Efficient and stabilized molecular doping of hole-transporting materials driven by a cyclic-anion strategy for perovskite solar cells.

Bis(trifluoromethane)sulfonimide lithium salt (Li-TFSI) is commonly used as an effective dopant to improve the performance of the hole-transporting material (HTM) in n-i-p perovskite solar cells (PSCs). However, the ultra-hygroscopic and migratory nature of Li-TFSI leads to inferior stability of PSCs. Here, we report on a strategy to regulate the anion unit in Li-TFSI from linear to cyclic, constructing a new dopant, lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide (Li-CYCLIC), for the state-of-the-art poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA). Mechanistic and experimental results reveal that the cyclic anion CYCLIC- exhibits stronger interaction with Li+ and PTAA˙+ compared with the linear anion TFSI-, thus significantly restraining the moisture absorption and migration of Li+ and improving the thermodynamic stability of PTAA˙+CYCLIC-. With this molecular engineering, the resulting PSCs based on Li-CYCLIC obtained an improved efficiency, along with remarkably enhanced stability, retaining 96% of the initial efficiency after over 1150 hours under continuous 1 sun illumination in an N2 atmosphere, yielding an extrapolated T 80 of over 12 000 hours. In a broader context, the proposed strategy of linear-to-cyclic doping provides substantial guidance for the subsequent advancement in the development of effective dopants for photoelectric devices.

Polymer-acid-metal quasi-ohmic contact for stable perovskite solar cells beyond a 20,000-hour extrapolated lifetime.

The development of a robust quasi-ohmic contact with minimal resistance, good stability and cost-effectiveness is crucial for perovskite solar cells. We introduce a generic approach featuring a Lewis-acid layer sandwiched between dopant-free semicrystalline polymer and metal electrode in perovskite solar cells, resulting in an ideal quasi-ohmic contact even at elevated temperature up to 85 °C. The solubility of Lewis acid in alcohol facilitates nondestructive solution processing on top of polymer, which boosts hole injection from polymer into metal by two orders of magnitude. By integrating the polymer-acid-metal structure into solar cells, devices exhibit remarkable resilience, retaining 96% ± 3%, 96% ± 2% and 75% ± 7% of their initial efficiencies after continuous operation in nitrogen at 35 °C for 2212 h, 55 °C for 1650 h and 85 °C for 937 h, respectively. Leveraging the Arrhenius relation, we project an impressive T80 lifetime of 26,126 h at 30 °C.

Approach to Significantly Enhancing the Electrochromic Performance of PANi by In Situ Electrodeposition of the PANi@MXene Composite Film.

Electrochromic materials (ECMs) are capable of reversibly adjusting their transmittance or reflectance properties in response to changes in the external biasing voltages. In this study, we enhanced the electrochromic and electrochemical properties of polyaniline (PANi) effectively through the incorporation of MXene Ti2CTx using an in situ composite strategy. This improvement in the electrochromic and electrochemical properties observed can be attributed to the intermolecular forces between the aniline group of PANi and the terminal groups of MXene Ti2CTx sheets. The presence of hydrogen bonds between the PANi monomers and the MXene sheets was confirmed through theoretical calculations and photoluminescence results, which effectively improved the composite interfaces. Additionally, the PANi@MXene composite films were successfully prepared through a simple one-step in situ polymerization process, as verified by SEM and XPS characterization. The electrochemical studies revealed enhanced electronic conductivity, a high ion diffusion coefficient, and a narrow energy redox gap, all contributing to the excellent electrochemical properties observed. Overall, our results demonstrate that the MXene Ti2CTx composition effectively enhances the electrochromic performance of PANi. The PANi@MXene composite films exhibited a high optical modulation range, rapid switching response time, good thermal radiation regulation, and excellent operational stability. This composite strategy significantly improves the performance and practical applicability of ECMs.

Trace Doping: Fluorine-Containing Hydrophobic Lewis Acid Enables Stable Perovskite Solar Cells.

With the rapid development in perovskite solar cell (PSC), high efficiency has been achieved, but the long-term operational stability is still the most important challenges for the commercialization of this emerging photovoltaic technology. So far, bi-dopants lithium bis(trifluoromethylsulfonyl)-imide (Li-TFSI)/4-tert-butylpyridine (t-BP)-doped hole-transporting materials (HTM) have led to state-of-the art efficiency in PSCs. However, such dopants have several drawbacks in terms of stability, including the complex oxidation process, undesirable ion migration and ultra-hygroscopic nature. Herein, a fluorine-containing organic Lewis acid dopant bis(pentafluorophenyl)zinc (Zn-FP) with hydrophobic property and high migration barrier has been employed as a potential alternative to widely employed bi-dopants Li-TFSI/t-BP for poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA). The resulting Zn-FP-based PSCs achieve a maximum PCE of 20.34 % with hysteresis-free current density-voltage (J-V) scans. Specifically, the unencapsulated device exhibits a significantly advanced of operational stability under the International Summit on Organic Photovoltaic Stability protocols (ISOS-L-1), maintaining over 90 % of the original efficiency after operation for 1000 h under continuous 1-sun equivalent illumination in N2 atmosphere in both forward and reverse J-V scan.

A new strategy for constructing a dispiro-based dopant-free hole-transporting material: spatial configuration of spiro-bifluorene changes from a perpendicular to parallel arrangement.

Due to the low intrinsic hole mobility caused by the orthogonal conformation of two fluorene units in Spiro-OMeTAD which is a classic hole-transporting material (HTM) in perovskite solar cells (PSCs), Spiro-OMeTAD based PSCs generally can only obtain high performances through a sophisticated doping process with dopants/additives, which adds to the cost and complicacy of device fabrication, and also adversely affects the stability of PSC devices. Herein, a novel dispiro-based HTM, WH-1, is designed by cleverly replacing the central carbon atom of Spiro-OMeTAD with cyclohexane, and the spatial configuration of the HTM is changed from vertical orthogonality of the two fluorene units to a parallel arrangement, which is beneficial for the formation of a homogeneous and compact HTM film on the surface of the perovskite film, improvement of intermolecular electronic coupling and intrinsic hole mobility. WH-1 is obtained by two-step facile synthesis with a high yield from commercially available materials. WH-1 is used in PSCs as a dopant-free HTM, which is the first time that the dispiro-based molecule has been applied as a dopant-free HTM, and a power conversion efficiency (PCE) of 19.57% is obtained, rivaling Li-TFSI/t-BP doped Spiro-OMeTAD in PCE (20.29%), and showing obvious superior long-term stability.

Towards ultra-wide operation range and high sensitivity: Graphene film based pressure sensors for fingertips.

Remarkable research efforts have been devoted to replicate the tactile sensitivity of human skin. Unfortunately, so far flexible pressure sensors reported barely fit the tactile requirements for fingertips, which could endure a pressure over 100 kPa and also can sense a gentle touch. It is vital to develop flexible pressure sensors which can ensure high sensitivity and wide operation range simultaneously, to satisfy the demands of mimicking the pressure sensing function of fingertips. In this work, a mini-size, light-weight but high-performance graphene film based pressure sensor is presented. Owing to the advanced structure with fluctuations on surface and fluffy-layered structure in cross-section of the graphene film, this pressure sensor shows an extraordinary performance of high sensitivity of 10.39 kPa-1 (0-2 kPa), ultra-wide operation range up to 200 kPa, impressively stable repeatability, high working frequency, rapid response and recovery time. Moreover, the demonstrated results of the detection of traditional Chinese medicine wrist-pulse waveform and the bionic fingertip tactile sensors, suggest the great application potential of the obtain device in biomedical field and bionic skins field.

Intelligent Biomimetic Chameleon Skin with Excellent Self-Healing and Electrochromic Properties.

Animals such as chameleons possess a natural ability to adjust their skin color as a preventive measure to deter any potential threat and to self-heal damaged skin tissues. Inspired by this, we present here a copolymer film possessing biomimetic properties that simultaneously integrates electrochromic triphenylamine and self-healing Diels-Alder groups. The flexible and stretchable copolymer film acts like natural chameleon skin, which exhibits significant color variation and also possesses excellent self-healing properties. These remarkable features make it a promising material for overcoming the crack-generation issue inherited by conventional biomimetic chameleon skin. Moreover, a flexible and wearable skin device based on the copolymer film with silver fabric as a electrode has also been fabricated. The electrochromic and self-healing properties were verified for the copolymer film, and it has been elucidated that the intelligent biomimetic "chameleon skin" was a new step toward the development of highly advanced biomimetic materials and devices.

A Strategy To Boost the Efficiency of Rhodanine Electron Acceptor for Organic Dye: From Nonconjugation to Conjugation.

Rhodanine-3-acetic acid is a very important and common electron acceptor of organic dye for dye-sensitized solar cells (DSSCs). However, the photovoltaic performances of organic dyes with rhodanine-3-acetic acid are relatively poor in the great majority of cases due to its nonconjugated structure between rhodanine ring and carboxyl anchoring group. Herein, a rhodanine derivative with conjugated structure between rhodanine ring and anchoring group is first employed as electron acceptor for TiO2-based DSSCs. Organic dye with this conjugated electron acceptor can not only maintain wide absorption spectrum but also greatly improve the electronic structure and adsorption geometry on TiO2, which significantly enhances the electron injection and slows the charge recombination. So the power conversion efficiency of DSSC based on organic dye CRD-I with this conjugated electron acceptor is increased by 2 times as compared with DSSC based on organic dye RD-I with nonconjugated rhodanine-3-acetic acid. Moreover, it is also found that CRD-I is superior to RD-I with respect to DSSC stability and binding ability to TiO2. This work unambiguously demonstrates that the conjugated rhodanine derivative is a highly promising electron acceptor and provides a new strategy for high-efficiency rhodanine-based organic dyes in DSSCs.

In situ growth of hierarchical NiS2 hollow microspheres as efficient counter electrode for dye-sensitized solar cell.

Hierarchical NiS2 hollow microspheres (HM-NiS2) were successfully in situ grown on FTO by a one-step hydrothermal method, and then tested as the counter electrode (CE) for dye-sensitized solar cell (DSSC) for the first time. The SEM images reveal that the hierarchical NiS2 microspheres were successfully grown on FTO substrate. It is worth noting that some of the shells are partially broken, which is advantageous for providing more electrolyte adsorptions and electrocatalytic active sites. The electrocatalytic ability and electrochemical properties of the HM-NiS2 were studied by cyclic voltammetry, electrochemical impedance spectroscopy and Tafel polarization. The power conversion efficiency of 7.84% is achieved for the DSSC based on HM-NiS2 CE, which is close to that of the DSSC using Pt CE (7.89%). The results indicate that the in situ fabricated HM-NiS2 CE may be a good candidate for high efficiency and low-cost DSSCs.

Theoretical investigation of phenothiazine-triphenylamine-based organic dyes with different π spacers for dye-sensitized solar cells.

Three phenothiazine-triphenylamine-based organic dyes (CD-1, CD-2 and CD-3) are designed based on the dye WD-8. The geometries, electronic structures, and electronic absorption spectra of these dyes before and after binding to TiO2 are studied by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The calculated geometries indicate that these dyes show good steric hindrance effect which is advantage to inhibit the close intermolecular π-π aggregation effectively. The lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energy levels of these dyes could ensure positive effect on the process of electron injection and dye regeneration. The simulated spectra of CD-1∼3 show better absorption than that of WD-8 in the low energy zone. All the calculated results demonstrate that these dyes could be used as potential sensitizers for DSSCs and show better performances than WD-8.

Theoretical study of carbazole-triphenylamine-based dyes for dye-sensitized solar cells.

Three carbazole-triphenylamine-based dyes (D1, D2, D3) are designed. The geometries, electronic structures, and electronic absorption spectra of these dyes are studied by DFT and TD-DFT. The calculated geometries indicate that these dyes are all noncoplanar, which can help to inhibit the close intermolecular π-π aggregation effectively. The LUMO and HOMO energy levels of these dyes can be ensuring positive effect on the process of electron injection and dye regeneration. The trend of the calculated HOMO-LUMO gaps nicely compares with the spectral data. The calculated results of these dyes demonstrate that these dyes can be used as potential sensitizers for TiO(2) nanocrystalline solar cells.