire photovoltaic device with C101 dye as a sensitizer, the pure HM-TiO2-based solar cells showed an ultrahigh photovoltage up to 0.853 V. Finally, by employing the as-obtained HM-TiO2 as the scattering layer and optimizing the architecture of dye-sensitized solar cells, both higher photovoltage and incident photon-to-electron conversion efficiency value were harvested with respect to TiO2 nanoparticles-based dye-sensitized solar cells, resulting in a high power conversion efficiency of 9.79%. This work provides a promising strategy to develop photoanode materials with outstanding photoelectric conversion performance.

Inside-out Ostwald ripening: A facile process towards synthesizing anatase TiO2 microspheres for high-efficiency dye-sensitized solar cells

A facile inside-out Ostwald ripening route to the morphology-controlled preparation of TiO2 microspheres is developed. Here, TiO2 hollow microspheres (HM) and solid microspheres (SM) are prepared by adjusting the volume ratio of isopropanol (IPA) to acetylacetone (Acac) in the solvothermal process. During the formation process of HM, precipitation of solid cores, subsequent deposition of outer shells on the surface of cores, and simultaneous core dissolution and shell recrystallization are observed, which validate the inside-out Ostwald ripening mechanism. Design and optimization of the properties (pore size, surface area, and trap state) of TiO2 microspheres are vital to the high performance of dyesensitized solar cells (DSSCs). The optimized TiO2 microspheres (rHM and rSM) obtained by post-processing on recrystallization, possess large pore sizes, high surface areas and reduced trap states (Ti3+ and oxygen vacancy), and are thus ideal materials for photovoltaic devices. The power conversion efficiency of DSSCs fabricated using rHM photoanode is 11.22%, which is significantly improved compared with the 10.54% efficiency of the rSM-based DSSC. Our work provides a strategy for synthesizing TiO2 microspheres that simultaneously accommodate different physical properties, in terms of surface area, crystallinity, morphology, and mesoporosity.

Diketopyrrolopyrrole or benzodithiophene-arylamine small-molecule hole transporting materials for stable perovskite solar cells

Two simple small-molecular arylamine derivatives 4-methoxy-N-(4-methoxyphenyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)aniline (OMeTPA-DPP) and 4,4′-(4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) (OMeTPA-BDT) linked with diketopyrrolopyrrole or benzodithiophene moieties have been synthesized. The new compounds show better thermal stability than spiro-OMeTAD. The steady-state and time-resolved photoluminescence demonstrate that the new compounds have good hole extraction ability. The perovskite solar cells employing OMeTPA-BDT show a comparable power conversion efficiency with that of spiro-OMeTAD. After more than 200 hours of aging under one sun illumination, the residual efficiencies of the PSCs based on OMeTPA-DPP, OMeTPA-BDT and spiro-OMeTAD are 8.69%, 11.15% and 9.08%, respectively. The results demonstrate that the newly-developed compounds can act as efficient hole transporting materials for stable perovskite solar cells.

Broad spectral-response organic D–A–π–A sensitizer with pyridine-diketopyrrolopyrrole unit for dye-sensitized solar cells

In this work, four D–A–π–A sensitizers PDPP-I–IV based on pyridine-flanked DPP moieties (PDPP) were designed and synthesized for dye-sensitized solar cells. Remarkably, the incorporated electron-withdrawing unit of pyridine-flanked DPP improves the light-harvesting ability and modifies the electrochemical and absorption properties, generating a broader IPCE wavelength responding region. The electrochemical experiments and time-resolved photoluminescence measurements indicate the ability of electron-injection into the TiO2 conductive band from the excited sensitizer. The transient absorption spectra were measured to investigate the feasibility of the dynamics for oxidized-state sensitizer regeneration. The IPCE spectra demonstrate the broad spectral response region of these sensitizers. Especially, the IPCE of PDPP-III reached the near infrared (NIR) region (>800 nm) with the highest short-circuit current of 16.17 mA cm−2 in these sensitizers. Furthermore, the electrochemical impedance spectroscopy (EIS) experiments suggest that the electron-lifetime and charge recombination resistance increased when attaching the stereo substituted groups (R2) on the PDPP moiety, resulting in a higher open-circuit voltage (Voc). It can be found that PDPP-II based DSSCs with liquid electrolyte exhibited the highest Voc (523 mV) and power conversion efficiency (PCE) of 5.26%.

Enhancing the Photovoltaic Performance of Perovskite Solar Cells with a Down-Conversion Eu-Complex

Organometal halide perovskite solar cells (PSCs) have shown high photovoltaic performance but poor utilization of ultraviolet (UV) irradiation. Lanthanide complexes have a wide absorption range in the UV region and they can down-convert the absorbed UV light into visible light, which provides a possibility for PSCs to utilize UV light for higher photocurrent, efficiency, and stability. In this study, we use a transparent luminescent down-converting layer (LDL) of Eu-4,7-diphenyl-1,10-phenanthroline (Eu-complex) to improve the light utilization efficiency of PSCs. Compared with the uncoated PSC, the PSC coated with Eu-complex LDL on the reverse of the fluorine-doped tin oxide glass displayed an enhancement of 11.8% in short-circuit current density (Jsc) and 15.3% in efficiency due to the Eu-complex LDL re-emitting UV light (300-380 nm) in the visible range. It is indicated that the Eu-complex LDL plays the role of enhancing the power conversion efficiency as well as reducing UV degradation for PSCs.

Surface states in TiO2 submicrosphere films and their effect on electron transport

Owing to their special three-dimensional network structure and high specific surface area, TiO2 submicrospheres have been widely used as electron conductors in photoanodes for solar cells. In recent years, utilization of TiO2 submicrospheres in solar cells has greatly boosted the photovoltaic performance. Inevitably, however, numerous surface states in the TiO2 network affect electron transport. In this work, the surface states in TiO2 submicrospheres were thoroughly investigated by charge extraction methods, and the results were confirmed by the cyclic voltammetry method. The results showed that ammonia can effectively reduce the number of surface states in TiO2 submicrospheres. Furthermore, in-depth characterizations indicate that ammonia shifts the conduction band toward a more positive potential and improves the interfacial charge transfer. Moreover, charge recombination is effectively prevented. Overall, the cell performance is essentially dependent on the effect of the surface states, which affects the electron transfer and recombination process.