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Crystal Chemical Parameters for the Eu(II) Luminescence in Solid-State Metal Hydrides 固态金属氢化物中 Eu(II) 发光的晶体化学参数
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-11-12 DOI: 10.1021/acs.chemmater.4c02148
Arjun Nain, Lukas Millahn, Markus Gebauer, Linda Schmidt, Holger Kohlmann
Metal hydrides are interesting hosts for activator ions, as they provide opportunities for the tuning of emission wavelengths in luminescent materials. The strong nephelauxetic effect of the hydride ion lowers the barycenter of the d levels and thus also the energy difference from the electronic ground state. General rules on this influence are lacking, however, due to the multitude of variables. Alkaline earth metal hydride halogenides MHX (M = Ca, Sr, Ba; X = Cl, Br, I) are ideally suited for examining the influence of crystal chemical parameters on luminescence properties because they crystallize isotypically in the tetragonal PbFCl type, a relatively simple crystal structure. MHX and Eu(II)-activated samples M0.99Eu0.01HX were synthesized by solid-state reactions and structurally characterized by X-ray and neutron powder diffraction, providing evidence of hydrogen positions. Refined crystal structure data for all nine compounds allow for elucidation of detailed crystal chemical systematics. From BaHCl to CaHI, the coordination of the cations changes from nine to eight, the crystal structure acquires a more pronounced layer character, and the bonding properties show a decreasing ionicity. These changes are also reflected in the luminescence spectra. For a given M, increasing the size of X has almost no influence on M–H distances but increases the emission wavelength considerably. The increasing nephelauxetic effect of halogen X is the most likely cause. Increasing the size of M for a constant X moderately increases M–H distances but strongly decreases the emission wavelength. Eu(II) luminescence in metal hydrides thus seems to be dominated by the M–H distances. The nephelauxetic effect of the halogen atoms is a secondary effect. Combining these effects with partial substitution of fluorine for hydrogen or one M for another offers ample opportunities for fine-tuning the luminescence properties of Eu(II) in metal hydride host compounds.
金属氢化物是活化剂离子的有趣宿主,因为它们为调整发光材料的发射波长提供了机会。氢化物离子的强新负电效应降低了 d 级的原心,从而也降低了与电子基态的能量差。然而,由于变量众多,目前还没有关于这种影响的一般规则。碱土金属氢化物卤化物 MHX(M = Ca、Sr、Ba;X = Cl、Br、I)非常适合研究晶体化学参数对发光特性的影响,因为它们的结晶类型为四方 PbFCl 型,晶体结构相对简单。通过固态反应合成了 MHX 和 Eu(II)-activated 样品 M0.99Eu0.01HX,并通过 X 射线和中子粉末衍射进行了结构表征,提供了氢位置的证据。所有九种化合物的精制晶体结构数据有助于阐明详细的晶体化学系统学。从 BaHCl 到 CaHI,阳离子的配位从 9 个变为 8 个,晶体结构具有更明显的层状特征,键合性质显示出离子性的下降。这些变化也反映在发光光谱中。对于给定的 M,X 的增大对 M-H 间距几乎没有影响,但会大大增加发射波长。最可能的原因是卤素 X 的霓虹灯效应不断增强。在 X 不变的情况下,增大 M 的大小会适度地增加 M-H 间距,但会强烈地减小发射波长。因此,Eu(II)在金属氢化物中的发光似乎主要受 M-H 间距的影响。卤素原子的氖光效应是次要效应。将这些效应与部分氟取代氢或一种 M 取代另一种 M 结合起来,为微调 Eu(II) 在金属氢化物宿主化合物中的发光特性提供了大量机会。
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引用次数: 0
Unveiling the Local Strain-Induced Structural Degradation Mechanisms in Li Excess Manganese Cathodes 揭示锂过量锰阴极中局部应变诱导的结构退化机制
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-11-11 DOI: 10.1021/acs.chemmater.4c01879
Mu Geun Son, Hyeonji Shin, Hoje Chun, Joonhee Kang
With the growing demand for high-capacity rechargeable batteries, continuous advancements in cathode materials are imperative. Among the candidate materials, Li-excess Mn-rich (LMR) cathodes, known for their superior capacity compared to traditional cathodes, are gaining attention for commercialization. However, Li2MnO3, predominantly used in LMR cathodes, undergoes structural degradation in the voltage plateau region, and its atomic-level mechanisms have not yet been precisely elucidated. Herein, we use first-principles density functional theory calculations to investigate the process of structural change and redox mechanisms of Li2MnO3 induced by local strain. Our studies suggest that local intrinsic strain significantly influences changes in redox mechanisms, Mn migration, and the formation of O–O dimers. Furthermore, the process of structural collapse due to strain was further confirmed through ab initio molecular dynamics calculations. As a final step, we observed the collapse process until all of the Li ions were completely removed from the structure. Our results, considering the effects of local strain, integrate existing degradation mechanisms of Li2MnO3 and provide advanced understanding and new insights for its improvement.
随着对高容量充电电池的需求日益增长,阴极材料的不断进步势在必行。在候选材料中,富含锰的锂离子(LMR)阴极以其优于传统阴极的容量而闻名,其商业化前景日益受到关注。然而,主要用于 LMR 阴极的 Li2MnO3 在电压高原区会发生结构退化,其原子级机制尚未得到精确阐明。在此,我们利用第一原理密度泛函理论计算研究了局部应变诱导的 Li2MnO3 结构变化过程和氧化还原机制。我们的研究表明,局部固有应变对氧化还原机制的变化、锰迁移和 O-O 二聚体的形成有显著影响。此外,应变导致的结构坍塌过程通过原子分子动力学计算得到了进一步证实。最后,我们观察了塌缩过程,直到所有的锂离子完全从结构中移除。考虑到局部应变的影响,我们的研究结果整合了 Li2MnO3 现有的降解机制,为改进其性能提供了先进的理解和新的见解。
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引用次数: 0
Deciphering NonCubic Phases in Au Microcrystallites via Under Potential Cu Deposition and Selective Growth of Noble Metal and Sulfide Overlayers 通过欠电位铜沉积和贵金属与硫化物覆盖层的选择性生长,解密金微晶中的非立方相
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-11-11 DOI: 10.1021/acs.chemmater.4c01821
Chaitali Sow, Gangaiah Mettela, Suchithra Puliyassery, Giridhar U. Kulkarni
Identification of the crystal phase domain in a given crystallite requires high-resolution electron microscopy and selected area diffraction techniques. However, it is an immense challenge to prepare the samples and identify the polymorphic domains in a crystallite, specifically when the size of the domains is in the μm regime. Here, the well-known Cu electroless process has been used to map the fcc lattice domains from a group of mixed phases in Au crystallites. The Cu growth was selective on the fcc domains, while the noncubic lattice regions (i.e., body-centered orthorhombic and body-centered tetragonal, together called bc(o,t) lattices) remained free of Cu. In spite of the similar lattice mismatches, the Cu deposition is mainly governed by the isotropic geometry of the fcc surfaces, irrespective of the crystal morphology. The obtained Au–Cu structures have served as seeds to grow bimetals (Au–Ag, Au–Pd, and Au–Pt) and metal–semiconductors/heterostructures (Au–CuS and Au–Cu2O) with anisotropic geometry.
要识别给定晶粒中的晶体相域,需要使用高分辨率电子显微镜和选区衍射技术。然而,如何制备样品并识别晶粒中的多态晶域是一项巨大的挑战,特别是当晶域的尺寸达到微米级时。在这里,著名的无电解铜工艺被用来绘制金晶粒中一组混合相的 fcc 晶格畴。铜的生长选择性地作用于 fcc 晶域,而非立方晶格区域(即体中心正方晶格和体中心四方晶格,合称 bc(o,t) 晶格)则不含铜。尽管存在类似的晶格错配,但无论晶体形态如何,铜的沉积主要受 fcc 表面各向同性几何结构的影响。所获得的金-铜结构可作为生长双金属(金-银、金-钯和金-铂)和具有各向异性几何形状的金属半导体/异质结构(金-铜氧化物和金-铜氧化物)的种子。
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引用次数: 0
Enhanced C(sp3)–H Selective Oxidation Using Efficient Polyoxometalate-Based Metal–Organic Framework Photocatalysts Synergized with Ir Metalloligands and Polyoxometalates 使用与 Ir 金属配体和聚氧化金属酸盐协同作用的高效聚氧化金属酸盐基金属有机框架光催化剂增强 C(sp3)-H 选择性氧化作用
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-11-09 DOI: 10.1021/acs.chemmater.4c02040
Jing Wang, Luoning Li, Yanan Liu, Zelong Yuan, Pengtao Ma, Jingping Wang, Jingyang Niu
Achieving efficient selective visible light-induced oxidation of benzyl C(sp3)–H to more valuable double-bonded compounds holds significant promise for organic synthesis. In this work, we fabricated an example of Ir metalloligand-modified POMOF crystalline material, CI-SiW, which is noteworthy as the first example of POM immobilized in a metalloligand-modified MOF via coordination bonding. Under the excitation of visible light (10 W, λ = 410 nm), CI-SiW can catalyze the efficient oxidation of benzyl C(sp3)–H of isochromane with a turnover number and turnover frequency of 954 and 1740 h–1, respectively. Excitingly, CI-SiW displays the best TOF compared with previous photocatalysts under the same conditions, realizing the maximum yield with the minimum amount of photocatalyst. Furthermore, CI-SiW had good cyclic and structural stability, and a 90.4% yield was still obtained after three reaction cycles.
实现可见光诱导的苄基 C(sp3)-H 高效选择性氧化为更有价值的双键化合物,为有机合成带来了巨大前景。在这项工作中,我们制备了一种Ir金属配体修饰的POMOF晶体材料CI-SiW,这是第一个通过配位键将POM固定在金属配体修饰的MOF中的实例。在可见光(10 W,λ = 410 nm)的激发下,CI-SiW 可催化异铬烷的苄基 C(sp3)-H 高效氧化,其周转次数和周转频率分别为 954 和 1740 h-1。令人兴奋的是,在相同条件下,CI-SiW 与之前的光催化剂相比显示出最佳的 TOF,以最少的光催化剂用量实现了最大的产率。此外,CI-SiW 还具有良好的循环稳定性和结构稳定性,在三个反应循环后仍能获得 90.4% 的产率。
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引用次数: 0
Phosphonium Cation-Based Ferroelectric 1D Halide Perovskite-Like Semiconductor for Mechanical Energy Harvesting 基于鏻阳离子的铁电 1D 卤化物类 Perovskite 半导体用于机械能收集
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-11-09 DOI: 10.1021/acs.chemmater.4c01446
Prabhanjan Pradhan, Prabhat Kumar, Ravi Kumar Bandaru, Rambabu Dandela, Rupak Banerjee, Biplab K. Patra
Organic–inorganic halide perovskites (OIHPs) have attracted tremendous attention from researchers because of their diverse applications in optoelectronics, sensing, catalysis, memory, photodetectors, and medical diagnostics. The presence of inherent ferroelectricity in these perovskite materials facilitates the separation of photogenerated electron–hole pairs. Here, we report a large phosphonium cation-based methyl triphenyl phosphonium lead bromide (MTPLB) perovskite-like semiconductor with a direct band gap of 3.49 eV, which shows ferroelectricity in both nanoscale and bulk at room temperature. The material exhibits a phase transition temperature of 477 K, a polarization saturation of 0.26 μC/cm2, and a d33 of 5.2 pC/N. MTPLB displays a robust piezoelectric response, as confirmed via advanced piezoresponse force microscopy (PFM). Further, we have fabricated nanogenerator devices with varying ratios of MTPLB and poly(vinylidene fluoride) (PVDF) composites for mechanical and biomechanical energy harvesting. We report an enhanced piezoresponse in all devices with the best response in the device with a 2% MTPLB loading in the PVDF matrix due to the triggering of the electroactive phases in PVDF. The improved output response, operational durability, and flexibility of the composite-based devices underscore their potential for advanced technological applications in electronics, actuators, sensors, and mechanical energy-harvesting processes.
有机-无机卤化物包晶(OIHPs)因其在光电、传感、催化、记忆、光电探测器和医疗诊断等领域的广泛应用而引起了研究人员的极大关注。这些包晶材料固有的铁电性有利于光生电子-空穴对的分离。在此,我们报告了一种基于大型鏻阳离子的甲基三苯基溴化鏻铅(MTPLB)类包晶半导体,其直接带隙为 3.49 eV,在室温下具有纳米级和块体铁电性。这种材料的相变温度为 477 K,极化饱和度为 0.26 μC/cm2,d33 为 5.2 pC/N。先进的压电响应力显微镜(PFM)证实,MTPLB 具有强大的压电响应。此外,我们还利用不同比例的 MTPLB 和聚(偏二氟乙烯)(PVDF)复合材料制作了纳米发电机装置,用于机械和生物机械能采集。我们的报告显示,由于聚偏二氟乙烯(PVDF)中电活性相的触发作用,所有装置的压电响应都得到了增强,其中 PVDF 基体中 MTPLB 含量为 2% 的装置响应最佳。这种基于复合材料的器件在输出响应、运行耐久性和灵活性方面都有所改进,凸显了其在电子、致动器、传感器和机械能量收集工艺等先进技术应用领域的潜力。
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引用次数: 0
Discerning Thermal Transition Behavior of Conjugated Polymers through In Situ Optical Characterization of Oriented Films 通过取向薄膜的原位光学表征辨别共轭聚合物的热转变行为
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-11-08 DOI: 10.1021/acs.chemmater.4c02003
Harry M. Schrickx, Caleb Moore, Abdullah Al Shafe, Alireza Samadani, Nrup Balar, Doan Vu, Jeromy J. Rech, Wei You, Brendan T. O’Connor
The thermomechanical properties of conjugated polymers (CPs) play a crucial role in device morphological, mechanical, and thermal stability and influence device processing parameters. However, the thermal transition behavior of CPs can be difficult to characterize, particularly as the molecular complexity increases. Here, we introduce a characterization technique that is an effective and sensitive approach to observing and defining thermal transitions in CPs. Our approach combines strain alignment with in situ polarized ultraviolet–visible absorption spectroscopy, which we name AFIPS. By monitoring changes in the absorption spectra and dichroism, we demonstrate the ability to effectively identify and characterize thermal transitions undetected using calorimetry. We use this in situ characterization method along with dynamic mechanical analysis (DMA) to probe the thermal transitions of various CPs, including F8T2, P3HT, PCDTBT, PTB7-Th, PM6, and PBnDT-FTAZ. We show that the measurement has a unique response to glass transitions (Tg), cold crystallization (Tcc), liquid crystal transitions, and melting. In this investigation, we uncover signatures of a Tg in PTB7-Th and a Tcc in PCDTBT. Using the AFIPS technique complements other thermomechanical measurements, such as DMA, while being simple and effective to implement, providing a valuable tool for polymer thin film characterization.
共轭聚合物 (CP) 的热机械性能在器件形态、机械和热稳定性方面起着至关重要的作用,并影响着器件的加工参数。然而,共轭聚合物的热转变行为很难表征,尤其是随着分子复杂性的增加。在此,我们介绍一种表征技术,它是观察和定义 CP 热转变的一种有效而灵敏的方法。我们的方法将应变配准与原位偏振紫外可见吸收光谱相结合,并将其命名为 AFIPS。通过监测吸收光谱和二色性的变化,我们展示了有效识别和表征量热法检测不到的热跃迁的能力。我们将这种原位表征方法与动态力学分析 (DMA) 结合使用,探测了各种 CP 的热跃迁,包括 F8T2、P3HT、PCDTBT、PTB7-Th、PM6 和 PBnDT-FTAZ。我们发现该测量方法对玻璃态转变(Tg)、冷结晶(Tcc)、液晶转变和熔化具有独特的响应。在这项研究中,我们发现了 PTB7-Th 的 Tg 和 PCDTBT 的 Tcc。使用 AFIPS 技术是对 DMA 等其他热力学测量方法的补充,而且简单有效,是聚合物薄膜表征的重要工具。
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引用次数: 0
Superconductor Discovery in the Emerging Paradigm of Materials Informatics 在材料信息学的新兴范式中发现超导体
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-11-08 DOI: 10.1021/acs.chemmater.4c01757
Huan Tran, Hieu-Chi Dam, Christopher Kuenneth, Vu Ngoc Tuoc, Hiori Kino
The past two decades have witnessed a tremendous number of computational predictions of hydride-based (phonon-mediated) superconductors, mostly at extremely high pressures, i.e., hundreds of gigapascals. These discoveries were strongly driven by Migdal–Éliashberg theory (and its first-principles computational implementations) for electron–phonon interactions, the key concept of phonon-mediated superconductivity. Dozens of predictions were experimentally synthesized and characterized, triggering not only enormous excitement in the community but also some debates. In this work, we review the computationally driven discoveries and the recent developments in the field from various essential aspects, including the theoretically based, computationally based, and, specifically, artificial intelligence/machine learning (AI/ML)-based approaches emerging within the paradigm of materials informatics. While challenges and critical gaps can be found in all of these approaches, AI/ML efforts specifically remain in their infancy for good reasons. However, there are opportunities in which these approaches can be further developed and integrated in concerted efforts, in which AI/ML approaches could play more important roles.
在过去的二十年里,对基于水化物(声子介导)的超导体进行了大量的计算预测,这些超导体大多处于极高的压力下,即数百千兆帕斯卡。这些发现是由米格达尔-埃利亚什伯格理论(及其第一原理计算实现)对电子-声子相互作用(声子介导超导的关键概念)的有力推动。数十项预言在实验中得到了综合和表征,不仅在学术界引起了巨大反响,也引发了一些争论。在这项工作中,我们从多个基本方面回顾了计算驱动的发现和该领域的最新发展,包括材料信息学范式中出现的基于理论、基于计算,特别是基于人工智能/机器学习(AI/ML)的方法。虽然所有这些方法都存在挑战和关键差距,但人工智能/机器学习方法仍处于起步阶段,这是有充分理由的。不过,这些方法还有进一步发展和整合的机会,人工智能/ML 方法可以在其中发挥更重要的作用。
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引用次数: 0
New Energetic Dodecahydro-closo-Dodecaborates (N2H5)4X2[B12H12] (X = Cl and Br) with a Novel Hexagonal A4B2C Tunnel Structure 具有新型六角 A4B2C 隧道结构的新型高能十二氢共十二硼酸盐 (N2H5)4X2[B12H12] (X = Cl 和 Br)
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-11-07 DOI: 10.1021/acs.chemmater.4c02058
Rouzbeh Aghaei Hakkak, Thomas Schleid
Two new tetrahydrazinium dihalide dodecahydro-closo-dodecaborates (N2H5)4X2[B12H12] (X = Cl and Br) were successfully synthesized via the direct reaction of dihydrazinium dodecahydro-closo-dodecaborate (N2H4)2[B12H12] with hydrazinium halides (N2H5)Cl and (N2H5)Br in aqueous media. The resulting isotypic compounds crystallize monoclinically in the space group P21/c with similar unit-cell parameters (a = 681.98(4) pm, b = 1025.38(6) pm, c = 1325.38(8) pm, and β = 98.393(3)° for the chloride and a = 686.05(4) pm, b = 1032.51(6) pm, c = 1316.04(8), and β = 97.449(3)° for the bromide). Their crystal structure was elucidated using single-crystal X-ray diffraction techniques, unveiling a new unique arrangement for the composition A4B2C (A = hydrazinium, B = halide, and C = dodecahydro-closo-dodecaborate). This distinctive structural configuration sets it apart from compounds exhibiting other A4B2C arrangements, such as the spinel or double-perovskite structure type. In this new structure, the halide anions are coordinated by five hydrazinium cations, creating triangular bipyramidal polyhedra. These are interconnected via edge- and corner-sharing, resulting in the formation of hexagonal tunnels along the [100] direction. Within each of these tunnels, the [B12H12]2– clusters reside centrally located. Differential scanning calorimetry analyses demonstrate that these compounds contain a substantial amount of energy that is released during their thermal decomposition.
在水介质中,通过十二氢-氯-十二硼酸二肼(N2H4)2[B12H12]与卤化肼(N2H5)Cl 和(N2H5)Br 的直接反应,成功合成了两种新的四肼二卤化物(N2H5)4X2[B12H12](X- = Cl- 和 Br-)。生成的同型化合物在空间群 P21/c 中单斜结晶,具有相似的单胞参数(氯化物为 a = 681.98(4) pm、b = 1025.38(6) pm、c = 1325.38(8) pm 和 β = 98.393(3)°;溴化物为 a = 686.05(4) pm、b = 1032.51(6) pm、c = 1316.04(8) 和 β = 97.449(3)°)。利用单晶 X 射线衍射技术阐明了它们的晶体结构,揭示了 A4B2C(A = 肼,B = 卤化物,C = 十二氢-氯索-十二硼酸酯)组成的新的独特排列方式。这种独特的结构构造使其有别于其他 A4B2C 排列的化合物,如尖晶石或双过沸石结构类型。在这种新结构中,卤化阴离子由五个肼阳离子配位,形成三角形双锥多面体。这些多面体通过边角共享相互连接,从而沿着[100]方向形成六边形隧道。在每个隧道中,[B12H12]2- 团簇都位于中心位置。差示扫描量热分析表明,这些化合物在热分解过程中释放出大量能量。
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引用次数: 0
Atomic Regulation of Metal–Organic Framework Thin Film for Low-k Dielectric 用于低介电常数的金属有机框架薄膜的原子调控
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-11-07 DOI: 10.1021/acs.chemmater.4c02057
Meng Cao, Jisheng Song, Haonan Ren, Fan Yang, Rong Chen
With the development of integrated circuit miniaturization, the RC delay caused by the interconnect resistance of metal wires and the capacitance of interlayer dielectric materials limits the high integration and miniaturization of electronic devices. As a promising low-k dielectric material, metal–organic frameworks (MOFs) can effectively alleviate this problem. In this work, we report an atomic regulation strategy of ultralow k MIL-53 film, achieved by converting an Al2O3 seed layer deposited via atomic layer deposition (ALD) and subsequently modifying through atomic layer infiltration (ALI). Thanks to the linear relationship between the thickness of the MIL-53 film and the Al2O3 seed layer prepared by ALD, precise nanoscale control of the MIL-53 films was realized. To meet both mechanical and dielectric property requirements, ALI modification is introduced, effectively regulating Young’s modulus and hardness of MIL-53 films from 19.5 and 0.17 GPa to 29.1 and 0.36 GPa, respectively, while the dielectric constant can be tuned from 1.93 to 2.59. The reconciliation of these properties is achieved by regulating the porosity of the MIL-53 framework through the additional Al–O clusters during the ALI. Furthermore, the superhydrophobic properties (140.7°) and the nearly constant dielectric constant after 9 months of aging reflect its potential as a dielectric insulating material. The proposed preparation and modification strategy of MOF films based on atomic regulation has broad potential for application in low-k interconnect integrated circuits.
随着集成电路微型化的发展,金属线的互连电阻和层间介电材料的电容所造成的 RC 延迟限制了电子器件的高集成度和微型化。金属有机框架(MOFs)作为一种前景广阔的低介电材料,可以有效缓解这一问题。在这项工作中,我们报告了一种超低 k MIL-53 薄膜的原子调控策略,该策略是通过原子层沉积(ALD)转换沉积的 Al2O3 种子层,然后通过原子层渗透(ALI)进行改性而实现的。得益于 MIL-53 薄膜厚度与 ALD 制备的 Al2O3 种子层之间的线性关系,实现了对 MIL-53 薄膜的精确纳米级控制。为了满足机械和介电性质的要求,引入了 ALI 改性,有效地调节了 MIL-53 薄膜的杨氏模量和硬度,分别从 19.5 和 0.17 GPa 提高到 29.1 和 0.36 GPa,介电常数则从 1.93 调整到 2.59。这些特性的调和是通过在 ALI 过程中添加 Al-O 簇来调节 MIL-53 框架的孔隙率实现的。此外,超疏水特性(140.7°)和经过 9 个月老化后几乎恒定的介电常数也反映了其作为介电绝缘材料的潜力。所提出的基于原子调控的 MOF 薄膜制备和改性策略在低 K 值互连集成电路中具有广阔的应用前景。
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引用次数: 0
In Situ Monitoring Surface Reactions in Cryogenic Atomic Layer Etching of Silicon Nitride by Alternating Surface Modification with Hydrogen Fluoride Dose and Ar Plasmas 通过交替使用氟化氢剂量和氩等离子体进行表面改性,现场监测氮化硅低温原子层蚀刻过程中的表面反应
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-11-07 DOI: 10.1021/acs.chemmater.4c01835
Shih-Nan Hsiao, Makoto Sekine, Yuki Iijima, Masaru Hori
Cryogenic atomic layer etching (ALE) represents a promising technique for achieving subnanoscale material removal in semiconductor processes, owing to its unique self-limiting surface-adsorbing reactions. This paper presents a cryogenic ALE method for SiN, utilizing surface modification with a hydrogen fluoride (HF) dose and an Ar etch step for removing the modification layer. The surface reactions and etching mechanism were examined using in situ monitoring techniques, including spectroscopic ellipsometry and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). Our observations reveal a self-limiting etching behavior for SiN and a reduction in the etch amount per cycle (EPC) with a decreasing substrate temperature. During the HF dose step, in situ ATR-FTIR spectra indicate the formation of a surface-adsorbed layer containing ammonium fluorosilicate (AFS) on the SiN surface. Subsequently, during the Ar plasma etching step, both the AFS layer and the surface-adsorbed species were removed. At lower substrate temperatures, the stability of the AFS layer and surface-absorbed species increased, resulting in a reduction in EPC. Through the control of Ar ion energy and substrate temperature, the manipulation of EPC ranging from several nanometers to a few angstroms in atomic layer etching is achieved, offering potential utility in nanoscale device applications utilizing silicon nitride.
低温原子层蚀刻(ALE)因其独特的自限制表面吸附反应而成为半导体工艺中实现亚纳米尺度材料去除的一种前景广阔的技术。本文介绍了一种用于氮化硅的低温原子层蚀刻方法,利用氟化氢(HF)剂量进行表面改性,并通过氩气蚀刻步骤去除改性层。利用原位监测技术,包括光谱椭偏仪和衰减全反射傅立叶变换红外光谱(ATR-FTIR),对表面反应和蚀刻机理进行了研究。我们的观察结果表明,氮化硅的蚀刻行为具有自限性,随着基底温度的降低,每周期的蚀刻量(EPC)也会减少。在高频剂量步骤中,原位 ATR-FTIR 光谱显示在 SiN 表面形成了含有氟硅酸铵 (AFS) 的表面吸附层。随后,在氩等离子体蚀刻步骤中,AFS 层和表面吸附层都被去除。在较低的基底温度下,AFS 层和表面吸附物种的稳定性增加,导致 EPC 下降。通过控制氩离子能量和基底温度,在原子层蚀刻中实现了从几纳米到几埃的 EPC 操作,为利用氮化硅的纳米级器件应用提供了潜在的实用性。
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Chemistry of Materials
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