Collaborative Passivation for Dual Charge Transporting Layers Based on 4-(chloromethyl)benzonitrile Additive toward Efficient and Stable Inverted Perovskite Solar Cells.

Poor carrier transport capacity and numerous surface defects of charge transporting layers (CTLs), coupled with misalignment of energy levels between perovskites and CTLs, impact photoelectric conversion efficiency (PCE) of inverted perovskite solar cells (PSCs) profoundly. Herein, a collaborative passivation strategy is proposed based on 4-(chloromethyl) benzonitrile (CBN) as a solution additive for fabrication of both [6,6]-phenyl-C61-butyric acid methylester (PCBM) and poly(triarylamine) (PTAA) CTLs. This additive can improve wettability of PTAA and reduce the agglomeration of PCBM particles, which enhance the PCE and device stability of the PSCs. As a result, a PCE exceeding 20% with a remarkable short circuit current of 23.9 mA cm-2 , and an improved fill factor of 81% is obtained for the CBN- modified inverted PSCs. Devices maintain 80% and 70% of the initial PCE after storage under 30% and 85% humidity ambient conditions for 1000 h without encapsulation, as well as negligible light state PCE loss. This strategy demonstrates feasibility of the additive engineering to improve interfacial contact between the CTLs and perovskites for fabrication of efficient and stable inverted PSCs.

Interface Defects Dependent on Perovskite Annealing Temperature for NiOX-Based Inverted CsPbI2Br Perovskite Solar Cells.

Nickel oxide (NiOX) is an ideal inorganic hole transport material for the fabrication of inverted perovskite solar cells owing to its excellent optical and semiconductor properties. Currently, the main research on developing the performance of NiOX-based perovskite solar cells focuses on improving the conductivity of NiOX thin films and preventing the redox reactions between metal cations (Ni3+ on the surface of NiOX) and organic cations (FA+ or MA+ in the perovskite precursors) at the NiOX/perovskite interface. In this study, a new type of interface defects in NiOX-based CsPbI2Br solar cells is reported. That is the Pb2+ from CsPbI2Br perovskites can diffuse into the lattice of NiOX surface as the annealing temperature of perovskites changes. The diffusion of Pb2+ increases the ratio of Ni3+/Ni2+ on the surface of NiOX, leading to an increase in the density of trap state at the interface between NiOX and perovskites, which eventually results in a serious decline in the photovoltaic performance of solar cells.

SnO2-Perovskite Interface Engineering Based on Bifacial Passivation via Multifunctional N-(2-Acetamido)-2-aminoethanesulfonic Acid toward Efficient and Stable Solar Cells.

Bifacial passivation on both electron transport materials and perovskite light-absorbing layers as a straightforward technique is used for gaining efficient and stable perovskite solar cells (PSCs). To develop this strategy, organic molecules containing multiple functional groups can maximize the effect of defect suppression. Based on this, we introduce N-(2-acetamido)-2-aminoethanesulfonic acid (ACES) at the interface between tin oxide (SnO2) and perovskite. The synergistic effect of multiple functional groups in ACES, including amino, carbonyl (C═O), and sulfonic acid (S═O) groups, promotes charge extraction of SnO2 and provides an improved energy level alignment for charge transfer. Furthermore, S═O in ACES effectively passivates the defects of uncoordinated Pb2+ in perovskite films, resulting in enhanced crystallinity and decreased nonradiative recombination at the buried interface. The power conversion efficiency (PCE) of related PSCs increases from 20.21% to 22.65% with reduced J-V hysteresis after interface modification with ACES. Notably, upon being stored at a low relative humidity of 40 ± 5% over 2000 h and high relative humidity of 80 ± 5% over 1000 h, the unencapsulated ACES-modified device retains up to 90% and 80% of their initial PCE, respectively. This study deepens defect passivation engineering on the buried interface of perovskites for realizing efficient and stable solar cells.

Efficient and Stable CuSCN-based Perovskite Solar Cells Achieved by Interfacial Engineering with Amidinothiourea.

Cuprous thiocyanate (CuSCN) emerges as a prime candidate among inorganic hole-transport materials, particularly suitable for the fabrication of perovskite solar cells. Nonetheless, there is an Ohmic contact degradation between the perovskite and CuSCN layers. This is induced by polar solvents and undesired purities, which reduce device efficiency and operational stability. In this work, we introduce amidinothiourea (ASU) as an intermediate layer between perovskites and CuSCN to overcome the above obstacles. The characterization results confirm that ASU-modified perovskites have eliminated trap-induced defects by strong chemical bonding between -NH- and C═S from ASU and under-coordinated ions in perovskites. The interfacial engineering based on the ASU also reduces the potential barrier between the perovskite and CuSCN layers. The ASU-treated perovskite solar cells (PSC) with a gold electrode obtains an improved power conversion efficiency (PCE) from 16.36 to 18.03%. Furthermore, after being stored for 1800 h in ambient air (relative humidity (RH) = 45%), the related device without encapsulation maintains over 90% of its initial efficiency. The further combination of ASU and carbon-tape electrodes demonstrates its potential to fabricate low-cost but stable carbon-based PSCs. This work finds a universal approach for the fabrication of efficient and stable PSCs with different device structures.

Evaporated Nickel Oxide Films with Slow Annealing and Interface Modification for Perovskite Solar Cells.

Electron-beam-evaporated nickel oxide (NiOx) films are known for their high quality, precise control, and suitability for complex structures in perovskite (PVK) solar cells (PSCs). However, untreated NiOx films have inherent challenges, such as surface defects, relatively low intrinsic conductivity, and shallow valence band maximum, which seriously restrict the efficiency and stability of the devices. To address these challenges, we employ a dual coordination optimization strategy. The strategy includes low heating rate annealing of NiOx films and using an aminoguanidine nitrate spin coating process on the surfaces of NiOx films to strategically modify NiOx films itself and the interface of NiOx/PVK. Under the synergistic effect of this dual optimization method, the quality of the films is significantly improved and its p-type characteristics are enhanced. At the same time, the interface defects and energy level alignment of the films are effectively improved, and the charge extraction ability at the interface is improved. The combined treatment significantly improved the efficiency of inverted PSCs, from 17.85% to 20.31%, and enhanced device stability under various conditions. This innovative dual-coordinated optimization strategy provides a clear and effective framework for improving the performance of NiOx films and inverted PSCs.

Effects of Lead Iodide Crystallization on Photovoltaic Performance of Perovskite Solar Cells by the Vapor-Solid Reaction Method.

The vapor-solid reaction method (VRM) is one of the promising techniques to prepare high-performance perovskite solar cells. Herein, PbI2 precursor films were prepared by vacuum evaporation. It was found that the PbI2 precursor films exhibit high crystallinity and orderly morphology at the substrate temperature of 110 °C. On this basis, the precursor films were prepared by VRM to obtain high-quality perovskite films and the power conversion efficiency (PCE) of perovskite solar cells (PSCs) devices reached 17.1%. In contrast, the PbI2 film precursor was prepared on the substrate without being heated and the PCE of the final PSCs devices was only 13.04%.

Efficient liquid exfoliation of KP15 nanowires aided by Hansen's empirical theory.

The KP15 nanowires with one-dimensional properties has a defect-free surface, high anisotropy, and carrier mobility which is desirable for the development of novel nanodevices. However, the preparation of nanoscale KP15 is still inefficient. In this work, the Hansen solubility parameters of KP15 were first obtained. Based on the Hansen's empirical theory, the concentration of liquid-exfoliated KP15 nanowires was improved to 0.0458 mg·mL-1 by a solution containing 50% water and 50% acetone. Approximately 79% of the KP15 nanowires had a thickness value below 50 nm and 60.9% of them had a width value below 100 nm. The thinnest KP15 nanowires reached 5.1 nm and had smooth boundaries. Meanwhile, strong temperature-dependent Raman response in exfoliated KP15 nanowires has been observed, which indicates a strong phonon-phonon coupling in those nanowires. This is helpful for non-invasive temperature measurements of KP15 nanodevices.

Modifying SnO2 with Polyacrylamide to Enhance the Performance of Perovskite Solar Cells.

Modification of the charge transport layers is an effective way to improve charge transport and performance of perovskite solar cells (PSCs). The ions in the ionic compounds used for the modification of SnO2 may migrate into the perovskite layer, which harms the stability of PSCs. In this work, a low-cost, water-soluble nonionic polymer polyacrylamide (PAM) is used to modify SnO2. The addition of PAM improves the uniformity, wettability, and electron mobility of the SnO2 film. Through the modification of SnO2, the defects of perovskite films are reduced and the grain size is increased. Furthermore, the energy-level alignment at the SnO2/perovskite interface is improved, which is beneficial to the transfer of electrons from perovskite to SnO2. Finally, the power conversion efficiency (PCE) of PSCs formed from modified SnO2 is enhanced to 22.59%. More importantly, the unencapsulated devices with modified SnO2 retain 90% of the initial value after storage for more than 1000 h under a relative humidity of 50%. These results indicate that modifying SnO2 using PAM is a promising strategy to improve the performance of PSCs.

Low-Dimensional-Networked Perovskites with A-Site-Cation Engineering for Optoelectronic Devices.

Low-dimensional-networked (LDN) perovskites denote materials in which the molecular structure adopts 2D, 1D, or 0D arrangement. Compared to conventional 3D structured lead halide perovskite (chemical formula: ABX3 where A: monovalent cations, B: divalent cations, X: halides) that have been studied widely as light absorber and used in current state-or-the-art solar cells, LDN perovskite have unique properties such as more flexible crystal structure, lower ion transport mobility, robust stability against environmental stress such as moisture, thermal, etc., making them attractive for applications in optoelectronic devices. Since 2014, reports on LDN perovskite materials used in perovskite solar cells, light emitting diodes (LEDs), luminescent solar concentrators (LSC), and photodetectors have been reported, aiming to overcome the obstacles of conventional 3DN perovskite materials in these optoelectronic devices. In this review, the variable ligands used to make LDN perovskite materials are summarized, their distinct properties compared to conventional 3D perovskite materials. The research progress of optoelectronic devices including solar cells, LEDs, LSCs, and photodetectors that used different LDNs perovskite, the roles and working mechanisms of the LDN perovskites in the devices are also demonstrated. Finally, key research challenges and outlook of LDN materials for various optoelectronic applications are discussed.

Dimensionality-Controlled Surface Passivation for Enhancing Performance and Stability of Perovskite Solar Cells via Triethylenetetramine Vapor.

Perovskite solar cells (PSCs) have achieved unprecedented progress in terms of enhancement of power conversion efficiency (PCE). Nevertheless, device stability is still an obstacle to the commercialization of this emerging photovoltaic technology. Though strategies such as compositional management and ligand engineering have been reported to tackle this critical issue, these methods often have drawbacks such as compromised device performance. Herein, we propose an approach combining material dimensionality control and interfacial passivation by a post-device treatment via triethylenetetramine (TETA) vapor to enhance both efficiency and stability of Cs0.05FA0.79MA0.16PbI2.5Br0.5-based PSCs. Results of X-ray diffraction and scanning electron microscopy show the formation of low-dimensional perovskites at the interface between the perovskite film and the hole transporting layer after the TETA vapor treatment. Measurements of the energy level alignment and electrochemical properties by ultraviolet photoelectron spectroscopy and impedance spectra confirm the reduced density of trap states and improved interfacial charge transport. Consequently, TETA-based treatment significantly enhances both efficiency (from 17.07 to 18.03%) and stability (PCE retention from 73.4 to 88.9%) of the PSCs under >65% relative humidity for 1000 h compared to the controlled device without TETA treatment. Furthermore, the TETA vapor also shows an advantageous effect of dramatically improving the performance of PSC devices, which initially had poor performance (from 6.8 to 10.5%) through surface defect passivation.

2D-3D Mixed Organic-Inorganic Perovskite Layers for Solar Cells with Enhanced Efficiency and Stability Induced by n-Propylammonium Iodide Additives.

Device instability has become an obstacle for the industrial application of organic-inorganic metal halide perovskite solar cells that has already demonstrated over 23% laboratory power conversion efficiency (PCE). It has been discovered that the sliding of A-site cations in the perovskite compound through and out of the three-dimensional [PbI6]4- crystal frame is one of the main reasons that are responsible for decomposition of the perovskite compound. Herein, we report an effective method to enhance the stability of the FA0.79MA0.16Cs0.05PbI2.5Br0.5 perovskite film through the incorporation of n-propylammonium iodide (PAI). Both density functional theory calculation and the X-ray diffraction patterns have confirmed the formation of two-dimensional (PA)2PbI4 with the Ruddlesden-Popper perovskite as a result of the reaction between PAI and PbI2 in the perovskite film. X-ray photoelectron spectroscopy reveals less -COOH (carboxyl) groups on the surface of the perovskite film containing (PA)2PbI4, which indicates the suppressed penetration of oxygen and moisture into the perovskite material. This is further confirmed by the surface water wettability test of the (PA)2PbI4 film that exhibits excellent hydrophobic property with over 110° contact angle. Ultraviolet photoelectron spectroscopy demonstrates the introduction of PAI additives that resulted in the upshift of the conduction band minimum of the perovskite by 160 meV, leading to a more favorable energy alignment with an adjacent electron transporting material. As a consequence, enhanced 17.23% PCE with suppressed hysteresis was obtained with the 5% PAI additive (molar ratio) in perovskite solar cells that retained nearly 50% of the initial efficiency after 2000 h in air without encapsulation under 45% average relative humidity.

Interface Engineering to Eliminate Hysteresis of Carbon-Based Planar Heterojunction Perovskite Solar Cells via CuSCN Incorporation.

A carbon electrode with low cost and high stability exhibited competitiveness for its practical application in organic-inorganic hybrid perovskite solar cells (PSCs). Nonetheless, issues such as poor interface contact with an adjacent perovskite layer and obvious hysteresis phenomenon are bottlenecks that need to be overcome to make carbon-based PSCs (C-PSCs) more attractive in practice. Herein, we report an effective method to enhance the interfacial charge transport of C-PSCs by introducing the CuSCN material into the device. Two types of CuSCN-assisted devices were studied in this work. One was based on the deposition of an ultrathin CuSCN layer between the perovskite absorber layer and the carbon cathode (PSK/CuSCN/C), and the other was by infiltrating CuSCN solution into the carbon film (PSK/C-CuSCN) by taking advantage of the macroporous structure of the carbon. We have found that the CuSCN incorporation by both methods can effectively address the hysteretic feature in planar C-PSCs. The origin for the hysteresis evolution was unraveled by the investigation of the energy alignment and the kinetics of interfacial charge transfer and hole trap-state density. The results have shown that both types of CuSCN-containing devices showed improved interfacial charge carrier extraction, suppressed carrier recombination, reduced trap-state density, and enhanced charge transport, leading to negligible hysteresis. Furthermore, the CuSCN-incorporated C-PSCs demonstrated enhanced device stability. The power conversion efficiency remained 98 and 91% of the initial performance (13.6 and 13.4%) for PSK/CuSCN/C and PSK/C-CuSCN, respectively, after being stored under a high humidity (75-85%) environment for 10 days. The devices also demonstrated extraordinary long-term stability with a negligible performance drop after being stored in air (relative humidity: 33-35%) for 90 days.

Hindered Formation of Photoinactive δ-FAPbI3 Phase and Hysteresis-Free Mixed-Cation Planar Heterojunction Perovskite Solar Cells with Enhanced Efficiency via Potassium Incorporation.

Organic-inorganic hybrid lead halide perovskite solar cells have demonstrated competitive power conversion efficiency over 22%; nevertheless, critical issues such as unsatisfactory device stability, serious current-voltage hysteresis, and formation of photo nonactive perovskite phases are obstacles for commercialization of this photovoltaics technology. Herein we report a facial yet effective method to hinder formation of photoinactive δ-FAPbI3 and hysteresis behavior in planar heterojunction perovskite solar cells based on K x(MA0.17FA0.83)1- xPbI2.5Br0.5 (0≤ x ≤ 0.1) through incorporation of potassium ions (K+). X-ray diffraction patterns demonstrate formation of photoinactive δ-FAPbI3 was almost completely suppressed after K+ incorporation. Density functional theory calculation shows K+ prefers to enter the interstitial sites of perovskite lattice, leading to chemical environmental change in the crystal structure. Ultrafast transient absorption spectroscopy has revealed that K+ incorporation leads to enhanced carrier lifetime by 50%, which is also confirmed by reduced trap-assisted recombination of the perovskite solar cells containing K+ in photovoltage decay. Ultraviolet photoelectron spectroscopy illustrates that K+ incorporation results in a significant rise of conduction band minimum of the perovskite material by 130 meV, leading to a more favorable energy alignment with electron transporting material. At the optimal content of 3% K+ (molar ratio, relative to the total monovalent cations), nearly hysteresis-free, enhanced power conversion efficiencies from 15.72% to 17.23% were obtained in this solar cell.