Non-Fullerene Acceptors Assisted Target Therapy for Interface Treatment Enable High Performance Inverted Perovskite Solar Cells.

Targeted treatment of the interface between electron transport layers (ETL) and perovskite layers is highly desirable for achieving passivating effects and suppressing carrier nonradiative recombination, leading to high performance and long-term stability in perovskite solar cells (PSCs). In this study, a series of non-fullerene acceptors (NFAs, Y-H, Y-F, and Y-Cl) are introduced to optimize the properties of the perovskite/ETL interface. This optimization involves passivating Pb2+ defects, releasing stress, and modulating carrier dynamics through interactions with the perovskite. Remarkably, after modifying with NFAs, the absorption range of perovskite films into the near-infrared region is extended. As expected, Y-F, with the largest electrostatic potential, facilitates the strongest interaction between the perovskite and its functional groups. Consequently, champion power conversion efficiencies of 21.17%, 22.21%, 23.25%, and 22.31% are achieved for control, Y-H-, Y-F-, and Y-Cl-based FA0.88Cs0.12PbI2.64Br0.36 (FACs) devices, respectively. This treatment also enhances the heat stability and air stability of the corresponding devices. Additionally, these modifier layers are applied to enhance the efficiency of Cs0.05(FA0.95MA0.05)0.95PbI2.64Br0.36 (FAMA) devices. Notably, a champion PCE exceeding 24% is achieved in the Y-F-based FAMA device. Therefore, this study provides a facile and effective approach to target the interface, thereby improving the efficiency and stability of PSCs.

Enhancing Hole Transport Uniformity for Efficient Inverted Perovskite Solar Cells through Optimizing Buried Interface Contacts and Suppressing Interface Recombination.

[4-(3,6-dimethyl-9H-carbazol-9yl)butyl]phosphonic acid (Me-4PACz) self-assembly material has been recognized as a highly effective approach for mitigating nickel oxide (NiOx) surface-related challenges in inverted perovskite solar cells (IPSCs). However, its uneven film generation and failure to effectively passivate the buried interface defects limit the device's performance improvement potential. Herein, p-xylylenediphosphonic acid (p-XPA) containing bilateral phosphate groups (-PO3H2) is introduced as an interface layer between the NiOx/Me-4PACz and the perovskite layer. P-XPA can flatten the surface of hole transport layer and optimize interface contact. Meanwhile, p-XPA achieves better energy level alignment and promotes interfacial hole transport. In addition, the bilateral -PO3H2 of p-XPA can chelate with Pb2+ and form hydrogen bond with FA+ (formamidinium cation),  thereby suppressing buried interface non-radiative recombination loss. Consequently, the IPSC with p-XPA buried interface modification achieves champion power conversion efficiency of 25.87% (certified at 25.45%) at laboratory scale (0.0448 cm2). The encapsulated target device exhibits better operational stability. Even after 1100 hours of maximum power point tracking at 50 ℃, its efficiency remains at an impressive 82.7% of the initial efficiency. Molecules featuring bilateral passivation groups optimize interfacial contact and inhibit interfacial recombination, providing an effective approach to enhancing the stability and efficiency of devices.

Multifunctional Imidazolidinyl Urea Additive Initiated Complex with PbI2 Toward Efficient and Stable Perovskite Solar Cells.

High-quality perovskite absorption layer is the fundamental basis for efficient and stable perovskite solar cells (PSCs). Due to the ionic nature of perovskite components, plentiful charged defects and suspension bonds remain on the surface of perovskite grains after continuous high-temperature annealing. Here, the complex initiated by the introduction of a multifunctional imidazolidinyl urea (IU) additive into the PbI2 precursor solution could serve as nucleation sites and crystallization templates for perovskite crystals to optimize the growth of high-quality perovskite films. By anchoring at the grain boundaries of perovskite films, IU molecules could passivate various types of defects, improve the hydrophobic properties, and inhibit lead leakage. Attributed to reduced defect density, improved charge transport, and inhibited α-FAPbI3 transition, the PSCs prepared based on IU additives achieved a champion power conversion efficiency of 23.18% (21.51% for the control PSCs) with negligible hysteresis and satisfactory stability.

A simple strategy to obtain graphitic carbon nitride modified TiO2layer for efficient perovskite solar cells.

The power conversion efficiency (PCE) of perovskite solar cells (PSCs) can be improved through the concurrent strategies of enhancing charge transfer and passivating defects. Graphite carbon nitride (g-C3N4) has been demonstrated as a promising modifier for optimizing energy level alignment and reducing defect density in PSCs. However, its preparation process can be complicated. A simple one-step calcination approach was used in this study to prepare g-C3N4-modified TiO2via the incorporation of urea into the TiO2precursor. This modification simultaneously tunes the energy level alignment and passivates interface defects. The comprehensive research confirms that the addition of moderate amounts of g-C3N4to TiO2results in an ideal alignment of energy levels with perovskite, thereby enhancing the ability to separate and transfer charges. Additionally, the g-C3N4-modified perovskite films exhibit an increase in grain size and crystallinity, which reduces intrinsic defects density and extends charge recombination time. Therefore, the g-C3N4-modified PSC achieves a champion PCE of 20.00%, higher than that of the control PSC (17.15%). Our study provides a systematic comprehension of the interfacial engineering strategy and offers new insights into the development of high-performance PSCs.

Oxide Nanoclusters on Ti3 C2 MXenes to Deactivate Defects for Enhanced Lithium Ion Storage Performance.

The commercialization of MXenes as anodes for lithium-ion batteries is largely impeded by low initial coulombic efficiency (ICE) and unfavorable cycling stability, which are closely associated with defects such as Ti vacancies (VTi ) in Ti3 C2 MXenes. Herein, an effective strategy is developed to deactivate VTi defects by in situ growing Al2 O3 nanoclusters on MXenes to alleviate the irreversible electrolyte decomposition and Li dendrites formation trend induced by defects, improving ICE and cycling stability. Furthermore, it is revealed that excessively lithiophilic VTi defects would impede Li ions diffusion due to their strong adsorption, leading to a locally nonuniform Li flux to these "hot spots," setting scene for the formation of Li dendrites. The Al2 O3 nanoclusters anchored on VTi sites can not only improve Li diffusion kinetics but also promote the homogeneous solid electrolyte interphase formation with small charge transfer resistance, achieving uniform Li deposition in a smaller overpotential without formation of Li dendrites. As expected, Ti3 C2 @Al2 O3 -11 electrode delivers a high ICE of 76.6% and an outstanding specific capacity of 285.5 mAh g-1 after 500 cycles, which is much higher than that of pristine Ti3 C2 sample. This work sheds light on modulating defects for high-performance energy storage materials.

Highly Orientational Order Perovskite Induced by In situ-generated 1D Perovskitoid for Efficient and Stable Printable Photovoltaics.

Employing low-dimensional perovskite has been proven to be a promising approach to enhance the efficiency and stability of perovskite solar cells. Here, thiopheniformamidine hydrochloride is introduced into CH3 NH3 PbI3 -based printable mesoscopic perovskite solar cells, to form 1D iodide lead thiophenamidine (TFPbI3 ) in situ. This judiciously designed low-dimensional perovskite can effectively passivate the defect of perovskite and induce the perovskite crystals to grow in a direction perpendicular to the substrate. Thus, the obtained 1D@3D perovskite could suppress the charge recombination and promote the charge transfer significantly. Benefiting from its dual effect and robustness, a significantly improved power conversion efficiency of 17.42% is yielded. The authors also develop high-performance printable mesoscopic perovskite solar cells with a champion efficiency approaching 13% for aperture area about 11.8 cm2 , as well as outstanding operational stability, retaining 90% of the original power conversion efficiency after 1000 hours of continuous illumination at the maximum power point in air.

Over 16% Efficient Solution-Processed Cu(In,Ga)Se2 Solar Cells via Incorporation of Copper-Rich Precursor Film.

Solution processing of Cu(In,Ga)Se2 (CIGS) absorber is a highly promising strategy for a cost-effective CIGS photovoltaic device. However, the device performance of solution-processed CIGS solar cells is still hindered by the severe non-radiative recombination resulting from deep defects and poor crystal quality. Here, a simple and effective precursor film engineering strategy is reported, where Cu-rich (CGI >1) CIGS layer is incorporated into the bottom of the CIGS precursor film. It has been discovered that the incorporation of the Cu-rich CIGS layer greatly improves the absorber crystallinity and reduces the trap state density. Accordingly, more efficient charge generation and charge transfer are realized. As a result of systematic processing optimization, the champion solution-processed CIGS device delivers an improved open-circuit voltage of 656 mV, current density of 33.15 mA cm-2 , and fill factor of 73.78%, leading to the high efficiency of 16.05%.

Promoting Energy Transfer Between Quasi-2D Perovskite Layers Toward Highly Efficient Red Light-Emitting Diodes.

Although tremendous progress has recently been made in quasi-2D perovskite light-emitting diodes (PeLEDs), the performance of red PeLEDs emitting at ≈650-660 nm, which have wide prospects for application in photodynamic therapy, is still limited by an inefficient energy transfer process between the quasi-2D perovskite layers. Herein, a symmetric molecule of 3,3'-(9H-fluorene-9,9-diyl)dipropanamide (FDPA) is designed and developed with two functional acylamino groups and incorporated into the quasi-2D perovskites as the additive for achieving high-performance red PeLEDs. It is demonstrated that the agent can simultaneously diminish the van der Waals gaps between individual perovskite layers and passivate uncoordinated Pb2+ related defects at the surface and grain boundaries of the quasi-2D perovskites, which truly results in an efficient energy transfer in the quasi-2D perovskite films. Consequently, the red PeLEDs emitting at 653 nm with a peak external quantum efficiency of 18.5% and a maximum luminance of 2545 cd m-2 are achieved, which is among the best performing red quasi-2D PeLEDs emitting at ≈650-660 nm. This work opens a way to further improve the electroluminescence performance of red PeLEDs.

When Aggregation-Induced Emission Meets Perovskites: Efficient Defect-Passivation and Charge-Transfer for Ambient Fabrication of Perovskite Solar Cells.

The intrinsic defects in perovskite film can serve as non-radiative recombination center to limit the performance and stability of metal halide perovskite solar cells (PSCs). The additive engineering in perovskite film is always applied to produce high-efficiency PSCs in recent years. Here, a typical donor-acceptor (D-A) structured aggregation-induced emission (AIE) molecule tetraphenylethene-2-dicyano-methylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TPE-TCF) was introduced into perovskite film. The D-A structure of TPE-TCF molecule provided additional charge transfer channels, contributing to transporting electron of TPE-TCF-based device. The cyano (C≡N) of TPE-TCF can interact with the uncoordinated Pb to from a relatively stable intermediate, PbI2 ⋅TPE-TCF, resulting in the slower crystal growth, reduced the defects at the grain boundaries and suppressed carrier recombination. As a consequence, the power conversion efficiency (PCE) of TPE-TCF-modified PSCs achieved a remarkably enhanced from 15.63 to 19.66 % with negligible hysteresis, which was prominent in methylammonium lead iodide-based devices fabricated under ambient condition. Furthermore, the PSCs modified by AIE molecule possessed an outstanding stability and maintain about 86 % of the initial PCE after 300 h storage in air at 25-35 °C with a high relative humidity (RH) of ≈85 %. This work suggests that incorporating AIE molecule into perovskite is a promising strategy for facilitating high-performance PSCs commercialization in ambient environment without glovebox.

Embedding of Ti3 C2 Tx Nanocrystals in MAPbI3 Microwires for Improved Responsivity and Detectivity of Photodetector.

Organic-inorganic hybrid MAPbI3 microwires show unique optoelectronic properties for high performances of photodetectors (PDs). However, the defects-assisted nonradiative recombination is harmful for carrier transport, which limits the performances improvement of MAPbI3 microwires PDs. Traditional organic passivation agents effectively combine the surface defects of microwires and also reduce the mobility of overall film based on the perovskite microwires. Therefore, the improvement of internal carrier transport of microwires and the mobility of integrated film simultaneously is a particular challenge for fabrication of performances enhanced perovskite microwires PDs. Here, the Ti3 C2 Tx NCs are fabricated by nonfocus laser irradiation in liquid environment, and hybrids the high conductive NCs in the MAPbI3 microwires. The presence of Ti3 C2 Tx NCs renders defects passivation, enhancement of crystalline orientation, charge transport, and carrier extraction for MAPbI3 microwires, and boots the mobility of microwires based film, leading to about tenfolds enhancement of performances of PDs than that of the control. The maximum responsivity and the detectivity of the Ti3 C2 Tx NCs embedded MAPbI3 microwires PDs reach to 1.70 A W-1 and 7.0 × 1011 Jones in visible window, respectively. The findings suggest that the laser generated high conductive Ti3 C2 Tx NCs is an effective additive for perovskite microwires to fabricate performances enhanced optoelectronics.

Managing Defects Density and Interfacial Strain via Underlayer Engineering for Inverted CsPbI2 Br Perovskite Solar Cells with All-Layer Dopant-Free.

Inorganic perovskite CsPbI2 Br has advantages of excellent thermal stability and reasonable bandgap, which make it suitable for top layer of tandem solar cells. Nevertheless, solution-processed all-inorganic perovskites generally suffer from high-density defects as well as significant tensile strain near underlayer/perovskite interface, both leading to compromised device efficiency and stability. In this work, the defect density as well as interfacial tensile strain in inverted CsPbI2 Br perovskite solar cells (PeSCs) is remarkably reduced by using a bilayer underlayer composed of dopant-free 2,2',7,7'-tetrakis(N,N-dip-methoxyphenylamine)-9,9'-spirobifluorene (Spiro-OMeTAD) and copper phthalocyanine 3,4',4″,4'″-tetrasulfonated acid tetrasodium salt (TS-CuPc) nanoparticles. As compared to control devices with pristine Spiro-OMeTAD, devices based on Spiro-OMeTAD/TS-CuPc exhibit remarkably improved photovoltaic performance and enhanced thermal/humidity stability due to the better perovskite crystallization, improved interfacial passivation, and hole-collection as well as efficient interfacial strain release. As a result, a champion efficiency of 14.85% can be achieved, which is approaching to the best reported for dopant-free and inverted all-inorganic PeSCs. The work thus provides an efficient strategy to simultaneously regulate the defects density and strain issue related to inorganic perovskites.

Synergistic Crystallization Modulation and Defects Passivation in Kesterite via Anion-Coordinate Precursor Engineering for Efficient Solar Cells.

It has been validated that enhancing crystallinity and passivating the deep-level defect are critical for improving the device performance of kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. Coordination chemistry interactions within the Cu-Zn-Sn-S precursor solution play a crucial role in the management of structural defects and the crystallization kinetics of CZTSSe thin films. Therefore, regulating the coordination environment of anion and cation in the precursor solution to control the formation process of precursor films is a major challenge at present. Herein, a synergetic crystallization modulation and defect passivation method is developed using P2S5 as an additive in the CZTS precursor solution to optimize the coordination structure and improve the crystallization process. The alignment of theoretical assessments with experimental observations confirms the ability of the P2S5 molecule to coordinate with the metal cation sites of CZTS precursor films, especially more liable to the Zn2+, effectively passivating the Zn-related defects, thereby significantly reducing the defect density in CZTSSe absorbers. As a result, the device with a power conversion efficiency of 14.36% has been achieved. This work provides an unprecedented strategy for fabricating high-quality thin films by anion-coordinate regulation and a novel route for realizing efficient CZTSSe solar cells.

Enhancing the Performance of Perovskite Light-Emitting Diodes via Synergistic Effect of Defect Passivation and Dielectric Screening.

Metal halide perovskites, particularly the quasi-two-dimensional perovskite subclass, have exhibited considerable potential for next-generation electroluminescent materials for lighting and display. Nevertheless, the presence of defects within these perovskites has a substantial influence on the emission efficiency and durability of the devices. In this study, we revealed a synergistic passivation mechanism on perovskite films by using a dual-functional compound of potassium bromide. The dual functional potassium bromide on the one hand can passivate the defects of halide vacancies with bromine anions and, on the other hand, can screen the charged defects at the grain boundaries with potassium cations. This approach effectively reduces the probability of carriers quenching resulting from charged defects capture and consequently enhances the radiative recombination efficiency of perovskite thin films, leading to a significant enhancement of photoluminescence quantum yield to near-unity values (95%). Meanwhile, the potassium bromide treatment promoted the growth of homogeneous and smooth film, facilitating the charge carrier injection in the devices. Consequently, the perovskite light-emitting diodes based on this strategy achieve a maximum external quantum efficiency of ~ 21% and maximum luminance of ~ 60,000 cd m-2. This work provides a deeper insight into the passivation mechanism of ionic compound additives in perovskite with the solution method.

Benzophenone: A Small Molecule Additive for Enhanced Performance and Stability of Inverted Perovskite Solar Cells.

In this study, we investigated the impact of benzophenone (BP), a small molecule additive, on the performance and stability of inverted perovskite solar cells (PSCs). Specifically, we introduced BP into the perovskite precursor solution of FAPbI3 to fabricate PSCs with an ITO/PEDOT:PSS/BP:FAPbI3/PCBM/C60/PCB/Ag architecture. The incorporation of BP with an optimum concentration of 2 mg mL-1 significantly enhanced the power conversion efficiency (PCE) of the inverted PSC from 13.12 to 18.84% with negligible hysteresis. Notably, the BP-based PSCs retained ∼90% of their initial PCE after being stored in ambient air with 30% relative humidity at 25 °C for 700 h. In contrast, control devices showed rapid degradation, retaining only 30% of their initial value within 300 h under the same conditions. We attributed the superior performance and stability of the BP-based PSCs to the grain boundary passivation of the perovskite film. The improvement was mainly attributed to the intermolecular interaction between the O-donor Lewis base BP material and both Pb2+ and FA+ in FAPbI3. This effectively suppresses trap-assisted recombination and promotes the conversion of the δ-phase to photoactive and stable α-phase FAPbI3. Overall, our findings suggest that BP is a promising additive for improving the performance and stability of inverted PSCs.

Concise synthesis of low-cost fullerene derivatives as electron transport materials for efficient air-processed invert perovskite solar cells.

Due to its excellent charge extraction ability, fullerene derivative phenyl-C61-butyric acid methyl ester (PCBM) is widely used as electron transport materials (ETM) in invert perovskite solar cells. However, the complicated synthetic routes and low productivity of PCBM limiting its commercial application. Moreover, the insufficient defect passivation ability of PCBM is contributed to inferior device performance because it lacks hetero-atoms/groups with lone pair electrons, it is highly desirable for exploration of new fullerene-based ETM with excellent photoelectric properties. Therefore, three new fullerene malonate derivatives were synthesized by simple two-step reaction with a high yield, and then developed as electron transport materials in invert perovskite solar cells which fabricated in air condition. The constituent thiophene and pyridyl group of the fullerene-based ETM can heighten the chemical interaction between under-coordinated Pb2+ and lone pair electrons of N, S atom by electrostatic interaction. Hence, the air-processed unencapsulated device with new fullerene-based electron transport materials (C60-bis(pyridin-2-ylmethyl) malonate (C60-PMME)) can obtain a enhanced power conversion efficiency (PCE) of 18.38%, which is significantly higher than the PCBM-based devices (16.64%). Additionally, the C60-PMME-based devices exhibit significantly more outstanding long-term stability than PCBM-based devices, owing to the strong hydrophobic properties of these new fullerene-based ETM. This study shows the promising potentials of these new low-cost fullerene derivatives as ETM to replace commercially used fullerene derivatives PCBM.

Tellurium Doping Inducing Defect Passivation for Highly Effective Antimony Selenide Thin Film Solar Cell.

Antimony selenide (Sb2Se3) is emerging as a promising photovoltaic material owing to its excellent photoelectric property. However, the low carrier transport efficiency, and detrimental surface oxidation of the Sb2Se3 thin film greatly influenced the further improvement of the device efficiency. In this study, the introduction of tellurium (Te) can induce the benign growth orientation and the desirable Sb/Se atomic ratio in the Te-Sb2Se3 thin film. Under various characterizations, it found that the Te-doping tended to form Sb2Te3-doped Sb2Se3, instead of alloy-type Sb2(Se,Te)3. After Te doping, the mitigation of surface oxidation has been confirmed by the Raman spectra. High-quality Te-Sb2Se3 thin films with preferred [hk1] orientation, large grain size, and low defect density can be successfully prepared. Consequently, a 7.61% efficiency Sb2Se3 solar cell has been achieved with a VOC of 474 mV, a JSC of 25.88 mA/cm2, and an FF of 64.09%. This work can provide an effective strategy for optimizing the physical properties of the Sb2Se3 absorber, and therefore the further efficiency improvement of the Sb2Se3 solar cells.

Grain boundary defects passivation by bridging diammonium toward stable and efficient perovskite solar cells.

The grain boundary defects of polycrystalline perovskite could induce severe carrier recombination loss to restrict the photovoltaic and stability advancement of perovskite-based solar cells (PSCs). Inserting fixed molar ratio organic cations spacers into halide perovskite slabs to reduce the dimension of the crystal structure is still limited in finding a compromise of efficiency and stability for the widened bandgap and increasing barriers for carrier transport. Here, we select a direct additive bridging engineering to introduce a rationally designed organic amine salt 1,4-Benzene diammonium iodide (BDAI2) with ammonium group on both terminals of the benzene ring to passivate the grain boundary and interface defects of perovskite. Bridging diammonium could ameliorate the interface contact and achieve electrostatic interactions with negatively charged traps (such as uncoordinated I-, PbI3-, and methylammonium vacancies) to inhibit cation migration, reduce halogen ion vacancy, and then suppress trap-induced recombination in perovskite. As a result, the bridging diammonium could improve the power conversion efficiency (PCE) from 19.86% to 21.91%. This study highlights the importance of rational bridging diammonium for perovskite surface modification and passivation to boost photovoltaic performance and stability.

Defect Passivation Using Trichloromelamine for Highly Efficient and Stable Perovskite Solar Cells.

Nonradiative recombination losses caused by defects in the perovskite layer seriously affects the efficiency and stability of perovskite solar cells (PSCs). Hence, defect passivation is an effective way to improve the performance of PSCs. In this work, trichloromelamine (TCM) was used as a defects passivator by adding it into the perovskite precursor solution. The experimental results show that the power conversion efficiency (PCE) of PSC increased from 18.87 to 20.15% after the addition of TCM. What's more, the environmental stability of PSCs was also improved. The working mechanism of TCM was thoroughly investigated, which can be ascribed to the interaction between the -NH- group and uncoordinated lead ions in the perovskite. This work provides a promising strategy for achieving highly efficient and stable PSCs.

Ionic Liquid Treatment for Highest-Efficiency Ambient Printed Stable All-Inorganic CsPbI3 Perovskite Solar Cells.

All-inorganic cesium lead triiodide (CsPbI3 ) perovskite is well known for its unparalleled stability at high temperatures up to 500 °C and under oxidative chemical stresses. However, upscaling solar cells via ambient printing suffers from imperfect crystal quality and defects caused by uncontrollable crystallization. Here, the incorporation of a low concentration of novel ionic liquid is reported as being promising for managing defects in CsPbI3 films, interfacial energy alignment, and device stability of solar cells fabricated via ambient blade-coating. Both theoretical simulations and experimental measurements reveal that the ionic liquid successfully regulates the perovskite thin-film growth to decrease perovskite grain boundaries, strongly coordinates with the undercoordinated Pb2+ to passivate iodide vacancy defects, aligns the interface to decrease the energy barrier at the electron-transporting layer, and relaxes the lattice strain to promote phase stability. Consequently, ambient printed CsPbI3 solar cells with power conversion efficiency as high as 20.01% under 1 sun illumination (100 mW cm-2 ) and 37.24% under indoor light illumination (1000 lux, 365 µW cm-2 ) are achieved; both are the highest for printed all-inorganic cells for corresponding applications. Furthermore, the bare cells show an impressive long-term ambient stability with only ≈5% PCE degradation after 1000 h aging under ambient conditions.

Heterojunction In Situ Constructed by a Novel Amino Acid-Based Organic Spacer for Efficient and Stable Perovskite Solar Cells.

The optical properties and stability of metal halide perovskites can be improved by reducing their dimensionality. Because defects at the perovskite film grain body and boundaries cause significant energetic losses by nonradiative recombination, perovskite films with manageable crystal size and macroscopic grains are essential to improve the photovoltaic properties. Through theoretical calculation models and experiments, we show that the carboxyl group of 4-ammonium butyric acid-based cation (4-ABA+) can interact with the three-dimensional (3D) perovskite to produce in situ a secondary grain growth by post-treatment. It passivates the trap defects and broadens the light absorption. 4-ABA+ could induce a 2D capping layer on top of 3D mixed cation-based perovskite to construct a 2D/3D heterojunction. The 4-ABA+-modified perovskite film consists of large-sized grains with extremely low trap state densities and possesses a longer charge carrier lifetime and good stability, resulting in efficient perovskite solar cells with a champion efficiency of 23.16% and a VOC of 1.20 V. We show that the 4-ABA+-treated devices outperform the 3-ammonium propionic acid (3-APA+)- and 5-ammonium valeric acid (5-AVA+)-treated ones. Moreover, the devices exhibit high stability under high humidity and continuous light soaking conditions. This work gives a hint that our approach based on 4-ABA+ treatment is key to achieving better electrical properties, a controlled crystal growth, and highly stable perovskite solar cells.