Metal Oxide Semiconductors for Dye‐ and Quantum‐Dot‐Sensitized Solar Cells

This Review provides a brief summary of the most recent research developments in the synthesis and application of nanostructured metal oxide semiconductors for dye sensitized and quantum dot sensitized solar cells. In these devices, the wide bandgap semiconducting oxide acts as the photoanode, which provides the scaffold for light harvesters (either dye molecules or quantum dots) and electron collection. For this reason, proper tailoring of the optical and electronic properties of the photoanode can significantly boost the functionalities of the operating device. Optimization of the functional properties relies with modulation of the shape and structure of the photoanode, as well as on application of different materials (TiO₂, ZnO, SnO₂) and/or composite systems, which allow fine tuning of electronic band structure. This aspect is critical because it determines exciton and charge dynamics in the photoelectrochemical system and is strictly connected to the photoconversion efficiency of the solar cell. The different strategies for increasing light harvesting and charge collection, inhibiting charge losses due to recombination phenomena, are reviewed thoroughly, highlighting the benefits of proper photoanode preparation, and its crucial role in the development of high efficiency dye sensitized and quantum dot sensitized solar cells.     

Cosensitized Quantum Dot Solar Cells with Conversion Efficiency over 12%

The improvement of sunlight utilization is a fundamental approach for the construction of high‐efficiency quantum‐dot‐based solar cells (QDSCs). To boost light harvesting, cosensitized photoanodes are fabricated in this work by a sequential deposition of presynthesized Zn–Cu–In–Se (ZCISe) and CdSe quantum dots (QDs) on mesoporous TiO₂ films via the control of the interactions between QDs and TiO₂ films using 3‐mercaptopropionic acid bifunctional linkers. By the synergistic effect of ZCISe‐alloyed QDs with a wide light absorption range and CdSe QDs with a high extinction coefficient, the incident photon‐to‐electron conversion efficiency is significantly improved over single QD‐based QDSCs. It is found that the performance of cosensitized photoanodes can be optimized by adjusting the size of CdSe QDs introduced. In combination with titanium mesh supported mesoporous carbon as a counterelectrode and a modified polysulfide solution as an electrolyte, a champion power conversion efficiency up to 12.75% (V_oc = 0.752 V, J_sc = 27.39 mA cm^?2, FF = 0.619) is achieved, which is, as far as it is known, the highest efficiency for liquid‐junction QD‐based solar cells reported.     

A Small‐Molecule “Charge Driver” enables Perovskite Quantum Dot Solar Cells with Efficiency Approaching 13%

Halide perovskite colloidal quantum dots (CQDs) have recently emerged as a promising candidate for CQD photovoltaics due to their superior optoelectronic properties to conventional chalcogenides CQDs. However, the low charge separation efficiency due to quantum confinement still remains a critical obstacle toward higher‐performance perovskite CQD photovoltaics. Available strategies employed in the conventional CQD devices to enhance the carrier separation, such as the design of type‐Ⅱ core–shell structure and versatile surface modification to tune the electronic properties, are still not applicable to the perovskite CQD system owing to the difficulty in modulating surface ligands and structural integrity. Herein, a facile strategy that takes advantage of conjugated small molecules that provide an additional driving force for effective charge separation in perovskite CQD solar cells is developed. The resulting perovskite CQD solar cell shows a power conversion efficiency approaching 13% with an open‐circuit voltage of 1.10 V, short‐circuit current density of 15.4 mA cm^?2, and fill factor of 74.8%, demonstrating the strong potential of this strategy toward achieving high‐performance perovskite CQD solar cells.     

A 3‐Fluoro‐4‐hexylthiophene‐Based Wide Bandgap Donor Polymer for 10.9% Efficiency Eco‐Friendly Nonfullerene Organic Solar Cells

Nonfullerene organic solar cells (NFOSCs) are attracting increasing academic and industrial interest due to their potential uses for flexible and lightweight products using low‐cost roll‐to‐roll technology. In this work, two wide bandgap (WBG) polymers, namely P(fTh‐BDT)‐C6 and P(fTh‐2DBDT)‐C6, are designed and synthesized using benzodithiophene (BDT) derivatives. Good oxidation stability and high solubility are achieved by simultaneously introducing fluorine and alkyl chains to a single thiophene (Th) unit. Solid P(fTh‐2DBDT)‐C6 films present WBG optical absorption, suitable frontier orbital levels, and strong π–π stacking effects. In addition, P(fTh‐2DBDT)‐C6 exhibits good solubility in both halogenated and nonhalogenated solvents, suggesting its suitability as donor polymer for NFOSCs. The P(fTh‐2DBDT)‐C6:3,9‐bis(2‐methylene‐(3‐(1,1‐dicyanomethylene)‐indanone))‐5,5,11,11‐tetrakis(5‐hexylthienyl)‐dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene (ITIC‐Th) based device processed using chlorobenzene/1,8‐diiodooctane (CB/DIO) exhibits a remarkably high power conversion efficiency (PCE) of 11.1%. Moreover, P(fTh‐2DBDT)‐C6:ITIC‐Th reaches a high PCE of 10.9% when processed using eco‐friendly solvents, such as o‐xylene/diphenyl ether (DPE). The cell processed using CB/DIO maintains 100% efficiency after 1272 h, while that processed using o‐xylene/DPE presents a 101% increase in efficiency after 768 h and excellent long‐term stability. The results of this study demonstrate that simultaneous fluorination and alkylation are effective methods for designing donor polymers appropriate for high‐performance NFOSCs.     

Carbon Nanotubes for Dye‐Sensitized Solar Cells

As one type of emerging photovoltaic cell, dye‐sensitized solar cells (DSSCs) are an attractive potential source of renewable energy due to their eco–friendliness, ease of fabrication, and cost effectiveness. However, in DSSCs, the rarity and high cost of some electrode materials (transparent conducting oxide and platinum) and the inefficient performance caused by slow electron transport, poor light‐harvesting efficiency, and significant charge recombination are critical issues. Recent research has shown that carbon nanotubes (CNTs) are promising candidates to overcome these issues due to their unique electrical, optical, chemical, physical, as well as catalytic properties. This article provides a comprehensive review of the research that has focused on the application of CNTs and their hybrids in transparent conducting electrodes (TCEs), in semiconducting layers, and in counter electrodes of DSSCs. At the end of this review, some important research directions for the future use of CNTs in DSSCs are also provided.     

Lead Selenide (PbSe) Colloidal Quantum Dot Solar Cells with >10% Efficiency

Low‐cost solution‐processed lead chalcogenide colloidal quantum dots (CQDs) have garnered great attention in photovoltaic (PV) applications. In particular, lead selenide (PbSe) CQDs are regarded as attractive active absorbers in solar cells due to their high multiple‐exciton generation and large exciton Bohr radius. However, their low air stability and occurrence of traps/defects during film formation restrict their further development. Air‐stable PbSe CQDs are first synthesized through a cation exchange technique, followed by a solution‐phase ligand exchange approach, and finally absorber films are prepared using a one‐step spin‐coating method. The best PV device fabricated using PbSe CQD inks exhibits a reproducible power conversion efficiency of 10.68%, 16% higher than the previous efficiency record (9.2%). Moreover, the device displays remarkably 40‐day storage and 8 h illuminating stability. This novel strategy could provide an alternative route toward the use of PbSe CQDs in low‐cost and high‐performance infrared optoelectronic devices, such as infrared photodetectors and multijunction solar cells.     

Ultrafast Flame Annealing of TiO2 Paste for Fabricating Dye‐Sensitized and Perovskite Solar Cells with Enhanced Efficiency

Mesoporous TiO₂ nanoparticle (NP) films are broadly used as electrodes in photoelectrochemical cells, dye‐sensitized solar cells (DSSCs), and perovskite solar cells (PSCs). State‐of‐the‐art mesoporous TiO₂ NP films for these solar cells are fabricated by annealing TiO₂ paste‐coated fluorine‐doped tin oxide glass in a box furnace at 500 °C for ≈30 min. Here, the use of a nontraditional reactor, i.e., flame, is reported for the high throughput and ultrafast annealing of TiO₂ paste (≈1 min). This flame‐annealing method, compared to conventional furnace annealing, exhibits three distinct benefits. First, flame removes polymeric binders in the initial TiO₂ paste more completely because of its high temperature (≈1000 °C). Second, flame induces strong interconnections between TiO₂ nanoparticles without affecting the underlying transparent conducting oxide substrate. Third, the flame‐induced carbothermic reduction on the TiO₂ surface facilitates charge injection from the dye/perovskite to TiO₂. Consequently, when the flame‐annealed mesoporous TiO₂ film is used to fabricate DSSCs and PSCs, both exhibit enhanced charge transport and higher power conversion efficiencies than those fabricated using furnace‐annealed TiO₂ films. Finally, when the ultrafast flame‐annealing method is combined with a fast dye‐coating method to fabricate DSSC devices, its total fabrication time is reduced from over 3 h to ≈10 min.     

Planar‐Structure Perovskite Solar Cells with Efficiency beyond 21%

Low temperature solution processed planar‐structure perovskite solar cells gain great attention recently, while their power conversions are still lower than that of high temperature mesoporous counterpart. Previous reports are mainly focused on perovskite morphology control and interface engineering to improve performance. Here, this study systematically investigates the effect of precise stoichiometry, especially the PbI₂ contents on device performance including efficiency, hysteresis and stability. This study finds that a moderate residual of PbI₂ can deliver stable and high efficiency of solar cells without hysteresis, while too much residual PbI₂ will lead to serious hysteresis and poor transit stability. Solar cells with the efficiencies of 21.6% in small size (0.0737 cm²) and 20.1% in large size (1 cm²) with moderate residual PbI₂ in perovskite layer are obtained. The certificated efficiency for small size shows the efficiency of 20.9%, which is the highest efficiency ever recorded in planar‐structure perovskite solar cells, showing the planar‐structure perovskite solar cells are very promising.     

Polymer Solar Cells with 90% External Quantum Efficiency Featuring an Ideal Light‐ and Charge‐Manipulation Layer

Rapid progress in the power conversion efficiency (PCE) of polymer solar cells (PSEs) is beneficial from the factors that match the irradiated solar spectrum, maximize incident light absorption, and reduce photogenerated charge recombination. To optimize the device efficiency, a nanopatterned ZnO:Al₂O₃ composite film is presented as an efficient light‐ and charge‐manipulation layer (LCML). The Al₂O₃ shells on the ZnO nanoparticles offer the passivation effect that allows optimal electron collection by suppressing charge‐recombination loss. Both the increased refractive index and the patterned deterministic aperiodic nanostructure in the ZnO:Al₂O₃ LCML cause broadband light harvesting. Highly efficient single‐junction PSCs for different binary blends are obtained with a peak external quantum efficiency of up to 90%, showing certified PCEs of 9.69% and 13.03% for a fullerene blend of PTB7:PC₇₁BM and a nonfullerene blend, FTAZ:IDIC, respectively. Because of the substantial increase in efficiency, this method unlocks the full potential of the ZnO:Al₂O₃ LCML toward future photovoltaic applications.     

TiO2纳米管的制备及应用研究进展

TiO2纳米管由于其表面积大、吸附能力强和电子迁移率高等特点而在光催化、太阳能电池、锂电池和传感器等领域中展现出巨大的应用潜力.综述了TiO2纳米管常用的几种制备方法,以及TiO2纳米管在相关应用领域中的最新研究进展.     

Hydrothermal Growth of TiO2 Nanorod Arrays and In Situ Conversion to Nanotube Arrays for Highly Efficient Quantum Dot‐Sensitized Solar Cells

TiO₂ nanorod (NR) and nanotube (NT) arrays grown on transparent conductive substrates are attractive electrode for solar cells. In this paper, TiO₂ NR arrays are hydrothermally grown on FTO substrate, and are in situ converted into NT arrays by hydrothermally etching. The TiO₂ NR arrays are reported as single crystalline, but the TiO₂ NR arrays are demonstrated to be polycrystalline with a bundle of 2–5 nm single crystalline nanocolumns grown along [001] throughout the whole NR from bottom to top. TiO₂ NRs can be converted to NTs by hydrothermal selective etching of the (001) core and remaining the inert sidewall of (110) face. A growth mechanism of the NR and NT arrays is proposed. Quantum dot‐sensitized solar cells (QDSCs) are fabricated by coating CdSe QDs on to the TiO₂ arrays. After conversion from NRs to NTs, more QDs can be filled in the NTs and the energy conversion efficiency of the QDSCs almost double.