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Improved properties of atomic layer deposited ruthenium via postdeposition annealing 沉积后退火工艺改善了钌原子层的性能
Pub Date : 2021-07-27 DOI: 10.1116/6.0001078
Michael Hayes, M. Jenkins, J. Woodruff, D. Moser, C. Dezelah, J. F. ConleyJr.
The resistivity, morphology, and effective work function of thin film ruthenium deposited by thermal atomic layer deposition (ALD) using η4-2,3-dimethylbutadiene ruthenium tricarbonyl [Ru(DMBD)(CO)3] and O2 are investigated before and after annealing at temperatures up to 500 °C. Annealing at 500 °C in either N2 or H2/N2 reduces the average resistivity of as-deposited 30 nm thick Ru films from 16.2 to as low as 13.7 or 9.1 μΩ cm, respectively, approaching the bulk value of Ru. X-ray diffraction shows that as-deposited films are polycrystalline hexagonal Ru. Annealing at 500 °C in either N2 or H2/N2 results in crystallite growth accompanied by a roughening of the surface from approximately 0.7 to 2.2 nm RMS, as shown by atomic force microscopy. Secondary ion mass spectroscopy shows low residual carbon and oxygen in as-deposited films. Annealing in N2 at 500 °C reduces only the carbon content, whereas annealing in H2/N2 at 500 °C results in a further reduction of carbon combined with reduction in oxygen as well. Using series of metal/oxide/silicon capacitors with varying oxide thickness, the effective work function of 500 °C H2/N2 annealed Ru films on ALD Al2O3 and HfO2 was determined to be approximately 4.9 and 5.3 eV, respectively. Using internal photoemission spectroscopy, the Ru/Al2O3 and Ru/HfO2 electron energy barrier heights were determined to be 3.4 ± 0.1 and 3.8 ± 0.1 eV, respectively.
研究了用η - 4,3 -二甲基丁二烯钌三羰基[Ru(DMBD)(CO)3]和O2制备的热原子层沉积(ALD)钌薄膜在500℃退火前后的电阻率、形貌和有效功函数。在500℃的N2或H2/N2中退火后,沉积的30 nm厚Ru膜的平均电阻率分别从16.2降低到13.7或9.1 μΩ cm,接近Ru的体积值。x射线衍射表明,沉积膜为多晶六方钌。原子力显微镜显示,在500°C的N2或H2/N2中退火会导致晶体生长,同时表面的RMS约为0.7至2.2 nm。二次离子质谱分析表明,沉积膜中残余碳和氧含量较低。在500°C的N2中退火只降低了碳含量,而在500°C的H2/N2中退火导致碳的进一步减少,同时也减少了氧。采用不同厚度的金属/氧化物/硅电容器,测定了500℃H2/N2退火Ru膜在ALD Al2O3和HfO2上的有效功函数分别约为4.9和5.3 eV。利用光电发射光谱测定Ru/Al2O3和Ru/HfO2的电子能垒高度分别为3.4±0.1和3.8±0.1 eV。
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引用次数: 3
Selective functionalization of partially etched SiNx to enhance SiO2 to SiNx etch selectivity 部分蚀刻SiNx的选择性官能化以提高SiO2对SiNx的蚀刻选择性
Pub Date : 2021-07-26 DOI: 10.1116/6.0001110
Ryan J. Gasvoda, Xue Wang, Prabhat Kumar, E. Hudson, S. Agarwal
Selective functionalization of SiO2 and SiNx surfaces is challenging after atmospheric exposure or after exposure to an etching plasma chemistry as both surfaces tend to have similar functional groups. Here, we show that a SiNx surface can be selectively functionalized over SiO2 with benzaldehyde after the first atomic layer etching (ALE) cycle. Similar to our previous work on pristine plasma-deposited SiO2 and SiNx surfaces [R. J. Gasvoda, Z. Zhang, E. A. Hudson, and S. Agarwal, J. Vac. Sci Technol. A 39, 040401 (2021)], this selective functionalization can be used to increase the overall SiO2 to SiNx etch selectivity during ALE. The surface reactions, composition, and film thickness during ALE were monitored using in situ surface infrared spectroscopy and in situ four-wavelength ellipsometry. Our ALE process consisted of alternating cycles of CFx deposition from a C4F6/Ar plasma and an Ar activation plasma with an average ion energy of ∼210 eV. The first ALE cycle removed the surface SiOxNy layer on the SiNx surface and created reactive sites for selective benzaldehyde attachment.
在大气暴露或蚀刻等离子体化学后,SiO2和SiNx表面的选择性功能化具有挑战性,因为这两个表面往往具有相似的官能团。在这里,我们证明了在第一次原子层蚀刻(ALE)循环后,苯甲醛可以选择性地在SiO2上功能化SiNx表面。与我们之前对原始等离子体沉积SiO2和SiNx表面的研究相似[R]。张志强,张志强,张志强。Sci抛光工艺。A 39, 040401(2021)],这种选择性功能化可用于提高ALE过程中SiO2到SiNx的整体蚀刻选择性。利用原位表面红外光谱和原位四波长椭偏仪监测了ALE过程中的表面反应、组成和膜厚度。我们的ALE过程由C4F6/Ar等离子体和Ar激活等离子体的CFx沉积交替循环组成,平均离子能量为~ 210 eV。第一次ALE循环去除SiNx表面的SiOxNy层,并产生选择性苯甲醛附着的反应位点。
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引用次数: 0
Elucidating energetics and kinetics in environmentally relevant mixed gas plasmas 阐明与环境相关的混合气体等离子体的能量学和动力学
Pub Date : 2021-07-26 DOI: 10.1116/6.0001080
Tara L. Van Surksum, E. R. Fisher
Understanding energy distributions and kinetic processes in low temperature plasmas is vital to increase their utility for a range of applications, in particular pollution remediation. Optical emission spectroscopy (OES) was employed to elucidate energetic and kinetic trends for several diatomic species in CH4/N2 and CH4/H2O plasma systems. Vast differences in rotational and vibrational temperatures between dissimilar plasma species were observed, indicating the internal temperatures of excited state species are not equilibrated with each other. In combination with energy partitioning results, species formation and destruction rates within the plasma were derived from time-resolved OES data. The results provide insight into molecule formation pathways, including that the formation of CN may be related to excited nitrogen species available in CH4/N2 plasmas.
了解低温等离子体中的能量分布和动力学过程对于提高其在一系列应用中的效用至关重要,特别是污染修复。利用光学发射光谱(OES)研究了CH4/N2和CH4/H2O等离子体体系中几种双原子物质的能量和动力学变化趋势。不同等离子体种之间的旋转和振动温度存在巨大差异,表明激发态种内部温度彼此之间不平衡。结合能量分配结果,等离子体内的物种形成和破坏率由时间分辨OES数据得出。这些结果提供了对分子形成途径的深入了解,包括CN的形成可能与CH4/N2等离子体中可用的激发态氮有关。
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引用次数: 0
Preparation and electronic structure of the WSe2/graphene/NiSex/Ni(111) heterostructure WSe2/石墨烯/NiSex/Ni(111)异质结构的制备与电子结构
Pub Date : 2021-07-26 DOI: 10.1116/6.0001134
Roberto Sant, M. Cattelan, S. Agnoli, G. Granozzi
In this work, a stacked heterostructure made up of single-layer WSe2 and graphene was created through a scalable and efficient way. Graphene was grown on a Ni (111) single crystal, producing an ordered and well-defined carbon overlayer that is strongly hybridized with the support, disrupting its peculiar conductive properties. A monolayer WSe2 was deposited on top of graphene by the simultaneous evaporation of metal W and elemental Se. We demonstrate here that the chalcogen can efficiently intercalate between graphene and the Ni surface, decoupling the two materials and forming a buffering NiSex layer. The concurrent selenization of both W and Ni effectively eliminates the need for an additional decoupling step in the synthesis of a free-standing graphene/Ni heterostructure. The formation process of the complex WSe2/Graphene/NiSex/Ni(111) heterostructure was studied by means of low-energy electron diffraction, x-ray photoelectron spectroscopy, angle-resolved ultraviolet photoelectron spectroscopy, and ex situ Raman spectroscopy. These analyses confirm the presence of single-layer WSe2 on top of a free-standing graphene.
在这项工作中,通过可扩展和高效的方法,创建了由单层WSe2和石墨烯组成的堆叠异质结构。石墨烯生长在Ni(111)单晶上,产生有序且定义明确的碳层,与载体强烈杂化,破坏其特有的导电性能。通过金属W和元素Se的同时蒸发,在石墨烯表面沉积了一层单层WSe2。我们在这里证明了硫可以有效地插入石墨烯和Ni表面之间,使两种材料解耦并形成缓冲的NiSex层。W和Ni的同时硒化有效地消除了在合成独立的石墨烯/Ni异质结构时需要额外的解耦步骤。采用低能电子衍射、x射线光电子能谱、角度分辨紫外光电子能谱、非原位拉曼光谱等手段研究了WSe2/石墨烯/NiSex/Ni(111)异质结构配合物的形成过程。这些分析证实了单层WSe2在独立石墨烯上的存在。
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引用次数: 0
Green CVD—Toward a sustainable philosophy for thin film deposition by chemical vapor deposition 绿色气相沉积—化学气相沉积薄膜的可持续发展理念
Pub Date : 2021-07-22 DOI: 10.1116/6.0001125
H. Pedersen, S. Barry, J. Sundqvist
Thin films of materials are critical components for most areas of sustainable technologies, making thin film techniques, such as chemical vapor deposition (CVD), instrumental for a sustainable future. It is, therefore, of great importance to critically consider the sustainability aspects of CVD processes themselves used to make thin films for sustainable technologies. Here, we point to several common practices in CVD that are not sustainable. From these, we offer a perspective on several principles for a sustainable, “Green CVD” philosophy, which we hope will spur research on how to make CVD more sustainable without affecting the properties of the deposited film. We hope that these principles can be developed by the research community over time and be used to establish research on how to make CVD more sustainable and that a Green CVD philosophy can develop new research directions for both precursor and reactor design to reduce the precursor and energy consumption in CVD processes.
薄膜材料是大多数可持续技术领域的关键组成部分,使薄膜技术,如化学气相沉积(CVD),成为可持续未来的工具。因此,批判性地考虑CVD工艺本身用于制造可持续技术薄膜的可持续性方面是非常重要的。在这里,我们指出了心血管疾病中几种不可持续的常见做法。从这些角度出发,我们提出了可持续的“绿色CVD”理念的几个原则,我们希望这将促进如何使CVD更具可持续性而不影响沉积膜的性能的研究。我们希望随着时间的推移,这些原则可以被研究界发展起来,并用于建立如何使CVD更具可持续性的研究,并且绿色CVD哲学可以为前驱体和反应器设计开辟新的研究方向,以减少CVD过程中的前驱体和能源消耗。
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引用次数: 13
Titanium monoxide and titanium dioxide thin film formation by magnetron sputtering and its thermodynamic model 磁控溅射制备氧化钛和二氧化钛薄膜及其热力学模型
Pub Date : 2021-07-21 DOI: 10.1116/6.0001065
S. V. Bulyarskiy, D. Koiva, V. S. Belov, E. Zenova, G. Rudakov, G. Gusarov
This work is devoted to the problem of the formation of titanium monoxide and dioxide by magnetron sputtering. Sputtering titanium in constant flows of oxygen and argon and constant magnetron power leads to the creation of equilibrium partial pressures of oxygen and titanium vapors. The conditions for the synthesis of nanocrystalline titanium monoxide at low temperatures were determined experimentally and substantiated by the thermodynamic method. An analysis is made by the method of minimizing the Gibbs free energy. We have obtained an expression for the ratio of the oxygen flow and the gas discharge power, the analysis of which makes it possible to determine the conditions for the formation of titanium oxide with a certain stoichiometric composition. The developed method for the analysis of equilibrium in the deposition chamber can be used to identify the conditions for the synthesis of other compounds that are important for practice, including oxides and chalcogenides, and the horizons of their use in nanoelectronics are constantly growing at the present time.
这项工作致力于磁控溅射形成氧化钛和二氧化钛的问题。在恒定的氧气和氩气流和恒定的磁控管功率下溅射钛会导致氧气和钛蒸气的平衡分压的产生。实验确定了低温合成纳米氧化钛的条件,并用热力学方法对其进行了验证。用最小吉布斯自由能法对其进行了分析。得到了氧流量与气体放电功率之比的表达式,通过对其分析,可以确定具有一定化学计量成分的氧化钛的形成条件。所开发的沉积室平衡分析方法可用于确定其他对实践很重要的化合物的合成条件,包括氧化物和硫族化合物,它们在纳米电子学中的应用范围目前正在不断扩大。
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引用次数: 0
Operando study of the preferential growth of SiO2 during the dry thermal oxidation of Si0.60Ge0.40(001) by ambient pressure x-ray photoelectron spectroscopy 用环境压力x射线光电子能谱研究Si0.60Ge0.40(001)干热氧化过程中SiO2的优先生长
Pub Date : 2021-07-19 DOI: 10.1116/6.0001174
S. P. Lorona, J. Diulus, Jo E. Bergevin, R. Addou, G. Herman
Controlling the grown oxide composition, the oxide/semiconductor interface properties, and the semiconductor surface composition is of interest for SiGe devices. We have used ambient-pressure x-ray photoelectron spectroscopy (AP-XPS) to study the initial stages of dry thermal oxidation of an epitaxial Si0.60Ge0.40(001) film on Si(001). Si 2p and Ge 3d chemical-state resolved AP-XPS was performed at 300 °C and O2 pressures ( P O 2 ) of 10−4, 10−2, and 1 mbar during oxide growth. The National Institute of Standards simulated electron spectra for surface analysis (SESSA) was used to analyze both the oxide composition and the thickness versus time for each pressure. At all three P O 2, the SESSA analysis indicated that oxidation proceeds via three oxide growth rate regimes: an initial rapid regime, an intermediate transitionary regime, and finally a quasisaturation slow regime. The Si and Ge oxidation rates were found to be pressure dependent during the rapid regime with both rates decreasing monotonically with decreasing pressure. Results indicated that Ge was much more sensitive to changes in P O 2 compared to Si. As a result, a decrease in P O 2 resulted in significant suppression of GeO2 formation compared to SiO2. Using SESSA, we were able to quantify the grown oxide composition and the thickness, both of which were strongly dependent on O2 pressure. The Ge composition, in Si1−xGexO2, was found to decrease monotonically with decreasing P O 2.
控制生长的氧化物组成,氧化物/半导体界面性质,以及半导体表面组成是SiGe器件的兴趣所在。我们利用常压x射线光电子能谱(AP-XPS)研究了Si0.60Ge0.40(001)外延薄膜在Si(001)上干热氧化的初始阶段。在氧化物生长过程中,在300°C和10−4、10−2和1 mbar的O2压力下进行Si 2p和Ge 3d化学态分解AP-XPS。使用美国国家标准研究所模拟表面分析电子能谱(SESSA)来分析每种压力下的氧化物成分和厚度随时间的变化。SESSA分析表明,在所有三个o2中,氧化通过三个氧化物生长速率机制进行:初始快速机制,中间过渡机制,最后是准饱和缓慢机制。在快速反应过程中,Si和Ge的氧化速率与压力有关,且随压力的降低而单调降低。结果表明,与Si相比,Ge对o2的变化更为敏感。结果表明,与SiO2相比,o2的减少对GeO2的形成有明显的抑制作用。使用SESSA,我们能够量化生长的氧化物成分和厚度,这两者都强烈依赖于O2压力。在Si1−xGexO2中,Ge的组成随着p2o的减小而单调降低。
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引用次数: 1
Functional plasma-sprayed hydroxylapatite coatings for medical application: Clinical performance requirements and key property enhancement 医用功能性等离子喷涂羟基磷灰石涂料:临床性能要求和关键性能增强
Pub Date : 2021-07-19 DOI: 10.1116/6.0001132
R. Heimann
Functional hydroxylapatite (HAp) coatings deposited by atmospheric plasma spraying on parts of hip and knee endoprosthetic implants, artificial dental roots, spinal implants, and other medical devices serve to aid in osseointegration by providing a biocompatible and osseoconductive/osseoinductive template for bone growth-supporting actions of cytokines and noncollagenous proteins and proteoglycans, mediated by transmembrane proteins such as integrins. To be successful in this task, HAp coatings need to be carefully designed and optimized by closely controlling key properties such as phase composition, degree of crystallinity, crystallographic texture, thickness, adhesion strength to the implant surface, porosity, pore size distribution, surface nanostructure and roughness, residual coating stresses, and dissolution kinetics during in vivo contact with extracellular fluid. As this contribution discusses salient aspects of design, properties, and application of HAp coatings, it attempts to chart ways toward improving their in vivo performance and, thus, may be considered a helping hand and guiding manual of instruction for their successful deposition. In this review, much contextual recourse has been taken to the work of the present author and his research group during the last two and a half decades.
通过大气等离子喷涂沉积在髋关节和膝关节内假体、人工牙根、脊柱植入物和其他医疗器械上的功能性羟基磷灰石(HAp)涂层,通过为细胞因子、非胶原蛋白和蛋白聚糖(由跨膜蛋白如整合素介导)的骨生长支持作用提供生物相容性和骨传导/骨诱导模板,有助于骨整合。为了成功完成这项任务,需要仔细设计和优化HAp涂层,严格控制关键性能,如相组成、结晶度、晶体结构、厚度、与植入物表面的粘附强度、孔隙率、孔径分布、表面纳米结构和粗糙度、残余涂层应力以及体内与细胞外液接触时的溶解动力学。由于这篇文章讨论了HAp涂层的设计、性能和应用的突出方面,它试图绘制出改善其体内性能的方法,因此,可以被认为是成功沉积HAp涂层的帮助之手和指导手册。在这篇综述中,许多上下文资源已被采取到目前的作者和他的研究小组在过去的二十五年的工作。
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引用次数: 4
Localized phase transition of TiO2 thin films induced by sub-bandgap laser irradiation 亚带隙激光辐照诱导TiO2薄膜的局域相变
Pub Date : 2021-07-15 DOI: 10.1116/6.0001088
Syeed E. Ahmed, Violet M. Poole, John D. Igo, Y. Gu, M. McCluskey
The ability to define the crystal phase of oxide semiconductors could benefit transparent electronics and catalysis. In this paper, laser-induced localized phase transitions of titanium dioxide (TiO2) thin films are reported. Irradiation was performed with a 532 nm continuous wave laser. Raman spectroscopy and micro-Raman mapping were used to identify the phase transformations. A Raman map of the anatase Eg mode (144 cm−1) and rutile Ag mode (608 cm−1) revealed the formation of crystalline microstructures due to the laser treatment. Laser irradiation under vacuum results in an anatase-to-rutile phase transition. Irradiating the rutile region in air changes the crystal structure back to anatase, despite the thermodynamic stability of rutile. The results suggest that irradiated photons are absorbed by defects, resulting in localized electronic excitation that leads to a mixture of amorphous and crystalline regions. The phase of the crystalline regions depends strongly on the ambient conditions (vacuum versus air).
确定氧化物半导体晶体相的能力将有利于透明电子学和催化。本文报道了激光诱导二氧化钛(TiO2)薄膜的局域相变。532 nm连续波激光照射。利用拉曼光谱和微拉曼映射技术对相变进行了识别。锐钛矿Eg模式(144 cm−1)和金红石Ag模式(608 cm−1)的拉曼图显示,由于激光处理,形成了晶体微观结构。真空激光照射导致锐钛矿向金红石相变。尽管金红石具有热力学稳定性,但在空气中辐照金红石区会使晶体结构变回锐钛矿。结果表明,辐照光子被缺陷吸收,导致局部电子激发,导致非晶态和结晶区混合。晶体区域的相很大程度上取决于环境条件(真空还是空气)。
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引用次数: 4
Wafer-level uniformity of atomic-layer-deposited niobium nitride thin films for quantum devices 量子器件原子层沉积氮化铌薄膜的片级均匀性
Pub Date : 2021-07-14 DOI: 10.1116/6.0001126
E. Knehr, M. Ziegler, S. Linzen, K. Ilin, P. Schanz, J. Plentz, M. Diegel, H. Schmidt, E. Il'ichev, M. Siegel
Superconducting niobium nitride thin films are used for a variety of photon detectors, quantum devices, and superconducting electronics. Most of these applications require highly uniform films, for instance, when moving from single-pixel detectors to arrays with a large active area. Plasma-enhanced atomic layer deposition (ALD) of superconducting niobium nitride is a feasible option to produce high-quality, conformal thin films and has been demonstrated as a film deposition method to fabricate superconducting nanowire single-photon detectors before. Here, we explore the property spread of ALD-NbN across a 6-in. wafer area. Over the equivalent area of a 2-in. wafer, we measure a maximum deviation of 1% in critical temperature and 12% in switching current. Toward larger areas, structural characterizations indicate that changes in the crystal structure seem to be the limiting factor rather than film composition or impurities. The results show that ALD is suited to fabricate NbN thin films as a material for large-area detector arrays and for new detector designs and devices requiring uniform superconducting thin films with precise thickness control.
超导氮化铌薄膜用于各种光子探测器、量子器件和超导电子器件。大多数这些应用需要高度均匀的薄膜,例如,当从单像素探测器移动到具有大有源区域的阵列时。等离子体增强原子层沉积(ALD)超导氮化铌是制备高质量保形薄膜的一种可行选择,并已被证明是一种制备超导纳米线单光子探测器的薄膜沉积方法。在这里,我们探索了ALD-NbN在6-in的属性分布。晶片区域。除以2英寸的等量面积。我们测量了临界温度和开关电流的最大偏差分别为1%和12%。对于更大的区域,结构表征表明晶体结构的变化似乎是限制因素,而不是薄膜成分或杂质。结果表明,ALD适合制造NbN薄膜,作为大面积探测器阵列的材料,以及需要均匀超导薄膜和精确厚度控制的新型探测器设计和器件。
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引用次数: 9
期刊
Journal of Vacuum Science and Technology
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