Amorphous carbon (a-C) materials have diverse interesting and useful properties, but the understanding of their atomic-scale structures is still incomplete. Here, we report on extensive atomistic simulations of the deposition and growth of a-C films, describing interatomic interactions using a machine learning (ML) based Gaussian Approximation Potential (GAP) model. We expand widely on our initial work [Phys. Rev. Lett. 120, 166101 (2018)] by now considering a broad range of incident ion energies, thus modeling samples that span the entire range from low-density ($sp^{2}$-rich) to high-density ($sp^{3}$-rich, "diamond-like") amorphous forms of carbon. Two different mechanisms are observed in these simulations, depending on the impact energy: low-energy impacts induce $sp$- and $sp^{2}$-dominated growth directly around the impact site, whereas high-energy impacts induce peening. Furthermore, we propose and apply a scheme for computing the anisotropic elastic properties of the a-C films. Our work provides fundamental insight into this intriguing class of disordered solids, as well as a conceptual and methodological blueprint for simulating the atomic-scale deposition of other materials with ML-driven molecular dynamics.
The deposition of boron-doped amorphous carbon thin films on SiO2 substrate was achieved via a focused ion beam-assisted chemical vapor deposition of triphenyl borane (C18H15B) and triphenyl borate (C18H15BO3). The existence of boron in the deposited film from triphenyl borane, with a precursor temperature of 90 °C, was confirmed by a core level X-ray photoelectron spectroscopy analysis. The film exhibited a semiconducting behavior with a band gap of 285 meV. Although the band gap was decreased to 197 meV after an annealing process, the film was still semiconductor. Additionally, a drastic red…
By molecular dynamics simulation, the chemical vapor deposition of amorphous carbon onto graphite and diamond surfaces was studied. In particular, we investigated the effect of source H/C ratio, which is the ratio of the number of hydrogen atoms to the number of carbon atoms in a source gas, on the deposition process. In the present simulation, the following two source gas conditions were tested: one was that the source gas was injected as isolated carbon and hydrogen atoms, and the other was that the source gas was injected as hydrocarbon molecules. Under the former condition, we found that a…
Biaxially textured MgO templates have been successfully fabricated on several amorphous polymer films including Kapton tapes, polyimide, Poly(methyl methacrylate) (PMMA), and photoresist films using ion-beam-assisted-deposition (IBAD). With a Y2O3 buffer layer on polymer surfaces, roughening of the polymer surfaces due to preferential ion beam sputtering can be effectively reduced to meet the surface compatibility requirement for IBAD-MgO texturing. In-plane full-width-at-half-maximum (FWHM) of ~10.7 degrees and out-of-plane FWHM ~ 3.5 degrees have been obtained on homoepitaxial MgO films grow…
Pulsed Laser Deposition allows to obtain W and W-Ta alloy coatings with different nanostructures, monitored by X-ray diffraction. The correlation between such structures and the elastic properties is investigated for amorphous-like, ultra-nano- and nano-crystalline coatings obtained by tuning the gas pressure during deposition, annealing temperature and Ta concentration. The full elastic characterization is achieved by surface Brillouin spectroscopy, interpreted by isotropic and anisotropic film models. Amorphous like coatings are obtained with He pressures of tens of Pa. In comparison with bu…
The growth of amorphous TiO2 and anisotropic-polycrystalline ZnO thin-films is studied by means of coarse-grained three-dimensional kinetic Montecarlo simulations under conditions typically encountered in Plasma Enhanced Chemical Vapor Deposition experiments. The approach developed considers fluctuations in the activation energy for surface diffusion of the coarse particles that are calculated on-the-fly and depends on the mesoscale local morphological/structural landscape. The basis of this approach --which is known to work well to simulate the growth of amorphous materials using a much simpl…
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…
In this work, we simulated the physical vapor deposition (PVD) process of Cu atoms on the amorphous SiO$_2$ substrate. The resulting Cu thin layer exhibit amorphous structure. The Cu liquid quenching from 2000 K to 50 K was also simulated with different cooling rate to form the Cu metallic glass for comparison. The Cu glasses from the two different processes (PVD and quenching) revealed the same radial distribution function but different local structure from the Voronoi tessellation analysis. The PVD glass exhibit higher densities and lower potential energy compared with the melt-quenched coun…
Crystallization is a key for ferroelectricity which is a collective behavior of microscopic electric dipoles. On the other hand, uncontrolled crystallization leads to uneven morphology and random crystal orientations, which undermines the application potential of ferroelectric thin films. In this work, we introduce a film fabrication method of low-temperature physical vapor deposition followed by restrained crystallization, with electrical properties monitored in real-time by in situ measurements. This method was adopted to fabricate films of 2-methylbenzimidazole (MBI), whose molecule crystal…
Organisms in nature can alter the short-range order of an amorphous precursor phase, thereby controlling the resulting crystalline structure. This phenomenon inspired an investigation of the effect of modifying the short-range order within the amorphous phase of a selected material. Amorphous thin films of aluminum oxide deposited by the atomic layer deposition method were found to vary structurally as a function of size. Thinner films, as predicted and also confirmed by atomistic simulations, exhibited more 4 coordinated alumina sites. These atomistic alterations were expected to change the a…
Atomic layer deposition (ALD) provides uniform and conformal thin films that are of interest for a range of applications. To better understand the properties of amorphous ALD films, we need improved understanding of their local atomic structure. Previous work demonstrated measurement of how the local atomic structure of ALD-grown aluminum oxide (AlOx) evolves in operando during growth by employing synchrotron high energy X-ray diffraction (HE-XRD). In this work, we report on efforts to employ electron diffraction pair distribution function (ePDF) measurements using more broadly available trans…
Supported carbon nanosheets and carbon nanotubes served as sacrificial templates for preparing spacious TiO2 photocatalytic thin films. Amorphous TiO2 was deposited conformally on the carbonaceous template material by atomic layer deposition (ALD). Upon calcination at 550°C, the carbon template was oxidatively removed and the as-deposited continuous amorphous TiO2 layers transformed into interlinked anatase nanoparticles with an overall morphology commensurate to the original template structure. The effect of type of template, number of ALD cycles and gas residence time of pollutant on the pho…
NbO2 is a potential material for nanometric memristor devices, both in the amorphous and the crystalline form. We fabricated NbO2 thin films using RF-magnetron sputtering from a stoichiometric target. The as-deposited films were amorphous regardless of the sputtering parameters. Post deposition vacuum annealing of the films was necessary to achieve crystallinity. A high degree of crystallinity was obtained by optimizing annealing duration and temperature. The resistivity of the material increases as it undergoes a structural transition from amorphous to crystalline with the crystalline films b…
By using molecular dynamics simulation, formation mechanisms of amorphous carbon in particular sp${}^3$ rich structure was researched. The problem that reactive empirical bond order potential cannot represent amorphous carbon properly was cleared in the transition process from graphite to diamond by high pressure and the deposition process of amorphous carbon thin films. Moreover, the new potential model which is based on electron distribution simplified as a point charge was developed by using downfolding method. As a result, the molecular dynamics simulation with the new potential could demo…
Pulsed laser deposition from a Nd:YAG laser was employed in production of hundreds of nanometer thick quasicrystalline Ti-Zr-Ni films on glass substrate. The influence of deposition temperature Ts on the structure, morphology and microstructure of the films across their thickness was investigated. The morphology and microstructure features were evaluated by X-ray diffraction and transmission electron microscopy techniques. The low deposition temperatures were found to produce films with nanometer sized grains embedded in an amorphous matrix. The grains exhibit quasicrystalline order. The highe…
Drawing inspiration from nature, where some organisms can control the short range order of amorphous minerals, we successfully manipulated the short range order of amorphous alumina by surface and size effects. By utilizing the Atomic Layer Deposition (ALD) method to grow amorphous nanometrically thin films, combined with state-of-the-art electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS), we showed experimentally that the short range order in such films is strongly influenced by size. This phenomenon is equivalent to the well-known size effect on lattice param…
The self-limiting nature of atomic layer deposition (ALD) makes it an appealing option for growing single layers of two-dimensional van der Waals (2D-VDW) materials. In this paper it is demonstrated that a single layer of a 2D-VDW form of SiO2 can be grown by ALD on Au and Pd polycrystalline foils and epitaxial films. The silica was deposited by two cycles of bis (diethylamino) silane and oxygen plasma exposure at 525 K. Initial deposition produced a three-dimensionally disordered silica layer; however, subsequent annealing above 950 K drove a structural rearrangement resulting in 2D-VDW; this…
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. Th…
Amorphous/crystalline multilayer structures of Fe-P alloys were deposited electrochemically using the single bath technique. Hall-Petch behavior of microhardness with respect to sublayer thickness was observed down to a sublayer thickness of 15 nm. For thinner sublayers, a hardness plateau was obtained. The transition at a sublayer thickness of 15 nm coincides with the loss of the multilayer structure as observed in transmission electron microscopy. The transition is a possible result of a change in the amorphous to crystalline sublayer thickness ratio and the interface roughness development d…
Identification of formation of amorphous Si phase in SiOxNy films produced by plasma enhanced chemical vapor deposition
V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine（乌克兰国家科学院瓦·拉什卡廖夫半导体物理研究所）；Educational Scientific Institute of High Technologies, Taras Shevchenko National University of Kyiv（基辅塔拉斯舍甫琴科国立大学高等技术教育科学研究所）；National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”（乌克兰国立技术大学“伊戈尔·西科尔斯基基辅理工学院”）；Institute of Physics, National Academy of Sciences of Ukraine（乌克兰国家科学院物理研究所）
Additive solid immersion lenses for enhanced collection efficiency of shallow NV centers by pulsed laser deposition and structurization of high-k amorphous oxides
Leipzig University（莱比锡大学）；Felix Bloch Institute, Leipzig University（莱比锡大学费利克斯·布洛赫研究所）；SaxonQ GmbH（萨克森量子有限公司）；Department of Prosthetic Dentistry and Dental Material Science, Leipzig University（莱比锡大学假肢牙科与牙科材料科学系）
Amorphous metal oxide thin-film transistors (TFT) are fabricated using InOx-based semiconductors doped with TiO2, WO3 or SiO2. Although density of dopant is low in the film, change in the electrical properties showed strong dependence on the dopant species. We found that the dependence could be reasonably explained by the bond-dissociation energy. By incorporating the dopant with higher bond-dissociation energy, the film becomes less sensitive to oxygen partial pressure used during sputtering deposition and remains electrically stable to thermal annealing treatment. The concept of bond-dissoci…
Electron beam induced deposition with tungsten hexacarbonyl W(CO)6 as precursors leads to granular deposits with varying compositions of tungsten, carbon and oxygen. Depending on the deposition conditions, the deposits are insulating or metallic. We employ an evolutionary algorithm to predict the crystal structures starting from a series of chemical compositions that were determined experimentally. We show that this method leads to better structures than structural relaxation based on guessed initial structures. We approximate the expected amorphous structures by reasonably large unit cells th…
Here we report mid infrared (mid-IR) photothermal response of multi layer MoS2 thin film grown on crystalline (p-type silicon and c-axis oriented single crystal sapphire) and amorphous substrates (Si/SiO2 and Si/SiN) by pulsed laser deposition (PLD) technique. The photothermal response of the MoS2 films was measured as changes in the resistance of MoS2 films when irradiated with mid IR (7 to 8.2 μm) source. We show that it is possible to enhance the temperature coefficient of resistance (TCR) of the MoS2 thin film by controlling the interface through proper choice of substrate and growth condi…
In this paper we demonstrate experimentally that crystalline phases appear in amorphous titanium oxide upon processing with ultrafast laser pulses. Amorphous titanium thin films were produced by plasma-enhanced chemical vapor deposition (PECVD) and exposed to femtosecond laser pulses. Formation of rutile phase was confirmed by X-ray diffraction, Raman measurements and electron backscattering diffraction. A rang of processing parameters for the crystallization is reported and possible background mechanisms are discussed.
Crystalline wurtzite zinc oxide (w-ZnO) can be used as a wide band gap semiconductor for light emitting devices and for transparent or high temperature electronics. The use of amorphous zinc oxide (a-ZnO) can be an advantage in these applications. In this paper we report on X-ray amorphous a-ZnOx thin films (~500 nm) deposited at cryogenic temperatures by reactive magnetron sputtering. The substrates were cooled by a nitrogen flow through the copper substrate holder during the deposition. The films were characterized by X-ray diffraction (XRD), Raman, infrared, UV-Vis-NIR spectroscopies, and e…
We used the Coherent Grazing Incidence Small Angle X-Ray Scattering (Co-GISAXS) technique to study the average kinetics and nanoscale dynamics during early-stage a-WSi$_2$ sputter deposition. The kinetic and dynamic properties are examined as a function of pressure, which is known to be a critical factor in determining final surface roughness. Surface growth kinetics and dynamics are characterized by time parameters extracted from the height-height structure factor and correlation functions. The roughness at a given length scale reaches a maximum before relaxing down to a steady state. The lat…
Al2O3 thin films have been deposited at substrate temperatures between 500°C to 600°C by reactive magnetron sputtering using an additional arbitrary substrate bias to tailor the energy distribution of the incident ions. The films were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The film structure being amorphous, nanocrystalline, or crystalline was correlated with characteristic ion energy distributions. The evolving crystalline structure is connected with different levels of displacements per atom (dpa) in the growing film as being derived from…
Bulk rhenium trioxide (ReO3) has an unusually high electrical conductivity and, being nanosized, has promising catalytic properties. However, the production of pure ReO3 thin films is challenging due to the difficulty to stabilize rhenium in a 6+ oxidation state. Here we present a novel approach for the deposition of ReOx (x = 1.6-2.9) thin films using reactive high power impulse magnetron sputtering (r-HiPIMS) from a metallic rhenium target in a mixed Ar/O2 atmosphere. The thin films were deposited in the gas-sustained self-sputtering regime, observed during r-HiPIMS process according to curr…
Wires of sp-hybridized carbon atoms are attracting interest for both fundamental aspects of carbon science and for their appealing functional properties. The synthesis by physical vapor deposition has been reported to provide sp-rich carbon films but still needs to be further developed and understood in detail. Here the synthesis of carbon-atom wires (CAWs) has been achieved by nanosecond pulsed laser deposition (PLD) expoliting the strong out-of-equilibrium conditions occurring when the ablation plasma is confined in a background gas. Surface Enhnaced Raman scattering (SERS) spectra of deposi…
Monatomic antimony thin films have recently attracted attention for applications in phase change memory, nanophotonics, and 2D materials. Although some promising results have been reported, the true potential of Sb thin films is still hindered by the scalability issue and the lack of reliable bottom-up production. Here we demonstrate the growth of Sb thin films on a lattice-matching and amorphous substrates using pulsed laser deposition (PLD). C-axis out-of-plane textured Sb thin films were successfully deposited on Sb$_2$Te$_3$ and SiO$_2$\Si$_3$N$_4$ substrates. In the case of growth on Sb$_…
We report on the results of an extensive campaign of optical and mechanical characterization of the ion-beam sputtered oxide layers (Ta$_2$O$_5$, TiO$_2$, Ta$_2$O$_5$-TiO$_2$, SiO$_2$) within the high-reflection coatings of the Advanced LIGO, Advanced Virgo and KAGRA gravitational-wave detectors: refractive index, thickness, optical absorption, composition, density, internal friction and elastic constants have been measured; the impact of deposition rate and post-deposition annealing on coating internal friction has been assessed. For Ta$_2$O$_5$ and SiO$_2$ layers, coating internal friction i…
We report on the synthesis and characterization of nanocrystalline delta-MoN by crystallization of amorphous thin films grown on (100) Si by reactive sputtering at room temperature. Films with chemical composition MoN were grown using a deposition pressure of 5mTorr with a reactive mixture of Ar/(Ar+N2)=0.5. The as-grown films display mostly amorphous structure. Nanocrystalline delta-MoN phase is obtained after annealing at temperatures above 600 °C. The superconducting critical temperature Tc depends on film thickness. Thick films (170 nm) annealed at 700 °C for 30 min display a Tc = 11.2 K (…
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
The current generation of advanced gravitational wave detectors utilize titania-doped tantala/silica multilayer stacks for their mirror coatings. The properties of the low-refractive-index silica are well known; however, in the absence of detailed direct measurements, the material parameters of Young's modulus and coefficient of thermal expansion (CTE) of the high refractive index material, titania-doped tantala, have been assumed to be equal to values measured for pure tantala coatings. In order to ascertain the true values necessary for thermal noise calculations, we have undertaken measurem…
We study the deposition of tetrahedral amorphous carbon (ta-C) films from molecular dynamics simulations based on a machine-learned interatomic potential trained from density-functional theory data. For the first time, the high $sp^3$ fractions in excess of 85% observed experimentally are reproduced by means of computational simulation, and the deposition energy dependence of the film's characteristics is also accurately described. High confidence in the potential and direct access to the atomic interactions allow us to infer the microscopic growth mechanism in this material. While the widespr…
Amorphous mixed titania-tantala coatings are key components of Bragg reflectors in the gravitational wave detectors (GWDs). Attaining the lowest possible values of optical absorption and mechanical losses in the coatings is of paramount importance for GWDs, and this requires a complex optimization of the coating deposition and post-deposition annealing. We present here a systematic investigation of the optical properties and internal friction of amorphous mixed titania-tantala coatings grown by ion beam sputtering. We consider coatings with six different cation mixing ratios and we study them …
Bulk amorphous materials have been studied extensively and are widely used, yet their atomic arrangement remains an open issue. Although they are generally believed to be Zachariasen continuous random networks, recent experimental evidence favours the competing crystallite model in the case of amorphous silicon. In two-dimensional materials, however, the corresponding questions remain unanswered. Here we report the synthesis, by laser-assisted chemical vapour deposition, of centimetre-scale, free-standing, continuous and stable monolayer amorphous carbon, topologically distinct from disordered…
Atomic layer deposition of ultrathin HfO2 on unmodified graphene from HfCl4 and H2O was investigated. Surface RMS roughness down to 0.5 nm was obtained for amorphous, 30 nm thick hafnia film grown at 180 degrees C. HfO2 was deposited also in a two-step temperature process where the initial growth of about 1 nm at 170 degrees C was continued up to 10-30 nm at 300 degrees C. This process yielded uniform, monoclinic HfO2 films with RMS roughness of 1.7 nm for 10-12 nm thick films and 2.5 nm for 30 nm thick films. Raman spectroscopy studies revealed that the deposition process caused compressive b…
We prepared thin layers of amorphous silicon by deposition of a liquid-phase polysilane precurser on glass substrate. Raman scattering provides evidence for residual tensile stress in the silicon, which is evaluated quantitatively. Under treatment with hydrofluoric acid, this stress leads to spiral cracks in the silicon. We explain the process of crack formation and examine this phenomenon both analytically and numerically, the latter with the finite element method (FEM). The FEM yields the geometry correction factor for such spiral cracks in terms of the Griffith criterion. This allows for th…
This paper reports on the deposition of amorphous and crystalline thin films of Ga2O3 by reactive pulsed direct current magnetron sputtering from a liquid gallium target onto fused (f-) quartz and c plane (c-) sapphire substrates, where the temperature of the substrate is varied from room temperature (RT) to 800°C. The deposition rate (up to 37 nm/min at RT on f-quartz and 5 nm/min at 800°C on c-sapphire) is two to five times higher than the data given in the literature for radio frequency sputtering. Deposited onto unheated substrates, the films are X-ray amorphous. Well-defined X-ray diffrac…
Using isothermal and temperature-dependent electrical measurements, we investigated the resistive switching mechanism of amorphous titanium oxide thin films deposited by a plasma-enhanced atomic layer deposition method between two aluminum electrodes. We found a bipolar resistive switching behavior in the high temperature region (> 140 K), and two activation energies of shallow traps, 0.055 eV and 0.126 eV in the ohmic current regime. We also proposed that the bipolar resistive switching of amorphous TiO2 thin films is governed by the transition of conduction mode from a bulk-limited SCLC mode…
Thermal conductivity of amorphous carbon thin films
用$3ω$方法测量了非晶碳薄膜在80- 400 K温度范围内的热导率$Λ$。样品薄膜的范围从通过远程等离子体沉积制备的软a-C：H（室温下的$Λ= 0.20$ W m $^{-1}$ K $^{-1}$）到具有大部分从过滤弧源沉积的$sp^3$键合碳的非晶金刚石（$Λ= 2.2$ W m $^{-1}$ K $^{-1}$）。连续介质理论提供了电导率随质量密度变化的唯象描述。热导率与由测量的原子密度和纵向声速计算的最小热导率吻合得很好。
Microscopy and diffraction measurements are presented of ultrathin binary alloy films of ruthenium and molybdenum that are obtained by standard sputter deposition. For compositions close to Ru50Mo50, we find the films to be amorphous. The amorphicity of the films is accompanied by a significant reduction of the roughness with respect to the roughness of equally thick films of either ruthenium or molybdenum. We ascribe this to the absence of the grain structure that is characteristic of the polycrystalline films of the separate elements.
In this work, we investigate the correlation between morphology, composition, and the mechanical properties of metallic amorphous tungsten-oxygen and amorphous tungsten-oxide films deposited by Pulsed Laser Deposition. This correlation is investigated by the combined use of Brillouin Spectroscopy and the substrate curvature method. The stiffness of the films is strongly affected by both the oxygen content and the mass density. The elastic moduli show a decreasing trend as the mass density decreases and the oxygen-tungsten ratio increases. A plateaux region is detected in correspondence of the …
