Enhanced Interface Compatibility by Ionic Dendritic Molecules To Achieve Efficient and Stable Perovskite Solar Cells.

Poly(3-hexylthiophene) (P3HT) represents a promising hole transport material for emerging perovskite solar cells (PSCs) due to its appealing merits of high thermal stability and appropriate hydrophobicity. Nonetheless, large energy losses at the P3HT/perovskite interface lead to unsatisfied efficiency and stability of the devices. Herein, two ionic dendritic molecules, 3,3'-(2,7-bis(3,6-bis(bis(4-methoxyphenyl)amino)-9H-carbazol-9-yl)-9H-fluorene-9,9-diyl)bis(N,N,N-trimethylpropan-1-aminium) iodide and 3,3'-(2,7-bis(bis(4-(bis(4-methoxyphenyl)amino)phenyl)amino)-9H-fluorene-9,9-diyl)bis(N,N,N-trimethylpropan-1-aminium) iodide, namely, MPA-Cz-FAI and MPA-PA-FAI, are rationally designed as the interlayer to enhance interfacial compatibility. The dendritic backbone with conjugated structure endows the hole transport layer with high conductivity, derived from the more ordered microstructure with larger crystallization and higher connectivity of domain zones. Besides, a better energy level alignment is established between P3HT and perovskite, which enhances the charge extraction and transport yield. In addition, the peripheral methoxy groups enable effective defect passivation at the interface to suppress nonradiative recombination and the quaternary ammonium iodide serving as side chains enable efficient interfacial hole extraction contributing to enhanced charge collection yield. As a result, the dopant-free P3HT-based PSCs modified with MPA-Cz-PAI deliver a champion efficiency of 19.7%, significantly higher than that of the control devices (15.4%). More encouragingly, the unencapsulated devices demonstrate competitive environmental stability by retaining over 85% of its initial efficiency after 1500 h of storage under humid conditions (70% relative humidity). This work provides an effective molecular design strategy for interface engineering, envisaging a bright prospect for the further development of efficient and stable perovskite solar cells.

Sequential Molecule-Doped Hole Conductor to Achieve >23% Perovskite Solar Cells with 3000-Hour Operational Stability.

Although hole transport layers (HTLs) based on solution-processed doped Spiro-OMeTAD are extremely popular and effective for their remarkable performance in n-i-p perovskite solar cells (PSCs), their scalable application is still being held back by poor chemical stability and unsatisfied scalability. Essentially, the volatile components and hygroscopic nature of ionic salts often cause morphological deformation that deteriorate both device efficiency and stability. Herein, a simple and effective molecular implantation-assisted sequential doping (MISD) approach is strategically introduced to modulate spatial doping uniformity of organic films and fabricate all evaporated Spiro-OMeTAD layer in which phase-segregation free HTL is achieved accompanied with high molecular density, uniform doping composition, and superior optoelectronic characteristics. The resultant MISD-based devices attain a record power conversion efficiency (PCE) of 23.4%, which represents the highest reported value among all the PSCs with evaporated HTLs. Simultaneously, the unencapsulated devices realize considerably enhanced stability by maintaining over 90% of their initial PCEs in the air for 5200 h and after working at maximum power point under illumination for 3000 h. This method provides a facile way to fabricate robust and reliable HTLs toward developing efficient and stable perovskite solar cells.

Unveiling and Modulating the Interfacial Reaction at the Metal-Hole Conductor Heterojunction toward Reliable Perovskite Solar Cells.

Interfaces between functional layers in perovskite solar cells (PSCs) are of paramount importance in determining their efficiency and stability, but the interaction and stability of metal-hole conductor (HC) interfaces have received less attention. Here, we discover an intriguing transient behavior in devices which induces a profound efficiency fluctuation from 9 to 20% during the initial performance testing. Air exposure (e.g., oxygen and moisture) can significantly accelerate this nonequilibrium process and simultaneously enhance the device maximal efficiency. Structural analysis reveals that the chemical reaction between Ag and HC occurred during the metal deposition by thermal evaporation, leading to the formation of an insulating barrier layer at their interfaces, which results in a high charge-transport barrier and poor device performance. Accordingly, we propose a metal diffusion-associated barrier evolution mechanism to understand the metal/HC interfaces. To mitigate these detrimental effects, we strategically develop an interlayer strategy by introducing an ultrathin layer of molybdenum oxide (MoO3) between Ag and HC, which is found to effectively suppress the interfacial reaction, yielding highly reliable PSCs with instant high efficiency. This work provides new insights into understanding the metal-organic interfaces, and the developed interlayer strategy can be generally applicable to engineer other interfaces in realizing efficient and stable contacts.

Thermally Crosslinked Hole Conductor Enables Stable Inverted Perovskite Solar Cells with 23.9% Efficiency.

Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) represents the state-of-the-art hole transport material (HTM) in inverted perovskite solar cells (PSCs). However, unsatisfied surface properties of PTAA and high energy disorder in the bulk film hinder the further enhancement of device performance. Herein, a simple small molecule 10-(4-(3,6-dimethoxy-9H-carbazol-9-yl)phenyl)-3,7-bis(4-vinylphenyl)-10H-phenoxazine (MCz-VPOZ) is strategically developed for in situ fabrication of polymer hole conductor (CL-MCz) via a facile and low-temperature cross-linking technology. The resulting polymer CL-MCz offers high energy ordering and improved electrical conductivity, as well as appropriate energy-level alignment, enabling efficient charge carrier collection in the devices. Meanwhile, CL-MCz synchronously provides satisfied surface wettability and interfacial functionalization, facilitating the formation of high-quality perovskite films with fewer bulk iodine vacancies and suppressed carrier recombination. Significantly, the device with CL-MCz yields a champion efficiency of 23.9% along with an extremely low energy loss down to 0.41 eV, which represents the highest reported efficiency for non-PTAA-based polymer HTMs in inverted PSCs. Furthermore, the corresponding unencapsulated devices exhibit competitive shelf-life stability under various operational stressors up to 2500 h, reflecting high promises of CL-MCz in the scalable PSC application. This work underscores the promising potential of the cross-linking approach in preparing low-cost, stable, and efficient polymer HTMs toward reliable PSCs.