原子尺度构建二维材料的第一性原理计算研究

随着信息技术的不断进步,核心元器件朝着运行速度更快、能耗更低、尺寸更小的方向快速发展.尺寸不断减小导致的量子尺寸效应使得材料和器件呈现出许多与传统三维体系不同的新奇物性.从原子结构出发,预测低维材料物性、精准合成、表征、调控并制造性能良好的电子器件,对未来电子器件的发展及相关应用具有至关重要的意义.理论计算能在保持原子级准确度的情况下高效、低耗地预测材料结构、物性、界面效应等,是原子制造技术中不可或缺的重要研究手段.本综述从第一性原理计算角度出发,回顾了近年来其在二维材料结构探索、物性研究和异质结构造等方面的应用及取得的重要进展,并展望了在原子尺度制造背景下二维材料的发展前景.     

“原子制造:基础研究与前沿探索”专题编者按

制造技术的不断迭代发展带来了器件性能的飞跃,也推动着人类技术的进步.伴随着器件特征尺寸的不断缩小,制造技术先后经历了宏观制造、介观制造、微观制造和纳米制造等多个阶段,当前最具代表性的半导体工艺,已经从微米尺度走到最前沿的3 nm左右,并进一步向更小的尺度迈进.因此,制造技术进入到原子尺度已不再是遥不可及的梦想,而成为现在科技界研究前沿的现实对象.     

核酸-金属复合物及其在原子制造领域的应用

原子及近原子尺度制造是直接以原子为操纵对象,构建具有特定功能的原子尺度结构,并实现批量生产以满足所需要的前沿制造技术,是国际学术研究的前沿热点问题.本综述总结了核酸材料在精准原子制造中的应用及前景,从核酸材料的基本结构与功能出发,论述了DNA与金属原子相互作用的基本原理.从天然核酸材料、人工碱基"分子元素"、核酸纳米结构等方面分类介绍了核酸材料介导的精准原子制造的发展历程与突破性进展.最后,对该领域存在的一些挑战与机遇进行了系统性总结,并对其未来发展方向进行了展望.     

原子尺度材料三维结构、磁性及动态演变的透射电子显微学表征

原子表征与操控是实现原子制造必须突破的物理瓶颈之一.像差校正电子显微学方法因其优异的空间分辨率,为实现原子精细制造提供了有力的表征手段.因此,利用电子显微学手段,在原子尺度对原子制造的材料及器件进行三维结构和性能的协同表征,对于深入理解原子水平材料操控的物理机理具有非常重要的意义.纳米团簇及纳米颗粒是原子制造材料与器件研究的主要对象之一,具有丰富的物理化学性质和较高的可操纵性.本文探讨纳米团簇/颗粒结构三维定量表征、使役条件下纳米团簇/颗粒结构演变定量表征、纳米颗粒/晶粒结构-成分-磁性协同定量表征等诸多方法与实例,阐明了电子显微学表征手段的突破和发展为实现精细控制的原子制造材料提供了坚实基础.     

DNA折纸结构介导的多尺度纳米结构精准制造

原子及近原子尺度制造在近年来一直是物质科学领域被广泛探讨的前沿问题.当制造和加工的尺度从微米、纳米逐渐走向原子级别时,材料在常规尺度下所具备的性质已无法通过经典理论进行解释,相反地,会在这一尺度下展现出一系列新奇的特性.因而对材料极限制造尺度和颠覆性物性的不断追求始终是科学界共同关注的重点领域.作为一种在纳米尺度下对结构制造单元进行精细操控的先进手段,DNA纳米技术的开发和发展为纳米制造甚至原子制造提供了新的观点和思路,而DNA折纸术作为DNA纳米技术的重要组成部分,正在凭借其在结构制造过程当中的高度可编程性成为纳米尺度下进行各类物质精准制造的独特的解决方案,并可能为不同物质不同材料更小尺度和任意形状的精准构筑带来机遇.本文首先简单概述了DNA折纸术的基本原理和发展历程,然后根据制造策略的不同对DNA折纸结构的纳米制造的相关代表性工作做了总结,并在文末提出了对于DNA折纸结构在原子制造中的可行性的思考和未来发展方向的展望.     

表界面调控米级二维单晶原子制造

随着芯片尺寸不断缩小,短沟道效应、热效应日趋显著.开发全新的量子材料体系以实现高性能芯片器件应用已成为当前科技发展的迫切需求.二维材料作为一类重要的量子材料,其天然具备原子层厚度和平面结构,能够有效克服短沟道效应并兼容当代微纳加工工艺,非常有望应用于新一代高性能器件方向.与硅基芯片发展类似,二维材料芯片级器件应用必须基于高质量、大尺寸的二维单晶材料制造.然而,由于二维材料的表界面特性,现有体单晶制备技术不能完全适用于单原子层结构的二维单晶制造.因此,亟需发展新的制备策略以实现大尺寸、高质量的二维单晶原子制造.有鉴于此,本文重点综述表界面调控二维单晶大尺寸制备技术发展现状,总结梳理了米级二维单晶原子制造过程中的3个关键调控方向,即单畴生长调控、单晶衬底制备和多畴取向控制.最后,系统展望了大尺寸二维单晶在未来规模化芯片器件方向的潜在应用前景.     

低维原子/分子晶体材料的可控生长、物性调控和原理性应用

本文介绍了高鸿钧课题组在物理所20年来的部分代表性工作.研究的主要方向为低维纳米功能材料的分子束外延可控制备、生长机制、物性调控及其在未来信息技术中的原理性应用.从材料的可控制备入手,结合第一性原理的理论计算,阐明材料生长机制和结构与物性的关系,进而实现物性调控和原理性应用.主要内容有:1)纳米尺度"海马"分形结构的形成及其生长机制;2)STM分辨率的提高及最高分辨Si(111)-7×7原子图像的获得;3)固体表面上功能分子的吸附、组装及其机制;4)稳定、重复、可逆的纳米尺度电导转变与超高密度信息存储;5)固体表面上单分子自旋态的量子调控及其原理性应用;6)原子尺度上朗德g因子的空间分辨及其空间分布不均匀性的发现;7)晶圆尺寸、高质量、单晶石墨烯的制备及原位硅插层绝缘化;8)几种新型二维原子晶体材料的可控构筑及其物性调控;9)"自然图案化"的新型二维原子晶体材料及其功能化.这些工作为低维量子结构的构造、物性调控及其原理性应用奠定了基础.     

基于原子操纵技术的人工量子结构研究

扫描隧道显微镜原子操纵技术是指利用扫描探针在特定材料表面以晶格为步长搬运单个原子或分子的技术.它是纳米尺度量子物理与器件研究领域一种独特而有力的研究手段.利用这种手段,人们能够以原子或分子为单元构筑某些常规生长或微加工方法难以制备的人工量子结构,通过对格点原子、晶格尺寸、对称性、周期性的高度控制,实现对局域电子态、自旋序、以及能带拓扑特性等量子效应的设计与调控.原子操纵技术与超快测量及自动控制技术的结合,使得人们能够进一步研究原子级精准的量子器件,因而该技术成为探索未来器件新机理、新工艺的重要工具.本文首先简介原子操纵方法的发展过程和技术要点,然后分别介绍人工电子晶格、半导体表面人工量子点、磁性人工量子结构、人工结构中的信息存储与逻辑运算、单原子精度原型器件等方面的最新研究进展,以及单原子刻蚀和自动原子操纵等方面的技术进展,最后总结并展望原子操纵技术的应用前景和发展趋势.     

原子光刻

与光子和电子不间,原子的激发亚稳态具有方便操作的内能态结构,这使利用内能态的光学淬灭原理实现光刻技术成为现实.基于原子光学的中性原子束光刻技术是下一代光刻技术(the next generation lithography,NGL)的一种,它可分两种途径实现:激光驻波原子直沉积技术和亚稳态中性原子光刻技术.前者可以实现图案的纳米尺度特征、大面积平行沉积和高分辨率;后者结合有效的抗蚀剂,同样可以实现纳米图形制造,在基板上获得的尖锐边缘分辨率目前可达40 nm.两种途径的原理相差甚远,但最终获得的结果相似.     

金属纳米颗粒与二维材料异质结构的界面调控和物理性质

二维材料具有原子级光滑表面、纳米级厚度和超高的比表面积,是研究金属纳米颗粒与二维材料的界面相互作用,实时、原位观察金属纳米颗粒的表面原子迁移、结构演化和聚合等热力学行为的重要载体.设计和构筑金属纳米颗粒与二维材料异质结构界面,在原子尺度分析和表征界面结构,揭示材料结构和性能之间的相互关系,对于理解其相互作用和优化器件性能具有重要价值.本文总结了近年来金属纳米颗粒在二维材料表面成核、生长、结构演化及其表征的最新进展,分析了金属纳米颗粒对二维材料晶体结构、电子态、能带结构的影响,探讨了可能的界面应变、界面反应,及其对电学和光学等性质的调控,讨论了金属纳米颗粒对基于二维材料的场效应管器件和光电器件的性能提升策略.为从原子、电子层次揭示微结构、界面原子构型等影响金属纳米颗粒-二维材料异质结性能的物理机制,为金属-二维材料异质结构的研制及其在电子器件、光电器件、能源器件等领域的应用奠定了基础.     

激光驻波场中Cr原子运动轨迹与汇聚沉积的分析

利用半经典模型，从铬原子在激光驻波场中的运动方程出发，通过数值解方法模拟了铬原子在驻波场中的运动轨迹，并分析了原子的纵向速度分布和准直程度及球差对沉积条纹结构的影响，同时也讨论了基片摆放位置对沉积条纹结构的影响，并通过实验得到了纳米光栅条纹结构. 关键词： 激光驻波场 原子沉积 运动轨迹 沉积分布     

Low-temperature plasma enhanced atomic layer deposition of large area HfS_2 nanocrystal thin films

Hafnium disulfide(HfS2) is a promising two-dimensional material for scaling electronic devices due to its higher carrier mobility, in which the combination of two-dimensional materials with traditional semiconductors in the framework of CMOS-compatible technology is necessary. We reported on the deposition of HfS2 nanocrystals by remote plasma enhanced atomic layer deposition at low temperature using Hf(N(CH3)(C2H5))4 and H2S as the reaction precursors. Selflimiting reaction behavior was observed at the deposition temperatures ranging from 150℃ to 350℃, and the film thickness increased linearly with the growth cycles. The uniform HfS2 nanocrystal thin films were obtained with the size of nanocrystal grain up to 27 nm. It was demonstrated that higher deposition temperature could enlarge the grain size and improve the HfS2 crystallinity, while causing crystallization of the mixed HfO2 above 450℃. These results suggested that atomic layer deposition is a low-temperature route to synthesize high quality HfS2 nanocrystals for electronic device or electrochemical applications.     

Surface properties of diamond-like carbon films prepared by CVD and PVD methods

Diamond-like carbon (DLC) films have been deposited using three different techniques: (a) electron cyclotron resonance---plasma source ion implantation, (b) low-pressure dielectric barrier discharge, (c) filtered---pulsed cathodic arc discharge. The surface and mechanical properties of these films are compared using atomic force microscope-based tests. The experimental results show that hydrogenated DLC films are covered with soft surface layers enriched with hydrogen and sp$^{3}$ hybridized carbon while the soft surface layers of tetrahedral amorphous carbon (ta-C) films have graphite-like structure. The formation of soft surface layers can be associated with the surface diffusion and growth induced by the low-energy deposition process. For typical CVD methods, the atomic hydrogen in the plasmas can contribute to the formation of hydrogen and sp$^{3}$ hybridized carbon enriched surface layers. The high-energy ion implantation causes the rearrangement of atoms beneath the surface layer and leads to an increase in film density. The ta-C films can be deposited using the medium energy carbon ions in the highly-ionized plasma.     

Organic photovoltaics with high stability sustained for 100 days without encapsulation fabricated using atomic layer deposition

ZnO thin films with a rippled surface structure were used as electron‐collecting layers of inverted organic photovoltaics (OPVs). Using additional ultrathin layers of ZnO and TiO₂ fabricated using atomic layer deposition (ALD), not only the power‐conversion efficiency of the OPVs could be increased (up to 3.5%), but also the photovoltaic performance became nearly constant within 100 days without any additional encapsulations of the solar cells under ambient conditions.

     

Use of atomic layer deposition to improve the stability of silver substrates for in situ,high‐temperature SERS measurements

A method to stabilize silver surface‐enhanced Raman spectroscopy (SERS) substrates for in situ, high‐temperature applications is demonstrated. Silver island films grown by thermal evaporation were coated with a thin layer (from 2.5 to 5 nm) of alumina by atomic layer deposition (ALD), which protects and stabilizes the SERS‐active substrate without eliminating the Raman enhancement. The temporal stability of the alumina‐coated silver island films was examined by measurement of the Raman intensity of rhodamine 6G molecules deposited onto bare and alumina‐coated silver substrates over the course of 34 days. The coated substrates showed almost no change in SERS enhancement, while the uncoated substrates exhibited a significant decrease in Raman intensity. To demonstrate the feasibility of the alumina‐coated silver substrate as a probe of adsorbates and reactions at elevated temperatures, an in situ SERS measurement of calcium nitrate tetrahydrate on bare and alumina‐coated silver was performed at temperatures ranging from 25 to 400 °C. ALD deposition of an ultrathin alumina layer significantly improved the thermal stability of the SERS substrate, thus enabling in situ detection of the dehydration of the calcium nitrate tetrahydrate at an elevated temperature. Despite some loss of Raman signal, the coated substrate exhibited greater thermal stability compared to the uncoated substrate. These experiments show that ALD can be used to synthesize stable SERS substrates capable of measuring adsorbates and processes at high temperature. Copyright © 2009 John Wiley & Sons, Ltd.     

Review on Atomic Layer Deposition and Applications of Oxide Thin Films

Atomic layer deposition technique is able to grow conformal thin films over high aspect ratio structures. This article reviews the various aspects of oxides grown by this method including applications in photovoltaics and memristors. The main focus of this review is to concentrate on the oxides grown by atomic layer deposition and their growth mechanisms. The oxides deposited using atomic layer deposition are also likely to find application in memristor, an emerging field in the non volatile memories design with the ability to retain data and memory states even in power-off condition. The use of this technique to obtain oxides in surface modification of nanostructures gives the significance of these materials.     

Uniform light emission from electrically driven plasmonic grating using multilayer tunneling barriers

Light emission by inelastic tunneling(LEIT)from a metal-insulator-metal tunnel junction is an ultrafast emission process.It is a promising platform for ultrafast transduction from electrical signal to optical signal on integrated circuits.However,existing procedures of fabricating LEIT devices usually involve both top-down and bottom-up techniques,which reduces its compatibility with the modern microfabrication streamline and limits its potential applications in industrial scale-up.Here in this work,we lift these restrictions by using a multilayer insulator grown by atomic layer deposition as the tunnel barrier.For the first time,we fabricate an LEIT device fully by microfabrication techniques and show a stable performance under ambient conditions.Uniform electroluminescence is observed over the entire active region,with the emission spectrum shaped by metallic grating plasmons.The introduction of a multilayer insulator into the LEIT can provide an additional degree of freedom for engineering the energy band landscape of the tunnel barrier.The presented scheme of preparing a stable ultrathin tunnel barrier may also find some applications in a wide range of integrated optoelectronic devices.     

Effect of precursor on growth and morphology of MoS2 monolayer and multilayer

The rise of two-dimensional (2D) material is one of the results of successful efforts of researchers which laid the path to the new era of electronics. One of the most exciting materials is MoS₂. Synthesis has been always a major issue as electronic devices need reproducibility along with similar properties for mass productions. Chemical vapor deposition (CVD) is one of the successful methods for 2D materials including graphene. Furthermore, the choice of starting materials for Mo and S source is crucial. The different source has different effects on the layers and morphology of MoS₂ films. In this work, we have extensively studied the CVD technique to grow few layers of MoS₂ with two precursors MoO₃ and MoCl₅, show remarkable changes. The MoO₃ source gives a triangular shaped MoS₂ monolayer while that of MoCl₅ can achieve uniform MoS₂ without triangle. The absence of geometric shapes with MoCl₅ is poorly understood. We tried to explain with MoCl₅ precursor, the formation of continuous monolayer of MoS₂ without any triangle on the basis of chemical reaction formalism mostly due to one step reaction process and formation of MoS₂ from gas phase to the solid phase. The film synthesized by MoCl₅ is more continuous and it would be a good choice for device applications.     

前驱体和退火温度对Nd2O3薄膜组分影响的定量研究

采用Nd(thd)₃和O₃作为反应前驱体, 利用先进的原子层淀积方法在P型硅(100)衬底上制备了超薄Nd₂O₃介质膜, 并在N₂气氛下进行了退火处理. 采用X射线光电子能谱仪对薄膜样品组分进行分析. 研究结果表明, 淀积过程中将前驱体温度从175 ℃提高到185 ℃后, 薄膜的质量得到提高, O/Nd 原子比达到1.82, 更接近理想的化学计量比, 介电常数也从6.85升高到10.32.     

Pre- and post-breakdown electrical studies in ultrathin Al2O3 films by conductive atomic force microscopy

The loss of local dielectric integrity in ultrathin Al₂O₃ films grown by atomic layer deposition is investigated using conducting atomic force microscopy. I–V spectra acquired at different regions of the samples by constant and ramping voltage stress are analyzed for their pre- and post-breakdown signatures. Based on these observations, the thickness dependent dielectric reliability and failure mechanism are discussed. Our results show that remarkable enhancement in breakdown electric field as high as 130 MV/cm is observed for ultrathin films of thickness less than 1 nm.