Accounts of materials research最新文献

{"title":"Silver Sulfide Nanocrystals and Their Photodetector Applications","authors":"Jisu Kwon, Yoonbin Shin, Yunmo Sung, Hyunmi Doh, Sungjee Kim","doi":"10.1021/accountsmr.4c00109","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00109","url":null,"abstract":"Silver sulfide nanocrystals (Ag<sub>2</sub>S NCs) exhibit unique infrared (IR) absorption and emission capabilities, drawing great interest for their broad applicability. These NCs are considered environmentally friendly alternatives to heavy metals such as lead (Pb), mercury (Hg), and cadmium (Cd) chalcogenides. This Account provides a comprehensive overview based on our research on Ag<sub>2</sub>S NCs. We investigated their synthesis over size and shape, surface stoichiometry control, postsynthetic surface composition change, and optoelectronic application. The work began with developing a synthesis protocol for the Ag<sub>2</sub>S NCs. Size-tunable and nearly monodisperse NCs were obtained through the precise control of precursor ratio. The ability to manipulate the size of the NCs enabled us to explore and adjust their optical properties. Another important aspect of the research focused on the mechanism of shape transformation. The evolution of the NCs from their initial spherical structure to more complex shapes such as rods and cubes was observed. Through rigorous investigations using a transmission electron microscope (TEM), we studied the relationship between the morphological changes and crystal facets. Investigations were also extended to surface chemistry, where methods were developed to tune the surface stoichiometry of Ag<sub>2</sub>S NCs. Perfectly stoichiometric-surfaced Ag<sub>2</sub>S NCs synthesized through ion-pair ligand-assisted surface reactions exhibited significantly increased photoluminescence (PL) and an enhanced epitaxial ZnS growth rate. Finally, we explored the cation exchange reactions of Ag<sub>2</sub>S NCs. The cation exchange reaction with indium (In) ions yielded AgInS<sub>2</sub> NCs with size-dependent crystal structures: tetragonal for small NCs and orthorhombic for large NCs. A critical size at around 4.3 nm was observed, representing a trade-off between a thermodynamically more stable tetragonal structure and an orthorhombic structure that preserves the anionic framework. Throughout this Account, we address the challenges for the application of Ag<sub>2</sub>S NCs and propose future directions including advancements in synthesis techniques, surface chemistry, and their applications. Ag<sub>2</sub>S NCs typically show limitations such as low chemical and electrical stability, which may originate from the low lattice energy and high concentration of cation vacancies. However, such unique features can be advantageous for some applications, for example, acceptor materials in photomultiplication (PM)-type photodiodes. PM-type photodiodes were developed by combining polymeric semiconductors and Ag<sub>2</sub>S NCs. These photodiodes can amplify signals by trapping electrons within Ag<sub>2</sub>S NCs. These NCs efficiently trap multiple charge carriers from donor materials, in which their typical disadvantage is reinterpreted as a beneficial attribute for advanced device applications. In order to enhance the elect","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"100 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142101859","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Silver Sulfide Nanocrystals and Their Photodetector Applications","authors":"Jisu Kwon, Yoonbin Shin, Yunmo Sung, Hyunmi Doh and Sungjee Kim*, ","doi":"10.1021/accountsmr.4c0010910.1021/accountsmr.4c00109","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00109https://doi.org/10.1021/accountsmr.4c00109","url":null,"abstract":"<p >Silver sulfide nanocrystals (Ag<sub>2</sub>S NCs) exhibit unique infrared (IR) absorption and emission capabilities, drawing great interest for their broad applicability. These NCs are considered environmentally friendly alternatives to heavy metals such as lead (Pb), mercury (Hg), and cadmium (Cd) chalcogenides. This Account provides a comprehensive overview based on our research on Ag<sub>2</sub>S NCs. We investigated their synthesis over size and shape, surface stoichiometry control, postsynthetic surface composition change, and optoelectronic application. The work began with developing a synthesis protocol for the Ag<sub>2</sub>S NCs. Size-tunable and nearly monodisperse NCs were obtained through the precise control of precursor ratio. The ability to manipulate the size of the NCs enabled us to explore and adjust their optical properties. Another important aspect of the research focused on the mechanism of shape transformation. The evolution of the NCs from their initial spherical structure to more complex shapes such as rods and cubes was observed. Through rigorous investigations using a transmission electron microscope (TEM), we studied the relationship between the morphological changes and crystal facets. Investigations were also extended to surface chemistry, where methods were developed to tune the surface stoichiometry of Ag<sub>2</sub>S NCs. Perfectly stoichiometric-surfaced Ag<sub>2</sub>S NCs synthesized through ion-pair ligand-assisted surface reactions exhibited significantly increased photoluminescence (PL) and an enhanced epitaxial ZnS growth rate. Finally, we explored the cation exchange reactions of Ag<sub>2</sub>S NCs. The cation exchange reaction with indium (In) ions yielded AgInS<sub>2</sub> NCs with size-dependent crystal structures: tetragonal for small NCs and orthorhombic for large NCs. A critical size at around 4.3 nm was observed, representing a trade-off between a thermodynamically more stable tetragonal structure and an orthorhombic structure that preserves the anionic framework. Throughout this Account, we address the challenges for the application of Ag<sub>2</sub>S NCs and propose future directions including advancements in synthesis techniques, surface chemistry, and their applications. Ag<sub>2</sub>S NCs typically show limitations such as low chemical and electrical stability, which may originate from the low lattice energy and high concentration of cation vacancies. However, such unique features can be advantageous for some applications, for example, acceptor materials in photomultiplication (PM)-type photodiodes. PM-type photodiodes were developed by combining polymeric semiconductors and Ag<sub>2</sub>S NCs. These photodiodes can amplify signals by trapping electrons within Ag<sub>2</sub>S NCs. These NCs efficiently trap multiple charge carriers from donor materials, in which their typical disadvantage is reinterpreted as a beneficial attribute for advanced device applications. In order to enhance the","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 9","pages":"1097–1108 1097–1108"},"PeriodicalIF":14.0,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142326277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Top-Down Fabrication of Chemical and Biological Sensors","authors":"Hohyung Kang, Ahyeon Cho, Seongcheol Park, Soo-Yeon Cho, Hee-Tae Jung","doi":"10.1021/accountsmr.4c00170","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00170","url":null,"abstract":"Fabrication of complex three-dimensional (3D) structures with micro/nanoscale dimensions is crucial for high-performing chemical and biological sensor applications. It not only enables the accurate detection and tracking of minuscule chemical and biological analytes but also determines the commercial viability and practical utilization of the sensors in future intricate applications. Among various structure fabrication approaches, top-down lithography provides invaluable tools for fabricating complex 3D micro/nanoscale structures in sensors, enabling the sensitive and selective detection of low concentration chemical and biological analytes. Moreover, it preserves the inherent advantages of top-down lithography as the sensor attributes, including (i) high-resolution and tight pitch 3D structures in long-range order, (ii) varied pattern shapes, dimensions, and densities, (iii) low device-to-device variation, (iv) high integrated circuit yield, (v) acceptable process cost and processability, and (vi) the ability to accommodate a wide range of materials. Given the variety of top-down lithographic methods available for fabricating sensors and the complex requirements of the sensor such as diverse target analytes, varying concentration levels, and different sensing environments, it is essential to have a comprehensive understanding of the technical nuances associated with each top-down lithography technique and its applications. However, there is a significant gap in the literature regarding targeted evaluations of top-down lithography methods for high-performance chemical and biological sensor fabrication as well as a clear articulation of sensor design rules.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"16 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142178207","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Porous Crystalline Frameworks as Ion-Conducting Solid-State Electrolytes","authors":"Hongwei Chen, Chenji Hu, Xiaoqing Zhang, Liwei Chen","doi":"10.1021/accountsmr.4c00156","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00156","url":null,"abstract":"Room-temperature Li⁺ conductors have been intensively revisited to develop high-safety solid-state batteries. While promising inorganic Li⁺ solid-state electrolytes (SSEs) with competitive ionic conductivity have been demonstrated, their practical applications are still hindered by manufacturing technology, cost constraints, and internal battery interfaces. Advances in the design and synthesis of periodic frameworks over the past decade have created a new platform for designing SSEs. These porous crystalline frameworks feature open channels that can be tailored into ion-hopping sites and guest-accessible voids, both essential for SSE construction. Framework-based SSEs uniquely merge the advantages of inorganic crystal-like ordered structures and the design flexibility of organic molecules, distinguishing them significantly from traditional inorganic or organic SSEs. Enhancing ionic conduction and exploring potential applications are two critical factors driving the rapid advancement of framework-based SSEs.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"4 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142178232","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Functional Covalent Organic Frameworks: Design Principles to Potential Applications","authors":"Yusran Yusran, Bo Miao, Shilun Qiu, Qianrong Fang","doi":"10.1021/accountsmr.4c00195","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00195","url":null,"abstract":"Covalent organic frameworks (COFs) represent an emerging class of crystalline porous polymers synthesized by linking predesigned organic building units into targeted repetitive networks. The unique features of COFs stem from their modular synthesis, allowing for precise control over the chemical composition and functionalization on both the skeleton and the pore walls. Topologically, COFs are defined not by their chemical nature but by the symmetry and dimensions of the building units, resulting in 2D and 3D structures with distinct surface areas, pore architectures, and arrangements of functional moieties. The combination of predesigned organic units into geometries results in frameworks that can be precisely controlled and modified. This control is vital for applications requiring materials with specific pore sizes, surface areas, and functional group distributions. Particularly, COFs show great potential in the field of gas storage and separation, energy storage and conversion, catalysis, sensing, environmental remediation, and many more. Hence, an effective designed approach to incorporate various functional properties into the structures is pivotal to manipulate the functional properties and potential applications of COFs.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"25 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142178234","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrically Stable Self-Assembled Monolayers Achieved through Repeated Surface Exchange of Molecules","authors":"Jiung Jang, Gyu Don Kong, Hyo Jae Yoon","doi":"10.1021/accountsmr.4c00190","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00190","url":null,"abstract":"Self-assembled monolayers (SAMs) are two-dimensional molecular ensembles. In molecular electronics, SAMs serve as active components for exploring structure-tunneling relationships due to their easy and simple fabrication and atomic-detailed (supra)molecular modifications. Single-component pure SAMs are commonly incorporated into tunneling junctions. However, pure SAMs are defective to some extent, which results in low electrical breakdown voltages and allows access to narrow bias windows through the junctions. Narrow bias windows ultimately limit the possible charge-transport channels to shallow molecular orbital energy levels such as the highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO), making it difficult to investigate charge transport through deeper molecular orbital (MO) energy levels such as sub-HOMOs and post-LUMOs.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"50 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142043308","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Component Engineering in Multinary Alloyed I-III-VI Type Semiconductor Nanocrystals for Photoluminescence and Electroluminescence","authors":"Lijin Wang, Zhe Yin, Aiwei Tang","doi":"10.1021/accountsmr.4c00161","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00161","url":null,"abstract":"Display technologies have been developed in an unprecedented way in the past one hundred years. The evolution of display technologies is remarkable, progressing from the initial cathode ray tube and rear projection technology to the second-generation advancements of plasma and liquid crystal displays. Now, with the ongoing development of light-emitting diodes (LEDs) technology, including organic LEDs (OLEDs) and quantum dot LEDs (QD-LEDs), we are looking forward to a transition toward mini-LED, micro-LED, and nano-LED technologies. This evolution is gradually rendering displays thinner, more convenient, high-definition, highly luminous, and cost-effective. At present, commercially available OLEDs technology is afflicted with drawbacks such as intricate solution processing, difficulties in achieving efficient mass production, and suboptimal stability, limiting its widespread adoption. QD-LEDs serve as a perfect complement to the limitations of OLEDs and demonstrate a large potential for application in the next generation of displays. Quantum dots (QDs) are nanocrystals (NCs) with a size of 1–10 nm. Since the 1980s, researchers have studied and developed these magic tiny particles. At present, Cd-based materials have been extensively studied, resulting in red-, green-, and blue-LEDs devices approaching or surpassing theoretical external quantum efficiency limits. And the lifetime of Cd-based LEDs has reached commercial standards expected for blue-LEDs. However, the intrinsic toxicity of Cd element limits their further development. In the past decades, several Cd-free QDs have been developed and extensively researched, including III-V type InP QDs, perovskite QDs, I-III-VI type QDs, II-VI type ZnSe QDs, carbon dots, and so on. Among these Cd-free QDs, I-III-VI type semiconductor nanocrystals demonstrate remarkable potential due to facile synthesis, large tunable luminescence range, and solution processability. Moreover, owing to its distinctive nonstoichiometric composition, the luminescence peak position can be readily tuned from the blue to near-infrared by means of straightforward component engineering. This Account presents an overview of the I-III-VI type NCs, starting with the photoluminescent properties regulated by component engineering. Interestingly, narrow-band emission can also be realized through component engineering. Then the construction of light-emitting diodes based on these materials is discussed, encompassing wide-band and narrow-band emission. Additionally, interface engineering is adopted for balancing carrier injection to enhance electroluminescent properties. Moreover, taking advantage of the wide-band emission characteristics of I-III-VI type NCs, white LEDs with high color rendering index can be fabricated by incorporating other blue-emitting materials. Finally, the present challenges and prospective solutions are proposed to propel the advancement of I-III-VI type NCs with high expectations.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"37 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142013983","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chemical Mechanisms and Biological Effects of Chiral Nanomaterials","authors":"Gaoyang Wang, Aihua Qu, Maozhong Sun, Jun Xu, Hua Kuang","doi":"10.1021/accountsmr.4c00158","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00158","url":null,"abstract":"Chirality exerts significant roles in biological systems and physiological processes; amino acids, sugars, peptides with multilevel structures, macromolecular proteins, and nucleic acids are all known to exhibit a single chiral structure. The characteristics of intrinsic chirality in a biological system determine the specificity of interactions between biomolecules and also influence a series of key processes in biological systems. Consequently, investigating chirality and the biogenesis of life is critical if we are to understand how the human body works. Although the influential role of chiral materials on biological processes has been investigated for several decades, the specific relationships between chirality and biological functionality have yet to be determined. In order to elucidate the specific role played by chirality in living processes, researchers have tended to focus on three essential aspects: (1) the origin of chirality and breaking the symmetry of life; (2) the amplification of chirality and the realization of high levels of homogeneous chirality in living systems, and (3) chirality transfer mechanisms in <i>vivo</i>.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"31 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141992067","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Heterogeneous Integration of Diamond","authors":"Oliver A. Williams, Soumen Mandal, Jerome A. Cuenca","doi":"10.1021/accountsmr.4c00126","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00126","url":null,"abstract":"The heterogeneous integration of materials offers new paradigms in many extreme applications, where single materials cannot solve the problem alone. Diamond has a plethora of superlative properties that make it attractive in a diverse array of applications, such as its unique combination of unrivalled thermal conductivity combined with high electrical impedance; single photon emission at room temperature; superlative acoustic wave velocity, and Debye temperature. Most of these properties are directly related to diamond’s atomically dense lattice of light carbon atoms, which has consequences such as difficulty in doping diamond n-type and low thermal coefficient of thermal expansion. This last property presents a significant problem for the growth of diamond on nondiamond materials as the linear coefficients of thermal expansion of other materials are often several times larger than diamond.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"4 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141994703","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Diamond Homoepitaxial Growth Technology toward Wafer Fabrication, Atomically Controlled Surfaces, and Low Resistivity","authors":"Kimiyoshi Ichikawa, Tsubasa Matsumoto, Takao Inokuma, Satoshi Yamasaki, Christoph E. Nebel, Norio Tokuda","doi":"10.1021/accountsmr.4c00123","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00123","url":null,"abstract":"Strong covalent bonds provide diamond with superior properties such as higher thermal conductivity, electron/hole mobilities, and wider bandgap than those of other semiconductors. This makes diamonds promising for next-generation power devices, optoelectronics, quantum technologies, and sensors. However, there are still challenges in realizing practical diamond electronic applications. Key issues include controlling the microwave plasma chemical vapor deposition (MPCVD) growth process to achieve a large size, smooth surfaces, and desired conductivity. Standard semiconductor processing techniques like polishing and ion implantation also need improvement for diamonds. This Account outlines three MPCVD growth technologies being investigated at Kanazawa University to address these challenges.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"26 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141986683","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}