Evidence for hydrogen two-level systems in atomic layer deposition oxides
M. S. Khalil, M. J. A. Stoutimore, S. Gladchenko, A. M. Holder, C. B. Musgrave, A. C. Kozen, G. Rubloff, Y. Q. Liu, R. G. Gordon, J. H. Yum, S. K. Banerjee, C. … 展开作者
M. S. Khalil, M. J. A. Stoutimore, S. Gladchenko, A. M. Holder, C. B. Musgrave, A. C. Kozen, G. Rubloff, Y. Q. Liu, R. G. Gordon, J. H. Yum, S. K. Banerjee, C. J. Lobb, K. D. Osborn
Two-level system (TLS) defects in dielectrics are known to limit the performance of electronic devices. We study TLS using millikelvin microwave loss measurements of three atomic layer deposited (ALD) oxide films--crystalline BeO ($\rm{c-BeO}$), amorphous $\rm{Al_2O_3}$ ($\rm{a-Al_2O_3}$), and amorphous $\rm{LaAlO_3}$ ($\rm{a-LaAlO_3}$)--and interpret them with room temperature characterization measurements. We find that the bulk loss tangent in the crystalline film is 6 times higher than in the amorphous films. In addition, its power saturation agrees with an amorphous distribution of TLS. Through a comparison of loss tangent data to secondary ion mass spectrometry (SIMS) impurity analysis we find that the dominant loss in all film types is consistent with hydrogen-based TLS. In the amorphous films excess hydrogen is found at the ambient-exposed surface, and we extract the associated hydrogen-based surface loss tangent. Data from films with a factor of 40 difference in carbon impurities revealed that carbon is currently a negligible contributor to TLS loss.
We report the epitaxial growth of Ca3SnO antiperovskite oxide films on (001)-oriented cubic yttria-stabilized zirconia (YSZ) substrates by using a conventional pulsed laser deposition (PLD) technique. In this work, a sintered Ca3SnO pellet is used as the ablation target. X-ray diffraction measurements demonstrate the (001) growth of Ca3SnO films with the antiperovskite structure and a cube-on-cube orientation relationship to the YSZ substrate. The successful synthesis of the antiperovskite phase is further confirmed by x-ray photoemission spectroscopy. These results strongly suggest that antip…
To visualize the topography of thin oxide films during growth, thereby enabling to study its growth behavior quasi real-time, we have designed and integrated an atomic force microscope (AFM) in a pulsed laser deposition (PLD) vacuum setup. The AFM scanner and PLD target are integrated in a single support frame, combined with a fast sample transfer method, such that in-situ microscopy can be utilized after subsequent deposition pulses. The in-situ microscope can be operated from room temperature (RT) up to 700$^\circ$C and at (process) pressures ranging from the vacuum base pressure of 10$^{-6}…
The authors report in situ Auger electron spectroscopy (AES) of the surfaces of complex oxides thin films grown by pulsed laser deposition (PLD). The authors demonstrate the utility of the technique in studying chemical composition by collecting characteristic Auger spectra of elements from samples such as complex oxide thin films and single crystals as well as metal foils. In the case of thin films, AES studies can be performed with single unit cell precision by monitoring thickness during deposition with reflection high energy electron diffraction (RHEED). The authors address some of the cha…
Variations in growth conditions associated with different deposition techniques can greatly affect the phase stability and defect structure of complex oxide heterostructures. We synthesized superlattices of the paramagnetic metal LaNiO3 and the large band gap insulator LaAlO3 by atomic layer-by-layer molecular beam epitaxy (MBE) and pulsed laser deposition (PLD) and compared their crystallinity, microstructure as revealed by high-resolution transmission electron microscopy images and resistivity. The MBE samples show a higher density of stacking faults, but smoother interfaces and generally hi…
Porous metal oxides with nano-sized features attracted intensive interest in recent decades due to their high surface area which is essential for many applications, e.g. Li ion batteries, photocatalysts, fuel cells and dye-sensitized solar cells. Various approaches were so far investigated to synthesize porous nanostructured metal oxides, including self-assembly and template-assisted synthesis. For the latter approach, forests of carbon nanotubes are considered as particularly promising templates, with respect to their one dimensional nature and the resulting high surface area. In this work, w…
Here we systematically explore the use of pulsed laser deposition technique (PLD) to grow three basic oxides that have rocksalt structure but different chemical stability in the ambient atmosphere: NiO (stable), MnO (metastable) and EuO (unstable). By tuning laser fluence, an epitaxial single-phase nickel oxide thin-film growth can be achieved in a wide range of temperatures from 10 to 750 °C. At the lowest growth temperature, the out-of-plane strain raises to 1.5%, which is five times bigger than that in a NiO film grown at 750 °C. MnO thin films that had long-range ordered were successfully …
Epitaxy of Fe3O4 on Si(001) by pulsed laser deposition using a TiN/MgO buffer layer
氧化物材料在硅（Si）衬底上的外延对于使用氧化物的各种物理性质如铁电性、铁磁性或超导性的未来功能器件具有极大的兴趣。最近，具有高自旋极化的载流子的材料已经成为自旋电子学中的氧化物-氧化物混合器件的关注点。在这里，我们报告的脉冲激光沉积磁铁矿（Fe 3 O 4）在Si（001）衬底上清洁的原位激光束高温处理。在沉积氮化钛（TiN）和氧化镁（MgO）的双缓冲层之后，可以生长高质量的外延磁铁矿层，如通过RHEED强度振荡和高分辨率X射线衍射所验证的。
This work is concerned with Al/Al-oxide(AlO$_{x}$)/Al-layer systems which are important for Josephson-junction-based superconducting devices such as quantum bits. The device performance is limited by noise, which has been to a large degree assigned to the presence and properties of two-level tunneling systems in the amorphous AlO$_{x}$ tunnel barrier. The study is focused on the correlation of the fabrication conditions, nanostructural and nanochemical properties and the occurrence of two-level tunneling systems with particular emphasis on the AlO$_{x}$-layer. Electron-beam evaporation with tw…
We deposit intrinsic hydrogenated amorphous silicon (a-Si:H) thin films by reactive pulsed laser deposition, for various hydrogen pressures in the 0-20 Pa range, at a low deposition temperature of 120C, and investigate the hydrogen incorporation, structural, optical, and electrical properties of the films, as a function of the ambient hydrogen pressure. The film thickness decreases linearly as the hydrogen pressure increases. The hydrogen content of the films is determined by infrared spectroscopy and the optical bandgap from UV-Vis-NIR transmittance and reflectance measurements. Electric meas…
Aluminum oxide thin films were deposited on silicon substrates under different deposition conditions using pulse pressure metal organic chemical vapour deposition (PP-MOCVD). The current study investigates into the growth mechanism of the deposited film and the control of the film morphology by varying the processing parameters of PP-MOCVD - choice of solvent, concentration, and presence of a shield. Aluminum sec-butoxide (ASB) was used as the aluminum source while hexane and toluene were used as the solvents. The films were deposited at 475oC at different precursor concentrations. It was obse…
In this work, the nucleation and growth mechanism of aluminum oxide (Al2O3) in the early stages of the direct atomic layer deposition (ALD) on monolayer epitaxial graphene (EG) on silicon carbide (4H-SiC) has been investigated by atomic force microscopy (AFM) and Raman spectroscopy. Contrary to what is typically observed for other types of graphene, a large and uniform density of nucleation sites was observed in the case of EG and ascribed to the presence of the buffer layer at EG/SiC interface. The deposition process was characterized by Al2O3 island growth in the very early stages, followed …
In this article, we report the process induced variation in the characteristics of PECVD deposited and thermally grown silicon dioxide (SiO2) thin film. We find key differences in the porosity, arrangement of the nano-pores, surface roughness, refractive index and electrical resistivity of the SiO2 thin films obtained by the two methods. While the occurrence of the nanoporous structure is an inherent property of the material and independent of the process of film growth or deposition, the arrangements of these nano-pores in the oxide film is process dependent. The distinct arrangements of the …
Highly-ordered and spatially-coherent cobalt slanted columnar thin films were deposited by glancing angle deposition onto silicon substrates, and subsequently oxidized by annealing at 475 $^{\circ}$C. Scanning electron microscopy, Raman scattering, generalized ellipsometry, and density functional theory investigations reveal shape-invariant transformation of the slanted nanocolumns from metallic to transparent metal-oxide core-shell structures with properties characteristic of spinel cobalt oxide. We find passivation of Co-SCTFs yielding CoAl$_2$O$_3$ core-shell structures produced by conforma…
Atomic layer deposition (ALD) is an essential tool in semiconductor device fabrication that allows the growth of ultrathin and conformal films to precisely form heterostructures and tune interface properties. The self-limiting nature of the chemical reactions during ALD provides excellent control over the layer thickness. However, in contrast to idealized growth models, it is experimentally challenging to create continuous monolayers by ALD because surface inhomogeneities and precursor steric interactions result in island growth during film nucleation. Thus, the ability to create pin-hole free…
Phase-selective growth of water-soluble strontium aluminate via sputtering deposition for freestanding oxide membranes
TU Wien（维也纳工业大学）；Université Caen Normandie（诺曼底大学）；CEA（法国原子能和替代能源委员会）；ENSICAEN（恩西西安高等学院）；CNRS（法国国家科学研究中心）；CIMAP UMR6252（CIMAP联合研究实验室6252）；Catalan Institute of Nanoscience and Nanotechnology (ICN2)（加泰罗尼亚纳米科学和纳米技术研究所）；CSIC（西班牙国家研究委员会）；BIST（巴塞罗那科学与技术研究院）；University of Geneva（日内瓦大学）；Leibniz-Institut für Kristallzüchtung（莱布尼兹晶体生长研究所）；ALBA Synchrotron Light Source（阿尔巴同步辐射光源）
Dielectric Deposition Enhanced Crystallization in Atomic-Layer-Deposited Indium Oxide Transistors Achieving High Gated-Hall Mobility Exceeding 100 cm2/Vs at Room Temperature
The integration of two-dimensional (2D) materials with functional non-2D materials such as metal oxides is of key importance for many applications, but underlying mechanisms for such non-2D/2D interfacing remain largely elusive at the atomic scale. To address this, we here investigate the nucleation stage in atomic layer deposition (ALD) of the important metal oxide HfO2 on chemical vapor deposited graphene using atomically resolved and element specific scanning transmission electron microscopy (STEM). To avoid any deleterious influence of polymer residues from pre-ALD graphene transfers we em…
Thin (approximately 10 nm) oxide buffer layers grown over lead-halide perovskite device stacks are critical for protecting the perovskite against mechanical and environmental damage. However, the limited perovskite stability restricts the processing methods and temperatures (<=110 C) that can be used to deposit the oxide overlayers, with the latter limiting the electronic properties of the oxides achievable. In this work, we demonstrate an alternative to existing methods that can grow pinhole-free TiOx (x = 2.00+/-0.05) films with the requisite thickness in <1 min without vacuum. This techniqu…
Copper oxide thin films are deposited on quartz substrates by DC magnetron sputtering and the effect of deposition temperature on their optoelectronic properties is examined in detail. Scanning Electron Microscopy (SEM), X-ray diffraction (XRD) analysis, Raman spectroscopy, UV-Vis spectroscopy, and four-probe sheet resistance measurements are used to characterize the surface morphology, structural, optical, and electrical properties respectively. Deposition is carried out at room temperature and between 200 and 300 °C. XRD analysis indicates that the oxide formed is primarily Cu$_2$O and the a…
In order to continue to improve integrated circuit performance and functionality, scaled transistors with short channel lengths and low thickness are needed. But the further scaling of silicon-based devices and the development of alternative semiconductor channel materials that are compatible with current fabrication processes is challenging. Here we report atomic-layer-deposited indium oxide transistors with channel lengths down to 8 nm, channel thicknesses down to 0.5 nm and equivalent dielectric oxide thickness down to 0.84 nm. Due to the scaled device dimensions and low contact resistance,…
The most popular way to produce graphene nowadays is chemical vapor deposition, where, surprisingly, H$_2$ gas is routinely supplied even though it is a byproduct itself. In this study, by identifying dominant growing pathways via multiscale simulations, we unambiguously reveal the central role hydrogen played in graphene growth. Hydrogen can saturate the edges of a growing graphene island to some extent, depending on the H$_2$ pressure. Although graphene etching by hydrogen has been observed in experiment, hydrogen saturation actually stabilizes graphene edges by reducing the detachment rates…
Films of graphene oxide (GO) were produced on the inner walls of glass microcapillaries via insertion of a GO water suspension followed by quick drying with a hot finger (no previous surface functionalization required). Individual capillaries from an array could also be selectively GO coated. Raman hyperspectral images revealed the films to be continuous along tens of centimeters. Furthermore, the films could be thermally reduced through an annealing process, which also decreased the concentration of defects. As a proof of principle application, the microcapillaries of photonic crystal fibers …
Homogeneous highly epitaxial LaSrMnO3 (LSMO) thin films have been grown on Yttria-stabilized-Zirconia (YsZ) / CeO2 buffer layers on technological relevant 4" silicon wafers using a Twente Solid State Technology B.V. (TSST) developed large area Pulsed Laser Deposition (PLD) setup. We study and show the results of the effect of an additional SrRuO3 buffer layer on the growth temperature dependent structural and magnetic properties of LSMO films. With the introduction of a thin SrRuO3 layer on top of the buffer stack, LSMO films show ferromagnetic behaviour for growth temperatures as low as 250C.…
Lanthanum manganite, LaMnO (LMO) is the parent compound for a class of hole doped(e.g. La1-xCaxMnO3, La1-xSrxMnO3) and electron doped (e.g. . La1-xCexMnO3, La1-xSnxMnO3) perovskite complex oxide materials. Strong correlation between the spin,lattice, charge and orbital degrees of freedom is a hallmark of these class of materials (popularly known as manganites). Competition and interplay of these degrees of freedom lead to a wide range of interesting electronic behavior including half-metallicity, colossal magneto-resistivity, etc. Although a lot of experimental research has been carried out on…
The Anode Hydrogen Release (AHR) mechanism at interfaces is responsible for the generation of defects, that traps charge carriers and can induce dielectric breakdown in Metal-Oxide-Semiconductor Field Effect Transistors. The AHR has been extensively studied at Si/SiO$_2$ interfaces but its characteristics at metal-silica interfaces remain unclear. In this study, we performed Density Functional Theory (DFT) calculations to study the hydrogen release mechanism at the typical Al/SiO$_2$ metal-oxide interface. We found that interstitial hydrogen atoms can break interfacial Al-Si bonds, passivating…
Reactive pulsed direct current magnetron sputtering deposition of semiconducting yttrium oxide thin film in ultralow oxygen atmosphere: A spectroscopic and structural investigation of growth dynamics
We report on the deposition of gallium oxide using microwave irradiation technique on III nitride epi layers. We also report on the first demonstration of a gallium oxide device, a visible blind deep UV detector, with GaN based heterostructure as the substrate. The film deposited in the solution medium, at less than 200 C, using a metalorganic precursor, was nanocrystalline. XRD confirms that as deposited film when annealed at high temperature turns polycrystalline beta gallium oxide. SEM shows the as deposited film to be uniform, with a surface roughness of 4 to 5 nm, as revealed by AFM. Inte…
Hole-doped perovskite bismuthates such as Ba$_{1-x}$K$_x$BiO$_3$ and Sr$_{1-x}$K$_x$BiO$_3$ are well-known bismuth-based oxide high-transition-temperature superconductors. Reported thin bismuthate films show relatively low quality, likely due to their large lattice mismatch with the substrate and a low sticking coefficient of Bi at high temperatures. Here, we report the successful epitaxial thin film growth of the parent compound strontium bismuthate SrBiO$_3$ on SrO-terminated SrTiO$_3$ (001) substrates by molecular beam epitaxy. Two different growth methods, high-temperature co-deposition or…
Clean hydrogen production through efficient and cost-effective electrochemical water splitting is highly promising to meeting future global energy demands. The design of Earth-abundant materials with both high activity for hydrogen evolution reaction (HER) and electrochemical stability in both acidic and alkaline environments summarize the outcomes needed for practical applications. Here, we report a non-noble 3d metal Cl-chemical doping of liquid phase exfoliated single/few-layer flakes of MoSe2 for creating MoSe2 nanoflakes/3d metal oxide-hydr(oxy)oxide hybrid HER-catalysts. We propose that …
The study on the electronic state of muon as pseudo-hydrogen (represented by the elemental symbol Mu) has long been appreciated as one of the few methods to experimentally access the electronic state of dilute hydrogen (H) in semiconductors and dielectrics. Meanwhile, theoretical predictions on the electronic state of H in these materials by first-principles calculations using density functional theory (DFT) do not always agree with the observed states of Mu, standing as an obstacle to integrating the findings of both Mu and H. In this paper, we provide resolution to this problem by a semi-qua…
