Antisite Defects Research Articles

Regulating Broadband Near‐Infrared Mechanoluminescence via Energy‐Level Engineering for Potential Biomechanical Imaging

AbstractNear‐infrared mechanoluminescent (NIR ML) materials have attracted attention due to their advantages, such as in situ and real‐time monitoring of biomechanical information in vivo. However, most ML materials are focused on the UV–vis light range, which limits their potential applications in the biological field. In this work, a broadband NIR ML material Ca2YGa3Ge2O12: 0.10Cr3+ (CYGGG: 0.10Cr3+) is successfully prepared by chemical co‐substitution and Cr3+ heavy doping. Density functional theory (DFT) calculations are used to determine the type of defects in the material, and the composite defects formed by interstitial oxygen (iO′′) and antisite defects (CaY′ ‐ YCa°) mostly dominate NIR ML. Cr3+ ions act as electronic bridges to regulate energy levels, becoming the key to turning on the Nd3+ ion's NIR ML. Finally, based on the excellent ML properties of CYGGG: 0.10Cr3+ and CYGGG: 0.10Cr3+, 0.01Nd3+, the ML composites can penetrate pork tissues of different compositions/thicknesses under stress loads. Potentially, this work tries to realize biological tissue stress imaging, providing a new way for the biological application of NIR ML materials.

Energetics of Point Defects in D0a Ag3Sn: First‐Principles Calculations

The Ag3Sn intermetallic compound is commonly found and acts as a strengthening factor in the key lead‐free solders based on Sn‐Ag‐Cu. The Ag3Sn phase exhibits also an asymmetric off‐stoichiometry, which necessitates the existence of constitutional point defects. The presence of point defects can, in general, sensitively affect the plastic deformation of materials and the strengthening role of Ag3Sn in particular. To understand the nature of the point defects and the compositional stability of Ag3Sn, the relaxed structures and the energies of single point defects (vacancies and antisite defects) in all three sublattices of Ag3Sn are calculated at 0 K using ab initio density functional theory (DFT) and the supercell method. The first‐principles‐based calculations predict that the AgSn antisite defect (Ag substitution for Sn) has the smallest enthalpy of formation, thus indicating that the AgSn antisite defect is the dominant point defect in Ag3Sn. The point defect concentrations as a function of Sn content are estimated using the DFT defect energies and the Wagner–Schottky model. The compositional dependence of the point defect concentrations gives new insights on the atomistic mechanisms of formation of nonstoichiometric Ag3Sn.

Balancing Layered Ordering and Lattice Oxygen Stability for Electrochemically Stable High-Nickel Layered Cathode for Lithium-ion Batteries

Despite the high-capacity nature of high-nickel cathode materials, achieving their practical implementation is challenging due to the susceptibility of atomic arrangement to calcining conditions. Extensive studies have enlightened the correlation between layered ordering and calcining conditions; nevertheless, the alterations in the electronic structure of lattice oxygen remain obscure. In this study, by comparing cathode materials with varying degrees of layered ordering, achieved through adjustments in calcination temperature and lithium equivalent, it is shown that although layered ordering increases, it compromises the electronic structure, creating a labile lattice oxygen environment. Fine structural analysis reveals that a higher local Li/O ratio in highly ordered cathode subsequently alters the band structure by narrowing the band gap between Ni 3d and O 2p, which enhances transition metal–oxygen covalency, and reduces the oxygen vacancy formation energy, adversely affecting cyclability. In highly ordered cathode, the tendency of lattice oxygen to reside within a Li-enriched environment arises from the changes in the favorability of non-paired antisite defects contingent upon the calcination temperature and lithium equivalent. This research underscores the need to balance layered ordering and lattice oxygen stability, offering important insights for the future design of high-nickel cathodes.

Residual Ferromagnetic Regions Affecting the First-Order Phase Transition in Off-Stoichiometric Fe-Rh.

Among the magnetocaloric materials featuring first-order phase transitions (FOPT), FeRh is considered as a reference system to study the FOPT because it is a "simple" binary system with a CsCl structure exhibiting a large adiabatic temperature change. Recently, ab initio theory predicted that changes in the Fe/Rh stoichiometry in the vicinity of equiatomic composition strongly influence the FOPT characteristics. However, this theoretical prediction was not clearly verified experimentally. Here, we investigated the composition dependence of the transitional hysteresis in FeRh. It is shown that a Fe excess of only 1 at. % induces a ferromagnetic state in the whole temperature range (from 5 K up to Tc) for a minor portion of the sample (≈10%), while 5 at. % is enough to completely eliminate the FOPT. Element-specific X-ray magnetic circular dichroism (XMCD) measurements suggest that this ferromagnetic contribution arises from residual FeRh ferromagnetic regions. We attribute the formation of such domains to Fe antisite defects, as Mössbauer spectroscopy demonstrates the presence of Fe atoms located at the 1b (Rh) sites in the CsCl-type structure. As a consequence, compared with the equiatomic composition, the slightly Fe-rich sample exhibits completely different FOPT properties, influencing the magnetocaloric performances. Thus, our study sheds light on the origin of the remarkable stoichiometric sensitivity of the FOPT behavior in FeRh. These insights have broader implications for understanding FOPT dynamics and the role of residual ferromagnetic domains.

Synthesis of Multifunctional Organic Molecules via Michael Addition Reaction to Manage Perovskite Crystallization and Defect

AbstractAdditive engineering plays a pivotal role in achieving high‐quality light‐absorbing layers for high‐performance and stable perovskite solar cells (PSCs). Various functional groups within the additives exert distinct regulatory effects on the perovskite layer. However, few additive molecules can synergistically fulfill the dual functions of regulating crystallization and passivating defects. Here, we custom‐synthesized 2‐ureido‐4‐pyrimidone (UPy) organic small molecules with diverse functional groups as additives to modulate crystallization and defects in perovskite films via the Michael addition reaction. Theoretical and experimental investigations demonstrate that the −OH groups in UPy exhibit significant effects in fixing uncoordinated Pb2+ ions, passivation of lead‐iodide antisite defects, alleviating hysteresis, and reducing non‐radiative recombination. Furthermore, the enhanced C=O and −NH2 motifs interact with the A‐site cation via hydrogen bonding, which relieves residual strain and adjusts crystal orientation. This strategy effectively controls perovskite crystallization and passivates defects, ultimately enhancing the quality of perovskite films. Consequently, the open‐circuit voltage of the UPy‐based p‐i‐n PSCs reaches 1.20 V, and the fill factor surpasses 84 %. The champion device delivers a power conversion efficiency of 25.75 %. Remarkably, the unencapsulated device maintained 96.9 % and 94.5 % of its initial efficiency following 3,360 hours of dark storage and 1,866 hours of 1‐sun illumination, respectively.

Catalytic Strategies Enabled Rapid Formation of Homogeneous and Mechanically Robust Inorganic‐Rich Cathode Electrolyte Interface for High‐Rate and High‐Stability Lithium‐Ion Batteries

AbstractLithium iron phosphate (LFP) cathode is renowned for high thermal stability and safety, making them a popular choice for lithium‐ion batteries. Nevertheless, on one hand, the fast charge/discharge capability is fundamentally constrained by low electrical conductivity and anisotropic nature of sluggish lithium ion (Li+) diffusion. On the other hand, the interface and internal structural degradation occurs when subjected to high‐rate condition. Herein, a multifunctional boron‐doping graphene/lithium carbonate (BG/LCO) nanointerfacial layer on surface of commercial LiFePO4 particles is designed, in which the BG layer catalyzes the rapid reaction of Li2CO3‐LiPF6 for homogeneous and mechanically robust inorganic LiF‐rich structure across the cathode‐electrolyte interphase (CEI), forms a conductive network to significantly enhance both electron and Li+ transport, and strengthens the FeO bonding to minimize both Fe loss and the formation of Fe‐Li antisite defects. Correspondingly, the modified LFP cathode achieves a high capability of 113.2 mAh g−1 at 10 C and extraordinary cyclic stability with 88.0% capacity retention over 1000 cycles as compared to the pristine LFP cathode with a capacity of only 94.0 mAh g−1 and 64.6% capacity retention. It also exhibits great enhancements of 20.1% and 3.7% at higher‐rate condition (room temperature/15 C) and the low temperature condition (−10 °C/1 C), respectively.

Dynamic Evolution of Antisite Defect and Coupling Anionic Redox in High-Voltage Ultrahigh-Ni Cathode.

High-voltage ultrahigh-Ni cathodes (LiNixCoyMn1-x-yO2, x≥0.9) can significantly enhance the energy density and cost-effectiveness of Li-ion batteries beyond current levels. However, severe Li-Ni antisite defects and their undetermined dynamic evolutions during high-voltage cycling limit the further development of these ultrahigh-Ni cathodes. In this study, we quantify the dynamic evolutions of the Li-Ni antisite defect using operando neutron diffraction and reveal its coupling relationship with anionic redox, another critical challenge restricting ultrahigh-Ni cathodes. We detect a clear Ni migration coupled with an unstable oxygen lattice, which accompanies the oxidation of oxygen anions at high voltages. Based on these findings, we propose that minimized Li-Ni antisite defects and controlled Ni migrations are essential for achieving stable high-voltage cycling structures in ultrahigh-Ni cathodes. This is further demonstrated by the optimized ultrahigh-Ni cathode, where reduced dynamic evolutions of the Li-Ni antisite defect effectively inhibit the anionic redox, enhancing the 4.5 V cycling stability.

Targeted Defect Repair and Multi-functional Interface Construction for the Direct Regeneration of Spent LiFePO4 Cathodes.

Due to the low economic benefits and environmental pollution of traditional recycling methods, the disposal of spent LiFePO4 (SLFP) presents a significant challenge. The capacity fade of SLFP cathode is primarily caused by lithium loss and formation of a Fe (III) phase. Herein, a synergistic repair effect is proposed to achieve defect repair and multi-functional interface construction for the direct regeneration of SLFP. Tannic acid (TA) forms a compact coating precursor for a carbon layer on SLFP with abundant functional groups and creates a mildly acidic environment to enhance the reducibility of thiourea (TU). Therefore, TU reduces Fe (III) to Fe (II) and repairs Li-Fe anti-site defects of SLFP, while at the same time acting as a source of N/S-doping elements for the carbon layer at a lower temperature (140°C). The multi-functional carbon layer improves the properties of the regenerated LiFePO4 (RLFP) due to the enhanced conductivity, structure maintenance and protection, and the improved kinetics of Li+ transport. Furthermore, the Fe─O and P─O bonds are strengthened, further enhancing the structural stability of the RLFP. Consequently, the RLFP demonstrates outstanding performance with a discharge capacity of 141.3 mAh g-1 and capacity retention of 72% after 1000 cycles at 1C.

Electronic Confinement-Restrained Anti-Site Defects in Sodium-Rich Phosphates Toward Multi-Electron Transfer and High Energy Efficiency.

Sodium (Na) super-ionic conductor structured Na3MnTi(PO4)3 (NMTP) cathodes have garnered interest owing to their cost-effectiveness and high operating voltages. However, the voltage hysteresis phenomenon triggered by anti-site defects ( -ASD), namely, the occupation of Mn2+ in the Na2 vacancies in NMTP, leads to sluggish diffusion kinetics and low energy efficiency. This study employs an innovative electronic confinement-restrained strategy to achieve the regulation of -ASD. Partial replacement of titanium (Ti) with electron-rich vanadium (V) favors strong electronic interactions with Mn2+, restraining Mn2+ migration. The results suggest that this strategy can significantly increase the vacancy formation energy and migration energy barrier of manganese (Mn), thus inhibiting -ASD formation. As proof of this concept, an Na-rich Na3.5MnTi0.5V0.5(PO4)3 (NMTVP) material is designed, wherein the electronic interaction enhanced the redox activity and achieved more Na+ storage under high-voltage. The NMTVP cathode delivered a reversible specific capacity of up to 182.7 mAh g-1 and output an excellent specific energy of 513.8Wh kg-1, corresponding to ≈3.2 electron transfer processes, wherein the energy efficiency increased by 35.5% at 30C. Through the confinement effect of electron interactions, this strategy provides novel perspectives for the exploitation and breakthrough of high-energy-density cathode materials in Na-ion batteries.

Investigation of structural and magnetic properties of Mg0.946Cu2.054O3 compound

The crystal structure of synthesized Mg0.946Cu2.054O3 compound was examined using Rietveld refinement of powder X-ray diffraction (XRD), revealing the presence of antisite defects in the form of substitution occupation of Mg atomic sites by Cu atoms upto ∼9 %. Detailed investigation by magnetic measurements around antiferromagnetic Néel transition around 95 K and below hints at the existence of paramagnetic component and short-range order due to presence of antisite defects, which is further supported by specific heat measurements.

Defect related anomalous mobility of small polarons in dielectric oxides at the example of congruent lithium niobate

Polarons play a major role in the description of optical, electrical and dielectrical properties of several ferroelectric oxides. The motion of those particles occurs by elementary hops among the material lattice sites. In order to compute macroscopic transport parameters such as charge mobility, normal (i.e. Fickian) diffusion laws are generally assumed. In this paper we show that when defect states able to trap the polarons for long times are considered, significant deviations from the normal diffusion behaviour arise. As an example of this behavior, we consider here the case of lithium niobate (LN). This can be considered as a prototypical system, having a rich landscape of interacting polaron types and for which a significant wealth of information is available in literature. Our analysis considers the case of a stoichiometric, defect-free lithium niobate containing a certain concentration of small electron polarons hopping on regular Nb sites, and compares it to the material in congruent composition, which is generally found in real-life applications and which is characterized by a large concentration of antisite NbLi defects. While in the first case the charge carriers are free polarons hopping on a regular Nb sublattice, in the second case a fraction of polarons is trapped on antisite defects. Thus, in the congruent material, a range of different hopping possibilities arises, depending on the type of starting and destination sites. We develop a formalism encompassing all these microscopic processes in the framework of a switching diffusion model which can be well approximated by a mobile–immobile transport model providing explicit expressions for the polaron mobility. Finally, starting from the Marcus–Holstein’s model for the polaron hopping frequency we verify by means of a Monte Carlo approach the diffusion/mobility of the different polarons species showing that, while free polarons obey the laws for normal diffusion as expected, bound polarons follow an anomalous diffusion behaviour and that in the case of the congruent crystal where mixed free and bound polaron transport is involved, our expressions indeed provide a satisfactory description.

Innovative In Situ Passivation Strategy for High-Efficiency Sb2(S,Se)3 Solar Cells.

An effective defect passivation strategy is crucial for enhancing the performance of antimony selenosulfide (Sb2(S,Se)3) solar cells, as it significantly influences charge transport and extraction efficiency. Herein, a convenient and novel in situ passivation (ISP) technique is successfully introduced to enhance the performance of Sb2(S,Se)3 solar cells, achieving a champion efficiency of 10.81%, which is among the highest recorded for Sb2(S,Se)3 solar cells to date. The first principles calculations and the experimental data reveal that incorporating sodium selenosulfate in the ISP strategy effectively functions as an in situ selenization, effectively passivating deep-level cation antisite SbSe defect within the Sb2(S,Se)3 films and significantly suppressing non-radiative recombination in the devices. Space-charge-limited current (SCLC), photoluminescence (PL), and transient absorption spectroscopy (TAS) measurements verify the high quality of the passivated films, showing fewer traps and defects. Moreover, the ISP strategy improved the overall quality of the Sb2(S,Se)3 films, and fine-tuned the energy levels, thereby facilitating enhanced carrier transport. This study thus provides a straightforward and effective method for passivating deep-level defects in Sb2(S,Se)3 solar cells.

Discovering the incorporation limits for wurtzite AlPyN1−y grown on GaN by metalorganic vapor phase epitaxy

We report on the growth of AlPN on GaN/sapphire templates by metalorganic vapor phase epitaxy using tertiarybutylphosphine (tBP) and NH3 as group-V precursors. P is easy to incorporate into the group-III lattice site, forming PAl anti-site defects and shrinking lattice constants that are even beyond AlN since Al is larger than P. We found that higher temperatures favor P incorporation on the N-sublattice, forming AlPyN1−y, while growth temperatures below 1000 °C result in dominant P incorporation on the Al-sublattice, forming PAl anisites. Similarly, larger NH3 flows stabilize GaN, leading to flat interfaces, but favor the formation of PAl. Furthermore, the P incorporation into AlPyN1−y is non-linear. At very low tBP flows, it initially increases to reach a maximum. Further increasing the tBP flow increases mostly the incorporation of P on the Al-sublattice, and the c-lattice constant decreases again. This leaves a small window of low V/III ratios below 5 and low P/N ratios of 1% or smaller, leading up to ∼4% P incorporation at typical growth temperatures of GaN. However, at such low V/III ratios, GaN is not stable even with N2 carrier gas and requires optimized switching sequences to minimize its decomposition and preserve flat interfaces. Eventually, a 10 nm coherent layer of AlP0.01N0.99 could be reproducibly grown on top of GaN channels with a smooth surface, an abrupt AlPN/GaN interface, and a two-dimensional electron gas with an electron mobility of ∼675 cm2/V s and a sheet carrier density of 1.5 × 1013 cm−2 at room temperature.

First‐principles study of helium incorporation in Pu‐La2Zr2O7 pyrochlore

AbstractHelium (He) exerts significant influence on the physicochemical, structural, and electronic properties of pyrochlores. This paper reviews recent advancements in computer simulations aimed at stabilizing nuclear waste, focusing on disordered structures of pyrochlores, zirconate pyrochlores, and high‐entropy pyrochlores. Using Pu‐La2Zr2O7 as a case study, we demonstrate how a first‐principles approach facilitates the understanding of how He modifies the structural and electronic properties of this system. The incorporation of He interstitials in Pu‐La2Zr2O7 typically leads to an expansion in lattice constant and volume swelling. Analysis of the formation energies in this system reveals that octahedral interstitial sites or zirconium (Zr) vacancy sites are favored for He occupation, resulting in the formation of substitutional He atoms. The low concentration of He atoms in Pu‐La2Zr2O7 reduces the formation energy of cation antisite defects. Bader charge analysis indicates that the < Zr‐O > bond exerts a greater influence on the irradiation resistance of the He‐Pu‐La2Zr2O7 system compared to the < La‐O > bond. Moreover, the capacity for He interstitials increases with higher Pu concentration in the octahedrons.

Effect of hydrothermally doped-Nb on structure and cycling stability of Li(Ni0.96Co0.04)O2

Nb5+ ions are hydrothermally incorporated into the hydroxide precursor of Li(Ni0.96Co0.04)O2 before lithiation. The hydrothermal doping of Nb results in particle size refinement and produces short- and long-ranged cation ordering that has not been observed in a Ni-rich layered cathode. The cation-ordered structure stabilizes the delithiated structure while the particle size refinement helps to absorb the strain energy generated during the H2 → H3 phase transformation near the charge end. 0.5 mol%-doped Li[Ni0.956Co0.039Nb0.005]O2 retains 96 % of the initial capacity after 100 cycles, which is remarkable despite its ultra-high Ni content. The cathode also delivers a discharge capacity of 227 mA h g−1. By contrast, the Li[Ni0.95Co0.04Al0.01]O2 maintains only 82 % of the initial capacity after 100 cycles. This finding highlights the importance of exploring different doping methods and the need to control and moderate the antisite defects which stabilize the delithiated structure to improve the cycling stability of ultra-high Ni-rich layered cathodes to a commercially viable level.

Dynamic Evolution of Antisite Defect and Coupling Anionic Redox in High‐Voltage Ultrahigh‐Ni Cathode

AbstractHigh‐voltage ultrahigh‐Ni cathodes (LiNixCoyMn1−x−yO2, x≥0.9) can significantly enhance the energy density and cost‐effectiveness of Li‐ion batteries beyond current levels. However, severe Li−Ni antisite defects and their undetermined dynamic evolutions during high‐voltage cycling limit the further development of these ultrahigh‐Ni cathodes. In this study, we quantify the dynamic evolutions of the Li−Ni antisite defect using operando neutron diffraction and reveal its coupling relationship with anionic redox, another critical challenge restricting ultrahigh‐Ni cathodes. We detect a clear Ni migration coupled with an unstable oxygen lattice, which accompanies the oxidation of oxygen anions at high voltages. Based on these findings, we propose that minimized Li−Ni antisite defects and controlled Ni migrations are essential for achieving stable high‐voltage cycling structures in ultrahigh‐Ni cathodes. This is further demonstrated by the optimized ultrahigh‐Ni cathode, where reduced dynamic evolutions of the Li−Ni antisite defect effectively inhibit the anionic redox, enhancing the 4.5 V cycling stability.

Amino Group-Aided Efficient Regeneration Targeting Structural Defects and Inactive FePO4 Phase for Degraded LiFePO4 Cathodes.

It is urgent to develop efficient recycling methods for spent LiFePO4 cathodes to cope with the upcoming peak of power battery retirement. Compared with the traditional metallurgical recovery methods that lack satisfactory economic and environmental benefits, the direct regeneration seems to be a promising option at present. However, a simple direct lithium replenishment cannot effectively repair and regenerate the cathodes due to the serious structural damage of the spent LiFePO4. Herein, the spent LiFePO4 cathodes are directly regenerated by a thiourea-assisted solid-phase sintering process. The density functional theory calculation indicates that thiourea has a targeted repair effect on the antisite defects and inactive FePO4 phase in the spent cathode due to the associative priority of amino group (─NH2) in thiourea with Fe ions: Fe3+─N > Fe2+─N. Meanwhile, the pyrolysis products of thiourea can also create an optimal reducing atmosphere and inhibit the agglomeration of particles in the high temperature restoration process. The regenerated LiFePO4 exhibits an excellent electrochemical performance, which is comparable to that of commercial LiFePO4. This targeted restoration has improved the efficiency of direct regeneration, which is expected to achieve large-scale recycling of spent LiFePO4.

Entropy engineering promotes thermoelectric performance while realizing P–N switchable conduction in BiSbSe1.5Te1.5

BiSbSe1.5Te1.5, a typical multi-layered compound, can be utilized to fabricate p-n junctions with the identical chemical composition by regulating the antisite defects and anion vacancies via defect engineering. However, the thermoelectric performance of n-type BiSbSe1.5Te1.5 is limited due to poor electrical transport properties. Entropy engineering is a novel strategy for expanding the space of performance optimization in materials science, including the field of thermoelectric. Herein, we realize a largely enhanced thermoelectric performance for n-type BiSbSe1.5Te1.5 by employing entropy engineering. Both mass field fluctuations and stress variations field are introduced simultaneously in the lattice, leading to additional phonon scattering. Moreover, nano-laminate structure, nanoscale interstices and holes are formed in the samples. All of these defects and nanoscale structures are especially efficient on trapping phonons. As a result, the optimizing electrical transport properties while maintaining low thermal conductivity are achieved, showcasing a peak ZT of 0.54 at 475 K and a remarkable average ZT of 0.45 between 300 and 550 K for n-type BiSbSe1.25Te1.75.These findings not only provide a way to enhance the thermoelectric performance of n-type BiSbSe1.5Te1.5 but also push forward the promise of the applications in fabricating well-matched p-n junctions using thermoelectric materials with the identical chemical composition.

Defect-driven ion storage on hexagonal boron nitride for fire-safe and high-performance lithium-ion batteries

The mass market adoption of electric vehicles has increased the risk of safety concerns, such as overheating and flammability. Rational design of fire-safe and high-capacity anodes with thermal tolerance, capable of fast-charging and long cycle-life, is crucial for the development of next generation Li-ion batteries operating under extreme conditions. Here we report a defect engineered hexagonal boron nitride (hBN) anode to mediate the safety dilemma. We demonstrate that the defects generated via cryomilling catalyze the reversible LiF formation and enable the pseudocapacitive type Li-ion storage on hBN. The non-flammability and excellent thermal tolerance of hBN allows high specific capacity (880 mAh/g @ 25 mA/g), rate performance (480 mAh/g @ 5 A/g) and stable cycling (5000 cycles) at 60 °C. The Li-ion full-cell with the defective hBN anode and the conventional cathode (LiNiMnCoO2) delivers significantly higher energy (400 Wh kg−1) and power density (1 kW kg−1) when compared to graphite/LiNiMnCoO2 full-cells (121 Wh kg−1 and 250 W kg−1). First-principles calculations confirm that nitrogen antisite (NBVN) defects are responsible for the electrochemical activation of otherwise inactive hBN. The strategy of defect-induced electrochemical activation opens up new avenues in the design of high-performance electrode materials for numerous secondary batteries.

Synthesis of Multifunctional Organic Molecules via Michael Addition Reaction to Manage Perovskite Crystallization and Defect.

Additive engineering plays a pivotal role in achieving high-quality light-absorbing layers for high-performance and stable perovskite solar cells (PSCs). Various functional groups within the additives exert distinct regulatory effects on the perovskite layer. However, few additive molecules can synergistically fulfill the dual functions of regulating crystallization and passivating defects. Here, we custom-synthesized 2-ureido-4-pyrimidone (UPy) organic small molecules with diverse functional groups as additives to modulate crystallization and defects in perovskite films via the Michael addition reaction. Theoretical and experimental investigations demonstrate that the -OH groups in UPy exhibit significant effects in fixing uncoordinated Pb2+ ions, passivation of lead-iodide antisite defects, alleviating hysteresis, and reducing non-radiative recombination. Furthermore, the enhanced C=O and -NH2 motifs interact with the A-site cation via hydrogen bonding, which relieves residual strain and adjusts crystal orientation. This strategy effectively controls perovskite crystallization and passivates defects, ultimately enhancing the quality of perovskite films. Consequently, the open-circuit voltage of the UPy-based p-i-n PSCs reaches 1.20 V, and the fill factor surpasses 84%. The champion device delivers a power conversion efficiency of 25.75%. Remarkably, the unencapsulated device maintained 96.9% and 94.5% of its initial efficiency following 3,360 hours of dark storage and 1,866 hours of 1-sun illumination, respectively.