The Journal of Physical Chemistry Letters最新文献

{"title":"Intrinsic Electric Fields Promote Delocalized Interlayer Excitons in Janus In2SSe Moiré Bilayers","authors":"Xinyong Meng,&nbsp;Wei Hu* and Jinlong Yang,&nbsp;","doi":"10.1021/acs.jpclett.5c0107810.1021/acs.jpclett.5c01078","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01078https://doi.org/10.1021/acs.jpclett.5c01078","url":null,"abstract":"<p >The moiré potential in van der Waals (vdW) moiré superlattices is well-established to significantly influence electronic structures and optical excitations. When Janus monolayers are employed to construct twisted bilayers, an additional degree of freedom─the out-of-plane Janus field─is introduced alongside the moiré potential, leading to modifications in both electronic and optical properties. While these two effects have been individually investigated in prior studies on excitons, the behavior of excitons under the simultaneous presence of both effects remained unexplored. In this study, we investigate, for the first time, the interplay between these two effects in twisted Janus In₂SSe. Our results demonstrate that the band structures and excitonic properties can be significantly modulated through variations in stacking sequences and intrinsic dipole orientations. This work provides a framework for the precise control of emission energy, exciton characteristics, and the spatial distribution of moiré excitons. We predict the coexistence of intrinsic Janus field-induced interlayer excitons and moiré potential-driven moiré excitons in twisted bilayer Janus In₂SSe. These findings not only elucidate the interaction between Janus fields and moiré potentials but also introduce a novel, multifaceted strategy for exciton manipulation.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 21","pages":"5272–5280 5272–5280"},"PeriodicalIF":4.8,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165856","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":"Quantifying Design Principles for Light-Emitting Materials with Inverted Singlet–Triplet Energy Gaps","authors":"Varun Rishi*,&nbsp;Ali Abou Taka,&nbsp;Hrant P. Hratchian and Laura M. McCaslin*,&nbsp;","doi":"10.1021/acs.jpclett.5c0082710.1021/acs.jpclett.5c00827","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00827https://doi.org/10.1021/acs.jpclett.5c00827","url":null,"abstract":"<p >Molecular engineering of organic emitter molecules with inverted singlet–triplet energy gaps (INVEST) has emerged as a powerful approach for enhancing fluorescence efficiency through triplet harvesting. In these unique materials, the first excited singlet state (S₁) lies below the lowest triplet state (T₁), enabling efficient reverse intersystem crossing. Previous computational studies have focused on accurately calculating the inverted energy gap and establishing qualitative structure–property relationships. Here, we present quantitative relationships that link the molecular structure to the S₁–T₁ energy gap, Δ<i>E</i>_ST, by introducing a benchmark set of 15 heptazine-based INVEST molecules (HEPTA-INVEST15). We identify a strong linear correlation (<i>R</i>² &gt; 0.94) between Δ<i>E</i>_ST and both the degree of intramolecular charge transfer and the deviation from a single-excitation character, as quantified by %<i>R</i>₁ values and transition density matrix norms. These trends persist across our expanded set of 44 mono-, di-, and tri-substituted heptazines (HEPTA-INVEST44), underscoring the generality of our findings. Notably, strongly electron-donating groups, such as −NH₂, minimize the magnitude of inverted gaps in mono-substituted heptazines yet produce the most negative Δ<i>E</i>_ST in certain tri-substituted derivatives, a result arising from competing resonance effects and excited-state aromaticity. Although Δ<i>E</i>_ST shows no clear correlation with Hammett parameters, our results reveal that physically meaningful, computable descriptors offer a mechanistic foundation for the future data-driven design of INVEST emitters. These findings pave the way for machine-learning approaches that connect the molecular structure to Δ<i>E</i>_ST without requiring high-level excited-state calculations.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 21","pages":"5213–5220 5213–5220"},"PeriodicalIF":4.8,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165861","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":"Interface Field Engineering of Weakly Alkaline-Treated PEDOT:PSS for Enhanced Performance and Stability of Tin-Based Perovskite Solar Cells","authors":"Yi Jing,&nbsp;Chensi Gong,&nbsp;Ao Shen,&nbsp;Jiale Yuan,&nbsp;Wenchao Huang,&nbsp;Wenzhen Lv,&nbsp;Runfeng Chen* and Ligang Xu*,&nbsp;","doi":"10.1021/acs.jpclett.5c0083010.1021/acs.jpclett.5c00830","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00830https://doi.org/10.1021/acs.jpclett.5c00830","url":null,"abstract":"<p >State-of-the-art tin-based perovskite solar cells (TPSCs) commonly use a water-based poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layer. However, the strong acidity of PEDOT:PSS, arising from the deprotonation of its −SO₃H group in PSS chains due to the low acid dissociation constant (p<i>K</i>_a), often degrades tin perovskite films, compromising both the device performance and stability of TPSCs. Here, we present a novel interface engineering strategy using ammonium hydroxide (NH₄OH) treated PEDOT:PSS, which effectively neutralizes acidic groups in PSS while simultaneously improving the quality of tin perovskite films due to preferentially oriented crystal growth. Besides, this strategy improves conductivity of the hole transport layer and effectively suppresses charge recombination due to the high-quality perovskite films. As a result, the devices achieve a remarkable power conversion efficiency of 13.3%, alongside significant improvements in stability. Notably, the unencapsulated devices retain 85% of their initial efficiency after approximately 1600 h in N₂. Our method marks a significant advancement, integrating enhanced efficiency with improved durability and offering a scalable pathway for the commercialization of tin-based perovskite photovoltaics.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 21","pages":"5258–5264 5258–5264"},"PeriodicalIF":4.8,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144166007","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":"Quantifying Design Principles for Light-Emitting Materials with Inverted Singlet–Triplet Energy Gaps","authors":"Varun Rishi, Ali Abou Taka, Hrant P. Hratchian, Laura M. McCaslin","doi":"10.1021/acs.jpclett.5c00827","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00827","url":null,"abstract":"Molecular engineering of organic emitter molecules with inverted singlet–triplet energy gaps (INVEST) has emerged as a powerful approach for enhancing fluorescence efficiency through triplet harvesting. In these unique materials, the first excited singlet state (S₁) lies below the lowest triplet state (T₁), enabling efficient reverse intersystem crossing. Previous computational studies have focused on accurately calculating the inverted energy gap and establishing qualitative structure–property relationships. Here, we present quantitative relationships that link the molecular structure to the S₁–T₁ energy gap, Δ<i>E</i>_ST, by introducing a benchmark set of 15 heptazine-based INVEST molecules (HEPTA-INVEST15). We identify a strong linear correlation (<i>R</i>² &gt; 0.94) between Δ<i>E</i>_ST and both the degree of intramolecular charge transfer and the deviation from a single-excitation character, as quantified by %<i>R</i>₁ values and transition density matrix norms. These trends persist across our expanded set of 44 mono-, di-, and tri-substituted heptazines (HEPTA-INVEST44), underscoring the generality of our findings. Notably, strongly electron-donating groups, such as −NH₂, minimize the magnitude of inverted gaps in mono-substituted heptazines yet produce the most negative Δ<i>E</i>_ST in certain tri-substituted derivatives, a result arising from competing resonance effects and excited-state aromaticity. Although Δ<i>E</i>_ST shows no clear correlation with Hammett parameters, our results reveal that physically meaningful, computable descriptors offer a mechanistic foundation for the future data-driven design of INVEST emitters. These findings pave the way for machine-learning approaches that connect the molecular structure to Δ<i>E</i>_ST without requiring high-level excited-state calculations.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"4 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088244","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":"Scalable Fabrication of Efficient Sky-Blue Perovskite Light-Emitting Diodes with Dual Salts","authors":"Zekun Wang,&nbsp;Kaijie Ni,&nbsp;Runqing Lu,&nbsp;Xinrui Wang,&nbsp;Zhi Zheng,&nbsp;Chang Yi* and Jianpu Wang*,&nbsp;","doi":"10.1021/acs.jpclett.5c0128810.1021/acs.jpclett.5c01288","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01288https://doi.org/10.1021/acs.jpclett.5c01288","url":null,"abstract":"<p >Bromide (Br)–chloride (Cl) mixing in three-dimensional (3D) perovskites provides an effective method for band gap engineering for blue emission. However, their low formation energy and poor solubility trigger rapid crystallization at room temperature, leading to extensive defect formation. Here, we introduce dual organic salts into the perovskite precursor solution to suppress crystallization and defect formation. Specifically, the tetraphenylphosphonium salt forms multiple weak interactions with lead halide octahedra, slowing 3D perovskite growth, while simultaneously directing the guanidinium slat to passivate A-site vacancies instead of forming low-dimensional perovskite. This strategy eliminates the need for antisolvent or post-treatment processes, enabling scalable device fabrication without compromising performance. As a result, sky-blue light-emitting diodes (LEDs) with active areas of 3 and 900 mm² exhibit peak external quantum efficiencies of 13.5% and 11.2% and maximum luminance values of 5493 and 843 cd m^–2, respectively. This work provides a useful route toward large-area blue perovskite LEDs.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 21","pages":"5281–5286 5281–5286"},"PeriodicalIF":4.8,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144166023","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":"Scalable Fabrication of Efficient Sky-Blue Perovskite Light-Emitting Diodes with Dual Salts.","authors":"Zekun Wang,Kaijie Ni,Runqing Lu,Xinrui Wang,Zhi Zheng,Chang Yi,Jianpu Wang","doi":"10.1021/acs.jpclett.5c01288","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01288","url":null,"abstract":"Bromide (Br)-chloride (Cl) mixing in three-dimensional (3D) perovskites provides an effective method for band gap engineering for blue emission. However, their low formation energy and poor solubility trigger rapid crystallization at room temperature, leading to extensive defect formation. Here, we introduce dual organic salts into the perovskite precursor solution to suppress crystallization and defect formation. Specifically, the tetraphenylphosphonium salt forms multiple weak interactions with lead halide octahedra, slowing 3D perovskite growth, while simultaneously directing the guanidinium slat to passivate A-site vacancies instead of forming low-dimensional perovskite. This strategy eliminates the need for antisolvent or post-treatment processes, enabling scalable device fabrication without compromising performance. As a result, sky-blue light-emitting diodes (LEDs) with active areas of 3 and 900 mm2 exhibit peak external quantum efficiencies of 13.5% and 11.2% and maximum luminance values of 5493 and 843 cd m-2, respectively. This work provides a useful route toward large-area blue perovskite LEDs.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"71 1","pages":"5281-5286"},"PeriodicalIF":6.475,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087724","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":"Correction to “Amorphous Silica Interlayer Unlocks Direct Epitaxial Growth of CsPbBr3 on Silicon via Slip-and-Stick Mechanism”","authors":"Christian Tantardini*,&nbsp;Simone Argiolas,&nbsp;Paola De Padova,&nbsp;Boris I. Yakobson,&nbsp;Aldo Di Carlo and Alessandro Mattoni*,&nbsp;","doi":"10.1021/acs.jpclett.5c0058610.1021/acs.jpclett.5c00586","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00586https://doi.org/10.1021/acs.jpclett.5c00586","url":null,"abstract":"","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 21","pages":"5287–5288 5287–5288"},"PeriodicalIF":4.8,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpclett.5c00586","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165863","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Gate Voltage Regulation of Surface Properties in Polyethylenimine-Doped Indium Oxide Transistors for Enhanced Detection of Low-Concentration NO2 at Room Temperature.","authors":"Chengyao Liang,Fuguo Wang,Jiongyue Hao,Zuodong Wang,Wei Jiang,Xi Yang,Wei Hu,Yong He","doi":"10.1021/acs.jpclett.5c00950","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00950","url":null,"abstract":"Nitrogen dioxide (NO2), a toxic environmental pollutant, requires high-performance sensors for ppb-level detection. While indium oxide thin-film transistors (In2O3 TFTs) show promise, conventional devices require costly vacuum equipment, unlike solution-processed spin-coating, which is suitable for scalable fabrication. Channel doping enhances gas sensing performance but degrades transistor output current. This work introduces polyethylenimine (PEI) as the electron dopant for solution-processed In2O3 TFTs. PEI provides abundant electrons for NO2 interaction, but the limited current-driving capability of resistive sensors fundamentally restricts their detection sensitivity to such low-amplitude signals. Gate voltage-regulated surface electronic states in thin films significantly enhance the current-driving capability, enabling ultrasensitive NO2 detection down to subppb concentrations. The 1% PEI-doped In2O3 TFT demonstrates a saturation drain current of 0.065 mA, representing a 1.91-fold enhancement over the undoped counterpart (0.034 mA). Furthermore, the optimized 1% PEI: In2O3 TFT achieves a 23% response toward 10 ppb NO2.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"108 1","pages":"5236-5243"},"PeriodicalIF":6.475,"publicationDate":"2025-05-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087738","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":"Bayesian Optimization with Gaussian Processes Assisted by Deep Learning for Material Designs","authors":"Shin Kiyohara*,&nbsp; and ,&nbsp;Yu Kumagai,&nbsp;","doi":"10.1021/acs.jpclett.5c0059210.1021/acs.jpclett.5c00592","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00592https://doi.org/10.1021/acs.jpclett.5c00592","url":null,"abstract":"<p >Machine learning (ML) approaches have become ubiquitous in the search for new materials in recent years. Bayesian optimization (BO) based on Gaussian processes (GPs) has become a widely recognized approach in material exploration. However, feature engineering has critical impacts on the efficiency of GP-based BO, because GPs cannot automatically generate descriptors. To address this limitation, this study applies deep kernel learning (DKL), which combines a neural network with a GP, to BO. The efficiency of the DKL model was comparable to or significantly better than that of a standard GP in a data set of 922 oxide data sets, covering band gaps, ionic dielectric constants, and effective masses of electrons, as well as in experimental data sets, the band gaps of 610 hybrid organic–inorganic perovskite alloys. When searching for the alloy with the highest Curie temperature among 4560 alloys, the standard GP outperformed the DKL model because a strongly correlated descriptor of the Curie temperature could be directly utilized. Additionally, DKL supports transfer learning, which further enhances its efficiency. Thus, we believe that BO based on DKL paves the way for exploring diverse material spaces more effectively than GPs.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 21","pages":"5244–5251 5244–5251"},"PeriodicalIF":4.8,"publicationDate":"2025-05-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpclett.5c00592","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165978","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bayesian Optimization with Gaussian Processes Assisted by Deep Learning for Material Designs.","authors":"Shin Kiyohara,Yu Kumagai","doi":"10.1021/acs.jpclett.5c00592","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00592","url":null,"abstract":"Machine learning (ML) approaches have become ubiquitous in the search for new materials in recent years. Bayesian optimization (BO) based on Gaussian processes (GPs) has become a widely recognized approach in material exploration. However, feature engineering has critical impacts on the efficiency of GP-based BO, because GPs cannot automatically generate descriptors. To address this limitation, this study applies deep kernel learning (DKL), which combines a neural network with a GP, to BO. The efficiency of the DKL model was comparable to or significantly better than that of a standard GP in a data set of 922 oxide data sets, covering band gaps, ionic dielectric constants, and effective masses of electrons, as well as in experimental data sets, the band gaps of 610 hybrid organic-inorganic perovskite alloys. When searching for the alloy with the highest Curie temperature among 4560 alloys, the standard GP outperformed the DKL model because a strongly correlated descriptor of the Curie temperature could be directly utilized. Additionally, DKL supports transfer learning, which further enhances its efficiency. Thus, we believe that BO based on DKL paves the way for exploring diverse material spaces more effectively than GPs.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"78 1","pages":"5244-5251"},"PeriodicalIF":6.475,"publicationDate":"2025-05-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087737","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}