Chemistry of Materials最新文献

{"title":"Guidelines for the Selection of Scintillators for Indirect Photon-Counting X-ray Detectors","authors":"J. Jasper van Blaaderen, Casper van Aarle, David Leibold, Pieter Dorenbos, Dennis R. Schaart","doi":"10.1021/acs.chemmater.4c03437","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03437","url":null,"abstract":"X-ray photon-counting detectors (PCDs) are a rapidly developing technology. Current PCDs used in medical imaging are based on CdTe, CZT, or Si semiconductor detectors, which directly convert X-ray photons into electrical pulses. An alternative approach is to combine ultrafast scintillators with silicon photomultipliers (SiPMs). Here, an overview is presented of different classes of scintillators, with the aim of assessing their potential application in scintillator-SiPM based indirect X-ray PCDs. To this end, three figures of merit (FOMs) are defined: the pulse intensity, the pulse duration, and the pulse quality. These FOMs quantify how characteristics such as light yield, pulse shape, and energy resolution affect the suitability of scintillators for application in indirect PCDs. These FOMs are based on emissive characteristics; a fourth FOM (ρZ_<i>eff</i>^3.5) is used to also take stopping power into account. Other important properties for the selection process include low self-absorption, low after-glow, possibility to produce sub-mm pitch pixel arrays, and cost-effectiveness. It is shown that material classes with promising emission properties are Ce³⁺- or Pr³⁺-doped materials, near band gap exciton emitters, plastics, and core–valence materials. Possible shortcomings of each of these groups, e.g., suboptimal emission wavelength, nonproportionality, and density, are discussed. Additionally, the engineering approach of quenching the scintillator emission, resulting in a targeted shortening of the decay time, and the possibility of codoping are explored. When selecting and/or engineering a material, it is important to consider not only the characteristics of the scintillator but also relevant SiPM properties, such as recharge time and photodetection efficiency.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"210 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Configuration Engineering of Plasmonic-Metal/Semiconductor Nanohybrids for Solar Fuel Production†","authors":"Tianyi Yang, Binbin Lu, Yong Zuo, Jianfeng Huang","doi":"10.1021/acs.chemmater.4c03170","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03170","url":null,"abstract":"Solar fuel production, which primarily focuses on harnessing solar energy to convert CO₂ into fuels or produce H₂ through water splitting, holds transformative potential for addressing global energy demands and environmental challenges. However, several obstacles still need to be overcome, particularly concerning the efficiency and scalability of solar fuel systems. Plasmonic-metal/semiconductor nanohybrids (PSNs) represent a cutting-edge class of photocatalysts designed to overcome current efficiency bottlenecks by merging the unique localized surface plasmon resonance (LSPR) properties of plasmonic metals with the catalytic efficiency of semiconductors, thereby enhancing the overall efficiency of light-driven solar-to-fuel conversion. Precise regulation of PSN structures is essential for guiding the extraction and flow of energy and charge carriers within the nanohybrids, which ultimately determines their photocatalytic performance. In this perspective, we aim to highlight the direct impact that the configuration of these nanohybrids has on the efficiency of solar fuel production through various triggered plasmonic energy transfer mechanisms. To this end, we begin with a brief introduction to the basic plasmonic effects and fundamental energy transfer mechanisms between plasmonic metals and semiconductors. We then provide representative examples of how PSNs with five categories of engineered configurations (namely, core–shell, yolk–shell, Janus/heterodimer/dumbbell, core–satellite, and other hierarchical structures) enhance solar fuel production through three primary mechanisms: plasmon-induced resonance energy transfer, light absorption/trapping, and hot electron injection. We conclude this Perspective by outlining the remaining challenges and research directions in this field.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"6 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tuning the Metal-Free Room Temperature Phosphorescence of Fluorene-Based Chromophores through Side-Group Molecular Engineering","authors":"Maxime Rémond, Hee Jung Kim, Yanghyun Auh, Kwang Keat Leong, Jinbo Kim, Hwandong Jang, Yongnam Ahn, Kiyoung Chang, Eunkyoung Kim","doi":"10.1021/acs.chemmater.4c03482","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03482","url":null,"abstract":"A series of bromofluorene-based metal-free dyes (<b>BrFX</b>) exhibiting room-temperature phosphorescence (<b>RTP</b>) were synthesized via a scalable two-step process in high yields from the linkage of 2-bromofluorene (<b>BrF</b>) through a ketone with different side group (<b>X</b>). Structural analysis of <b>BrFX</b> revealed that the ketone group was well conjugated with the fluorene group but less conjugated with the <b>X</b> side group. The nature of the <b>X</b> side group played a crucial role in fine-tuning emission maxima of <b>BrFX</b>. Moreover, incorporating aromatic side groups having low triplet energy effectively red-shifted RTP and increased its lifetime. Theoretical calculations using density functional theory revealed that the highest occupied molecular orbital was localized on the fluorene core, supporting these experimental observations. <b>BrFX</b> showed strong phosphorescence in diverse amorphous semiconducting hosts with quantum yields up to 65%, enabling their application in light-emitting electrochemical cells. These findings underscore the success of converting <b>BrFH</b> into its ketone analogs, <b>BrFX</b>, as an effective strategy to enhance both phosphorescence and electroluminescence, representing a notable advancement in <b>RTP</b> molecule design.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"49 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495904","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"First-Principles Statistical Mechanics Study of Magnetic Fluctuations and Order–Disorder in the Spinel LiNi0.5Mn1.5O4 Cathode","authors":"Graciela E. García Ponte, Sesha Sai Behara, Euan N. Bassey, Raphaële J. Clément, Anton Van der Ven","doi":"10.1021/acs.chemmater.4c02772","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02772","url":null,"abstract":"While significant magnetic interactions exist in lithium transition metal oxides, commonly used as Li-ion cathodes, the interplay between magnetic couplings, disorder, and redox processes remains poorly understood. In this work, we focus on the high-voltage spinel LiNi_0.5Mn_1.5O₄ (LNMO) cathode as a model system on which to apply a computational framework that uses first principles-based statistical mechanics methods to predict the finite temperature magnetic properties of materials and provide insights into the complex interplay between magnetic and chemical degrees of freedom. Density functional theory calculations on multiple distinct Ni–Mn orderings within the LNMO system, including the ordered ground-state structure (space group <i>P</i>4₃32), reveal a preference for a ferrimagnetic arrangement of the Ni and Mn sublattices due to strong antiferromagnetic superexchange interactions between neighboring Mn⁴⁺ and Ni²⁺ ions and ferromagnetic Mn–Mn and Ni–Ni couplings, as revealed by magnetic cluster expansions. These results are consistent with qualitative predictions using the Goodenough-Kanamori-Anderson rules. Simulations of the finite temperature magnetic properties of LNMO are conducted using Metropolis Monte Carlo. We find that a “semiclassical” Monte Carlo sampling method based on the Heisenberg Hamiltonian accurately predicts experimental magnetic transition temperatures observed in magnetometry measurements. This study highlights the importance of a robust computational toolkit that accurately captures the complex chemomagnetic interactions and predicts finite temperature magnetic behavior to help analyze experimental magnetic and magnetic resonance spectroscopy data acquired <i>ex situ</i> and <i>operando</i>.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"32 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486599","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chemistry of Materials Highlights Colloidal Semiconductor Nanocrystals","authors":"Paul D. Goring,&nbsp; and ,&nbsp;Sara E. Skrabalak*,&nbsp;","doi":"10.1021/acs.chemmater.5c0018310.1021/acs.chemmater.5c00183","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00183https://doi.org/10.1021/acs.chemmater.5c00183","url":null,"abstract":"","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 4","pages":"1335–1336 1335–1336"},"PeriodicalIF":7.2,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143478237","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Future of Colloidal Semiconductor Nanocrystals","authors":"Raffaella Buonsanti*,&nbsp; and ,&nbsp;Brandi Cossairt*,&nbsp;","doi":"10.1021/acs.chemmater.5c0002310.1021/acs.chemmater.5c00023","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00023https://doi.org/10.1021/acs.chemmater.5c00023","url":null,"abstract":"","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 4","pages":"1333–1334 1333–1334"},"PeriodicalIF":7.2,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143478249","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Future of Colloidal Semiconductor Nanocrystals","authors":"Raffaella Buonsanti, Brandi Cossairt","doi":"10.1021/acs.chemmater.5c00023","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00023","url":null,"abstract":"Figure 1. Pie chart showing the distribution of votes for various future applications of colloidal quantum dots based on a social media survey. This article has not yet been cited by other publications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"10 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chemistry of Materials Highlights Colloidal Semiconductor Nanocrystals","authors":"Paul D. Goring, Sara E. Skrabalak","doi":"10.1021/acs.chemmater.5c00183","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00183","url":null,"abstract":"Colloidal semiconductor nanocrystals have been hailed as the building blocks of next-generation nanotechnology. These solution-processed nanocrystals exhibit size-tunable optical and electronic properties, making them valuable for applications ranging from high-performance quantum dot displays to advanced biomedical imaging and even in photovoltaics. Their ability to bridge the gap between molecular chemistry and solid-state physics is central to such innovation, with the 2023 Nobel Prize in Chemistry recognizing the discovery and synthesis of quantum-confined colloidal semiconductor nanocrystals. Yet, as researchers push the frontiers of their potential, challenges persist that must be addressed to unlock their full potential in commercial and scientific pursuits. This Collection of recent papers on &lt;i&gt;Colloidal Semiconductor Nanocrystals&lt;/i&gt; from &lt;i&gt;Chemistry of Materials&lt;/i&gt; includes an invited editorial by Raffaella Buonsanti and Brandi Cossairt (DOI: 10.1021/acs.chemmater.5c00023), where they ask: What is next? This collection is built from their insight, with papers selected that emphasize (1) Mechanistic Insight and Synthetic Design, (2) Stability and the Nanocrystal Surface, (3) New Materials and the Use of Less Toxic Elements, and (4) Translation from Fundamental Science to Application. The synthetic design of colloidal semiconductor nanocrystals relies on precise control over nucleation and growth processes to achieve nanocrystals with uniform size, shape, and composition. This achievement provides nanocrystals with precisely tuned properties. Such nanocrystals are commonly prepared by the hot-injection method, with Kenis and co-workers (DOI: 10.1021/acs.chemmater.3c02751) providing insight into this method using an automated high-throughput experimental platform to collect a large experimental data set that could be used to train models for predicting synthetic outcomes using machine learning. This method focused on the widely studied CdSe system, which has also been advanced with the synthesis of CdSe-based heterostructures. These heterostructures include CdSe-Dot/CdS-Rod/PbS-Dot nanocrystals (DOI: 10.1021/acs.chemmater.4c02553) that are dual-emissive as well as CdSe/ZnSe Core/Shell and CdSe/ZnSe/ZnS Core/Shell/Shell nanocrystals (DOI: 10.1021/acs.chemmater.3c01333), where the latter quantum dots are green-emitting with a near-unity photoluminescence quantum yield. Heterostructured nanocrystals can be achieved through seeded methods as well as through chemical transformations, such as cation exchange, which in addition to producing the dual-emissive CdS-Rod system, was used to synthesize ZnSe-Dot/CdS-Rod nanocrystals (DOI: 10.1021/acs.chemmater.2c03278) as well as wurtzite InP nanocrystals (DOI: 10.1021/acs.chemmater.3c02226) from Cu&lt;sub&gt;3–&lt;i&gt;x&lt;/i&gt;&lt;/sub&gt;P nanocrystals. Mechanistic studies that reveal the intricacies of colloidal chemistry are central to achieving such structurally complex semiconductor nanocrystals, with advances also","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486601","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"HfO2 Area Selective Deposition via Substrate-Dependent Area Selective Atomic Layer Etching","authors":"Landon J. Keller, Seung Keun Song, Hannah R. M. Margavio, Sarah Atanasov, Jiun-Ruey Chen, Gregory N. Parsons","doi":"10.1021/acs.chemmater.4c03238","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03238","url":null,"abstract":"The development of new material–substrate systems and methods for area selective deposition (ASD) is vital to the manufacturing of next-generation microelectronics. Atomic layer deposition (ALD) and atomic layer etching (ALE) have been integrated to achieve ASD by reintroducing the initial nucleation delay during ALD on the surface, where no growth is desired, but many ALD processes show minimal nucleation delay on some materials. This work demonstrates the integration of HfO₂ thermal ALD (TDMAHf and H₂O) and thermal ALE (WF₆ and BCl₃) for HfO₂ ASD on Co/Si–H versus Ru/SiO₂ via the substrate-dependent film structuring and etching rate. At 275 °C, the quartz crystal microbalance shows the same growth rate on Co and Al₂O₃ during HfO₂ ALD, but significantly more HfO₂ is removed on Al₂O₃ than Co during HfO₂ ALE before etching stops on each surface. Ultrathin HfO₂ films deposited at 275 °C are amorphous on SiO₂ and partially structured on Co. After annealing at 600 °C, the ⟨−111⟩ monoclinic crystalline plane is observed in HfO₂ on SiO₂ and Co with additional orthorhombic and tetragonal crystalline planes observed on only Co. Spectroscopic ellipsometry and transmission electron microscopy show &gt;4 nm HfO₂ selectively grown via integrated ALD/ALE on metal versus dielectric without the use of organic nucleation inhibition. This work provides novel insights into chemical patterning of dielectric materials via integrated ALD/ALE and low-temperature control of structured materials for advanced atomic scale processing.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"65 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477678","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"End-To-End Learning of Classical Interatomic Potentials for Benchmarking Anion Polarization Effects in Lithium Polymer Electrolytes","authors":"Pablo A. Leon, Avni Singhal, Jurgis Ruza, Jeremiah A. Johnson, Yang Shao-Horn, Rafael Gomez-Bombarelli","doi":"10.1021/acs.chemmater.4c02529","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02529","url":null,"abstract":"Solid polymer electrolytes are an exciting solution for safe and stable solid lithium electrode battery systems but are hindered by low ionic conductivity and low lithium transference. All-atom molecular dynamics simulation has become an invaluable tool to probe lithium diffusion mechanisms and accelerate the discovery of promising polymer chemistries. Because of their low computational cost and despite their approximate nature, only classical interatomic potentials can access the time and length scales for appropriate statistics of polymer kinetics. Machine learning (ML) potentials trained end-to-end on ab initio data have proven more accurate but cannot be scaled to the necessary time- and length- scales yet. Historical approaches to parametrize classical force fields have been incremental, reliant on a manual combination of top-down and bottom-up fitting, and are often paywalled and hard to reproduce. We introduce a computational learning workflow to predict classical interatomic potential parameters using quantum mechanical computations as training data that combines the automation and end-to-end fitting of ML with traditional class 1 and class 2 functional forms. The fitting strategy produced potentials whose simulations improved the accuracy of lithium coordination environments, diffusivities, and conductivities relative to experimental approaches when compared to both naive and hand-tuned parameters for liquid and solid organic electrolyte systems. We show that chemistry-informed regularization is necessary to constrain predicted parameters in order to reproduce experimental solvation and kinetic properties. Finally, we explore the limitations of nonpolarizable, fixed point-charge schemes in describing electrolyte anions and compare the effects of two alternative schemes to fit point-charge distributions. The two strategies result in distinct lithium coordination mechanisms and highlight that closest parity to DFT forces and energies does not correlate to correct trends with lithium salt concentration in kinetic and solvation properties for fixed-point-charge classical interatomic potentials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"110 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}