The Journal of Physical Chemistry Letters最新文献

{"title":"Mitigating Ion Migration in a Mixed-Halide Perovskite via Laser Shock Annealing.","authors":"Chunpeng Song,Shihui Lou,Shenyi Deng,Menghan Li,Jingming Xin,Qiuju Liang,Jiangang Liu","doi":"10.1021/acs.jpclett.5c02594","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02594","url":null,"abstract":"Mixed-halide perovskites are susceptible to ion migration due to their high lattice flexibility, resulting in a decrease in device efficiency and the degradation of device stability. In this work, by utilizing the unique pulse characteristics and thermal effects of the nanosecond laser shock annealing (LSA) technique, we can effectively inhibit ionic migration in mixed-halide perovskites, which in turn ameliorates the optoelectronic properties of perovskites. The results show that, compared with traditional thermal annealing (TA), the perovskite films treated by LSA exhibit a more uniform ionic distribution, eliminating the nonphotoactive δ-phase caused by ionic segregation. The reduction in ionic migration is attributed to the enhanced interaction among the inter-ionic forces in the inorganic framework and the optimization of crystallization kinetics in a mixed-halide perovskite, resulting from the ultrafast shock pressure in the range of 0.95-1.64 GPa and the rapid heating/cooling thermal effects of LSA. Furthermore, the perovskite fabricated by LSA significantly reduces the defect density, mitigating defect-driven ionic migration. Therefore, the photophysical processes of perovskites were optimized, which extended the carrier lifetime and enhanced the carrier mobility. In conclusion, the LSA technique provides an efficient approach to addressing the problem of ion migration in mixed-halide perovskites by modulation of the crystal structure and ionic interactions.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"157 1","pages":"10345-10354"},"PeriodicalIF":6.475,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194808","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"F-Center-Mediated Formation of Metallic Li from Solid Electrolyte Interphases under High-Energy Electron-Beam Irradiation.","authors":"Wenbo Zhai,Wei Liu,Yi Yu","doi":"10.1021/acs.jpclett.5c02520","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02520","url":null,"abstract":"The solid electrolyte interphase (SEI) plays a critical role in governing interfacial kinetics and maintaining anode stability during electrochemical cycling. As such, elucidating the structure-property relationships of the SEI is essential but also highly challenging due to its inherent sensitivity. Recent advances in electron microscopy have greatly facilitated these efforts by enabling nanoscale structural characterization. However, the fundamental response of sensitive SEI to high-energy electron-beam exposure remains largely unexplored. Here the precipitation of metallic Li from SEI under electron-beam irradiation is revealed, which is driven by the accumulation of F-centers formed in Li2O, the dominant inorganic SEI component. Remarkably, an electron beam can also trigger the reverse transformation of Li into Li2O. The findings offer novel microstructural insights into the electron-beam-induced chemical dynamics of the SEI.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"78 1","pages":"10410-10415"},"PeriodicalIF":6.475,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194563","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Copper Doping Enables Superior Charge Separation for Enhanced Spin Coherence and CO2 Photoreduction in CsPbBr3 Quantum Dots.","authors":"Xiaoyang Li,Lin Cheng,Rongrong Hu,Qiaoyun Wu,Pan Liang,Shixi Qin,Zegui Yang,Bobo Yang,Jun Zou,Tianqing Jia,Zhenrong Sun,Donghai Feng","doi":"10.1021/acs.jpclett.5c02411","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02411","url":null,"abstract":"All-inorganic perovskite quantum dots have emerged as highly promising optoelectronic semiconductor nanomaterials, owing to their remarkable photoelectric properties. Herein, the copper ions were successfully doped into the CsPbBr3 lattice, introducing a new trap state that facilitates rapid electron trapping and significantly enhancing room-temperature hole spin signals. In addition, photocharging dynamics were investigated using a prepump-pump-probe methodology, revealing three photocharged state lifetimes of 72 and 680 μs and >15 min in copper-doped CsPbBr3 quantum dots (QDs), longer than that of the undoped ones. Furthermore, the copper-doped CsPbBr3 QDs demonstrated superior photocatalytic activity for CO2 reduction with an electron consumption rate of 72.3 μmol g-1 h-1, nearly 1.9 times higher than that of undoped CsPbBr3 QDs, due to the long-lived photocharged states. These findings unveil the pivotal role of dopant-mediated trap states in controlling spin coherence and charge dynamics, offering a versatile design framework for developing multifunctional perovskite QDs for spin-based optoelectronics and photocatalysis.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"23 1","pages":"10363-10370"},"PeriodicalIF":6.475,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High-Gain Self-Powered Photodetector Enabled by Type-II CsPbBr3 Single Crystal Wafer-CdSeS Quantum Dot Heterojunction for Weak Light Photodetection.","authors":"Xiangyu Huo,Xinying Liu,He Zhang,Xueying Cui,Ziyang Jiang,Siyuan Li,Yao Zhuo,Minghui Wang,Rui Liu,Tianliang Zhou,Jianxu Ding","doi":"10.1021/acs.jpclett.5c02599","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02599","url":null,"abstract":"To address the demand for high-sensitivity photodetectors under weak light conditions, we have designed a Type-II heterojunction photodetector based on CsPbBr3 single crystal wafers (SCWs) and CdSeS quantum dots (QDs). High-quality two-dimensional (2D) CsPbBr3 SCWs were grown using a space confined growth method, while zero-dimensional (0D) CdSeS QDs were prepared by thermal injection. The heterojunctions were constructed by partially coating the CsPbBr3 SCWs with the CdSeS QDs. Due to the staggered energy band alignment, the built-in electric field was established within the interface, significantly enhancing the separation of photogenerated carriers and effectively suppressing nonradiative recombination. Kelvin probe force microscopy (KPFM) measurements confirmed a surface potential difference of 0.69 V, validating the presence of the built-in field. The device exhibited a low dark current of 1.23 × 10-11 A and a detectivity (D*) of 1.2 × 1013 Jones under weak light illumination. At 5 V bias, the device demonstrated an external quantum efficiency (EQE) of 193%, indicating efficient photocarrier extraction. These results highlight the outstanding performance of the CsPbBr3-CdSeS Type-II heterojunction for weak light detection and provide a promising approach for high-performance photodetectors.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"56 1","pages":"10381-10389"},"PeriodicalIF":6.475,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145188990","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Donor-Acceptor Pairs Near Silicon Carbide Surfaces.","authors":"Anil Bilgin, Ian N Hammock, Alexander A High, Giulia Galli","doi":"10.1021/acs.jpclett.5c02376","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02376","url":null,"abstract":"<p><p>Donor-acceptor pairs (DAPs) in wide-bandgap semiconductors are promising platforms for the realization of quantum technologies, due to their optically controllable, long-range dipolar interactions. Specifically, Al-N DAPs in bulk silicon carbide (SiC) have been predicted to enable coherent coupling over distances exceeding 10 nm. However, their practical implementations require an understanding of the properties of these pairs near surfaces and interfaces. Here, using first-principles calculations, we investigate how the presence of surfaces influence the stability and optical properties of Al-N DAPs in SiC, and we show that they retain favorable optical properties comparable to their bulk counterparts, despite a slight increase in electron-phonon coupling. Furthermore, we introduce the concept of surface-defect pairs (SDPs), where an electron-hole pair is generated between a near-surface defect and an occupied surface state located in the bandgap of the material. We show that vanadium-based SDPs near OH-terminated 4H-SiC surfaces exhibit dipoles naturally aligned perpendicular to the surface, greatly enhancing dipole-dipole coupling between SDPs. Our results also reveal significant polarization-dependent modulation in the stimulated emission and photoionization cross sections of <i>V</i>-based SDPs, which are tunable by 2 orders of magnitude via the incident laser's polarization angle. The near-surface defects investigated here provide novel possibilities for the development of hybrid quantum-classical interfaces, as they can be used to mediate information transfer between quantum nodes and integrated photonic circuits.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"10371-10380"},"PeriodicalIF":4.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145190390","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"UV Resonance Raman Spectroscopic Marker Bands of Base Pair Formation During Nucleic Acids Assembly.","authors":"Aina-Sophie Schüen, Annika S Bumberger, Benedikt Bädorf, Dilaza Kendirlik, Stephanie Kath-Schorr, Stefan Grimme, Patrycja Kielb","doi":"10.1021/acs.jpclett.5c02171","DOIUrl":"10.1021/acs.jpclett.5c02171","url":null,"abstract":"<p><p>The controlled assembly of nucleic acids (NAs) underpins the function of DNA and RNA structures. Here, we demonstrate the use of UV resonance Raman (UVRR) spectroscopy as a chemically selective and label-free tool to inform one about the structural details of the molecular assembly of NAs and their underlying interactions with a particular focus on H-bonding between base pairs. Using experimental H/D exchange and hybrid DFT-based computational Raman spectra, we identify UVRR marker bands that involve vibrations of C=O, NH, and NH₂ groups, which are relevant to H-bonding interactions in guanine-cytosine (G-C) and adenine-thymidine (A-T) Watson-Crick base pairs. Analyzing peak shifts and changes in relative intensities of these marker bands that are consistent with computational spectra, we successfully follow the conformational assembly of oligonucleotide strands by recording their UVRR spectra during thermal hybridization to double helices. Variations in obtained thermal sigmoidal transitions can inform one on mechanistic details in complex DNA and RNA architectures.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"10390-10399"},"PeriodicalIF":4.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145197519","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Analytic Dipole Moments For Complete Active Space Linearized Pair-Density Functional Theory.","authors":"Helen S Clifford, Matthew R Hennefarth, Donald G Truhlar, Laura Gagliardi","doi":"10.1021/acs.jpclett.5c02466","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02466","url":null,"abstract":"<p><p>The accurate prediction of molecular dipole moments requires high-quality wave functions or electron densities. For systems exhibiting strong electron correlation, multireference methods are preferred to reliably describe molecular properties such as dipole moments. We derive and implement analytic expressions for permanent dipole moments of ground and excited states for linearized pair-density functional theory (L-PDFT), starting with state-averaged complete active space wave functions as reference functions. Dipole moments are evaluated via response theory as the first derivative of the L-PDFT energy with respect to an external electric field. We evaluated the performance of L-PDFT for acetylene, phenol, the spiro cation, and 20 aromatic molecules. L-PDFT consistently predicts accurate dipole moments near conical intersections and in regions of strong nuclear-electronic coupling. The ability to produce smooth and accurate dipole surfaces for diverse molecular systems establishes L-PDFT as a promising method for force field development, spectroscopic analysis, and generating machine-learning potentials.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"10400-10409"},"PeriodicalIF":4.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145197427","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ultrafast Singlet Exciton Dissociation in Y-Series Acceptors.","authors":"Jessica M de la Perrelle,Harrison J McAfee,Andrew Dolan,Zi Goh,Top Archie Dela Peña,Ruijie Ma,Jiaying Wu,David M Huang,Tak W Kee","doi":"10.1021/acs.jpclett.5c02415","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02415","url":null,"abstract":"Y-series acceptors are critical components of the highest-performance organic photovoltaic devices. When prepared as nanoparticles (NPs), Y-series acceptors are also highly effective photocatalysts for hydrogen (H2) evolution from water. Their performance is partially due to their unusual ability to dissociate excitons in the absence of an electron donor. The exciton dissociation is rapid and occurs within the pulse duration of most ultrafast spectrometers. Here, we use broadband compressed laser pulses to resolve exciton dissociation time constants in NPs of four Y-series acceptors: Y6, L8-BO, PC6, and PY-IT. We find that exciton dissociation is fastest in Y6 NPs, followed by PC6 NPs, PY-IT NPs, and L8-BO NPs, with time constants ranging from 28 ± 3 fs for Y6 NPs to 149 ± 16 fs for L8-BO NPs. The trend in the exciton dissociation rate correlates with the NP morphology, where fast exciton dissociation is associated with increased energetic disorder and mixed H/J aggregation. This study shows that exciton dissociation is a conserved property across a range of Y-series acceptors and occurs at sufficiently fast rates to outcompete most other photophysical processes.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"23 1","pages":"10306-10315"},"PeriodicalIF":6.475,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145182535","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Design of Transition Metal-Intercalated Carbon-Nitrogen-Boron Catalysts and Application to Electrocatalytic Carbon Monoxide Reduction.","authors":"Zhou Zheng,Yuxiang Min,Dewei Zhang,Xinshu Zhou,Shriya Gumber,Oleg V Prezhdo,Lai Xu","doi":"10.1021/acs.jpclett.5c02458","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02458","url":null,"abstract":"Catalysts for generating C2 products by the electrocatalytic CO reduction reaction (CORR) still exhibit low activity and selectivity, and the development of CORR electrocatalysts with high performance remains crucial. Therefore, new transition metal-inserted bilayer carbon-nitrogen-boron (C4NB) materials are reported. Calculations of the catalytic performance of seven screened catalysts showed that C4NB/V/C4NB has high activity and selectivity for ethanol with a limiting potential of -0.27 V. A descriptor, related to the ring charge, is found to predict the catalytic performance of the electrocatalysts. Our bilayer catalyst provides an idea for the development of high-performance catalysts, and the proposed new descriptor can be used to quickly predict the catalytic performance.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"39 1","pages":"10355-10362"},"PeriodicalIF":6.475,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145188916","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Impact of Diammonium Cation Dipole Moment on Charge Transport in 2D/3D Perovskite.","authors":"Zeping Ou,Yu Jie Zheng,Yi Pan,Kuan Sun","doi":"10.1021/acs.jpclett.5c02097","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02097","url":null,"abstract":"2D/3D heterojunction perovskite solar cells have emerged as a highly promising photovoltaic architecture, combining high efficiency and exceptional long-term stability. Understanding the energy band alignment at the 2D/3D interface is crucial for optimizing device performance. In this study, we utilize a multiscale computational framework─incorporating density functional theory, ab initio molecular dynamics, and nonadiabatic molecular dynamics simulations─to investigate how dipole engineering of diammonium cations in Dion-Jacobson (DJ) perovskites influences band structure, charge carrier dynamics, and nonradiative recombination mechanisms. Our results demonstrate that increasing the alkyl chain length of diammonium cations significantly enhances the electrostatic potential polarization. This modification not only increases the dipole moments but also strengthens the hydrogen bonding interactions with adjacent iodide anions. Notably, the increased dipole moment shifts the heterojunction band alignment from type-I to type-II, facilitating the spatial delocalization of electron-hole, reducing pure-dephasing and nonadiabatic coupling, thereby suppressing nonradiative recombination. Moreover, the dipole-induced built-in electric field promotes upward band bending and enhances work function, which together improve spatial charge localization, extend carrier recombination distances, and shorten carrier transport paths─optimizing carrier dynamics across the 2D and 3D phases. Additionally, the hydrogen bonding between diammonium cations and the [PbI6]4- framework suppresses FA rotation and strengthens cation-inorganic dynamic coupling, leading to reduced atomic vibrations. Rigid diammonium cations enhance low-frequency phonon vibration modes, which stabilize the type-II heterojunction and weaken nonadiabatic coupling. Conversely, π-conjugated diammonium cations introduce higher-frequency and molecular phonon vibration modes, accelerating the charge transport. This study establishes a mechanistic link between diammonium cations, dipole engineering, band structure modulation, and carrier dynamics in DJ-phase 2D/3D perovskites, providing essential design principles for developing high-efficiency and stable perovskite photovoltaics.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"105 1","pages":"10324-10335"},"PeriodicalIF":6.475,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145188924","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}