Ion-Exchange Polymer Network Enhanced Interfacial Compatibility for Stable and Efficient Inverted Perovskite Solar Cells.

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as a low-cost and water-processable hole transport material has been widely used in various optoelectronic devices. Although the incorporation of anionic polyelectrolyte PSS in PEDOT contributes to superior water solubility, the trade-off between efficiency and stability remains a challenging issue, limiting its reliable application in perovskite solar cells (PSCs). Herein, we proposed an ion-exchange (IE) strategy to effectively control the doping degree, interfacial charge dynamics, and reliability of PEDOT:PSS in PSCs. This IE approach based on hard cation-soft anion rules enabled effective anion exchange between PEDOT:PSS and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), which favored enhancing the film conductivity, regulating the perovskite crystallization, and reducing the carrier losses at the interfaces. Consequently, a notable increase of the open-circuit voltage from 0.88 to 1.02 V was realized, resulting in a champion efficiency of 18.7% compared to the control (15.4%) in inverted PSCs. More encouragingly, this IE strategy significantly promoted the thermal and environmental stability of unsealed devices by maintaining over 80% of initial efficiencies after 2000 h. This work provides an effective way to regulate the doping state of the PEDOT-based hole transport material and guides the development of robust polymeric conducting materials for efficient perovskite photovoltaics.

Conjugated Phosphonic Acids Enable Robust Hole Transport Layers for Efficient and Intrinsically Stable Perovskite Solar Cells.

High efficiency and long-term stability are the prerequisites for the commercialization of perovskite solar cells (PSCs). However, inadequate and non-uniform doping of hole transport layers (HTLs) still limits the efficiency improvements, while the intrinsic instability of HTLs caused by ion migration and accumulation is difficult to be addressed by external encapsulation. Here it is shown that the addition of a conjugated phosphonic acid (CPA) to the Spiro-OMeTAD benchmark HTL can greatly enhance the device efficiency and intrinsic stability. Featuring an optimal diprotic-acid structure, indolo(3,2-b)carbazole-5,11-diylbis(butane-4,1-diyl) bis(phosphonic acid) (BCZ) is developed to promote morphological uniformity and mitigate ion migration across both perovskite/HTL and HTL/Ag interfaces, leading to superior charge conductivity, reinforced ion immobilization, and remarkable film stability. The dramatically improved interfacial charge collection endows BCZ-based n-i-p PSCs with a champion power conversion efficiency of 24.51%. More encouragingly, the BCZ-based devices demonstrate remarkable stability under harsh environmental conditions by retaining 90% of initial efficiency after 3000 h in air storage. This work paves the way for further developing robust organic HTLs for optoelectronic devices.

Halides-Enhanced Buried Interfaces for Stable and Extremely Low-Voltage-Deficit Perovskite Solar Cells.

The perovskite buried interfaces have demonstrated pivotal roles in determining both the efficiency and stability of perovskite solar cells (PSCs); however, challenges remain in understanding and managing the interfaces due to their non-exposed feature. Here, we proposed a versatile strategy of pre-grafted halides to strengthen the SnO2 -perovskite buried interface by precisely manipulating perovskite defects and carrier dynamics through alteration of halide electronegativity (χ), thereby resulting in both favorable perovskite crystallization and minimized interfacial carrier losses. Specifically, the implementation of fluoride with the highest χ induces the strongest binding affinity to uncoordinated SnO2  defects and perovskite cations, leading to retarded perovskite crystallization and high-quality perovskite films with reduced residual stress. These improved properties enable champion efficiencies of 24.2% (the control: 20.5%) and 22.1% (the control: 18.7%) in rigid and flexible devices with extremely low voltage deficit down to 386 mV, all of which are among the highest reported values for PSCs with a similar device architecture. In addition, the resulting devices exhibit marked improvements in the device longevity under various stressors of humidity (>5000 h), light (1000 h), heat (180 h), and bending test (10 000 times). This method provides an effective way to improve the quality of buried interfaces toward high-performance PSCs.

Dynamic self-assembly of small molecules enables the spontaneous fabrication of hole conductors at perovskite/electrode interfaces for over 22% stable inverted perovskite solar cells.

The bottom hole transport layers (HTLs) are of paramount importance in determining both the efficiency and stability of inverted perovskite solar cells (PSCs), however, their surface nature and properties strongly interfere with the upper perovskite crystallization kinetics and also influence interfacial carrier dynamics. In this work, we strategically develop a simple, facile and spontaneous fabrication method of the HTL at the perovskite/electrode interface by dynamic self-assembly (DSA) of small molecules during perovskite crystallization. Different from the traditional layer-by-layer approach, this DSA strategy involves a bilateral movement of self-assembled molecules (SAMs) from perovskite solution, realizing simultaneous fabrication of the HTL and perovskite surface passivation. We design a multifunctional molecule, (4-(7H-benzo[c]carbazol-7-yl)butyl)phosphonic acid (BCB-C4PA), for the DSA process, to optimize both self-assembly ability and interfacial energy alignment. Benefitting from this unconventional DSA approach and BCB-C4PA, a champion PCE of 22.2% is achieved along with remarkable long-term environmental stability for over 2750 h, which is among the highest reported efficiencies for SAM-based PSCs. This investigation provides a creative, unique and effective molecular approach for preparing reliable charge transport layers, opening up new avenues for the further development of efficient interfacial contacts for PSCs.

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.

Blue-emitting NH4+-doped MAPbBr3 perovskite quantum dots with near unity quantum yield and super stability.

Novel NH4+-doped MA1-x(NH4)xPbBr3 perovskite quantum dots were synthesized at room temperature. The introduction of NH4+ results in larger lattice formation energy and better crystallinity of MA1-x(NH4)xPbBr3, which greatly reduces the defect density and inhibits non-radiative recombinations, and thus helps in achieving excellent stability and near unity blue-emitting photoluminescence quantum yields.

Exploring the electrochemical properties of hole transporting materials from first-principles calculations: an efficient strategy to improve the performance of perovskite solar cells.

Perovskite solar cells (PSCs) have been achieved with impressively dynamic improvement in power conversion efficiency (PCE), becoming the hottest topic in photovoltaics. One of the hot topics is to develop inexpensive and efficient hole transporting materials (HTMs). In the present work, we systematically investigated the impact of different atoms in the heteromerous structure on the performance of perovskite solar cells. In addition, the influence of the structural modification of the HTM molecular building blocks was also revealed. To further understand the relationship between the charge-transport properties and the structural modification, the electronic properties, reorganization energy, and hole transporting properties of a series of organic hole transporting materials were investigated using first-principles calculations combined with Marcus theory. Moreover, the orientation function µΦ (V, λ, r, θ, γ; Φ) was applied to quantitatively evaluate the overall carrier mobility of HTMs in PSCs. It is revealed that this model predicts the hole mobility of HTMs correctly. The calculated results indicate that hole transporting materials with heteroatoms and larger dimensional structures show higher hole mobility, which may significantly improve the photovoltaic performance of PSCs.