Nanoscale Multilayers Research Articles

X-ray reflectivity with a twist: Quantitative time-resolved X-ray reflectivity using monochromatic synchrotron radiation

We have developed an improved method of time-resolved x-ray reflectivity (XRR) using monochromatic synchrotron radiation. Our method utilizes a polycapillary x-ray optic to create a range of incident angles and an area detector to collect specular reflections. By rotating the sample normal out of the plane of the incident fan, we can separate the surface diffuse scatter from the reflectivity signal, greatly improving the quality of the XRR spectra compared to previous implementations. We demonstrate the time-resolved capabilities of this system, with the temporal resolution as low as 10 ms, by measuring XRR during the annealing of Al/Ni nano-scale multilayers, and use this information to extract the activation energy for interdiffusion in this system.

Erosion Resistance and Damage Mechanism of TiN/ZrN Nanoscale Multilayer Coating

Ceramic coating is an effective method for improving the erosion resistance of a material, particularly for titanium alloys. In this study, a TiN/ZrN (ceramic/ceramic) nanoscale multilayer coating is designed and prepared on the Ti6Al4V titanium alloy surface by the physical vapor deposition (PVD) process. The cross-sectional microstructure and phase composition are measured using SEM and XRD, respectively. The hardness, elastic modulus, and adhesion of the coating are measured by the nano-indentation and scratch method. The erosion test is conducted at a 45° angle with 100 m/s velocity using self-developed erosion equipment. The erosion resistance mechanisms of both the substrate and the coating are revealed more intuitively through a single sand particle impact test. The results show that the erosion resistance rate of the coating is 15.5 times higher than that of the titanium alloy substrate. The damage mechanisms of material removal of the coating include crack deflection, crack branching, and succeeding interaction between them when suffering an impacting load. These cracks are started from the droplets and the stress concentrations on the coating surface during the preparation of coating. They are the primary reasons for the decrease in the erosion resistance of the coating. This research is important for the optimization of the erosion-resistant coating structure.

Spontaneous Potential Oscillation Resulting in Copper Deposit with Ultra-Large Grains

There are three categories of spontaneous oscillations in copper electrodeposition. The first one is the formation of nano-scale multilayers of Cu2O and mixed Cu/Cu2O composites from an alkaline Cu2+-chelated solution. The second one is the formation of sub-microscale multilayers of Cu from a sulfuric acid system. The copper with sub-microscale multilayers composes of a series of horizontal grain boundaries, and the horizontal grain boundaries was formed with incorporation of organic compounds, namely plating additives. In this case, not only the grain boundaries are horizontal, but also the plating additives show a leveling capability to form a flat surface. The third one is the copper deposit formation with ultra-large grain (ULG) from a sulfuric acid plating system in this study. No organic compounds were incorporated in the copper-ULG and the surface, edges and corners of the copper-ULG, showing a single crystal outward appearance. The spontaneous oscillations waveform of ULG copper deposition was quite complicated, and it is caused by the changing/ageing of the organic compounds in the plating solution and the continuously changing of deposit surface area.

Extreme Ultraviolet Multilayer Nanostructures and Their Application to Solar Plasma Observations: A Review

The advent of nanoscale multilayer (ML) technology has led to great breakthroughs in many scientific and technological fields such as nano-manufacturing, bio-imaging, atto-physics, matter physics and solar physics. ML nanostructures are an enabling technology for the development of mirrors and reflective gratings having high efficiency at normal incidence in the extreme ultraviolet (EUV) range, a spectral region where conventional coatings show a negligible reflectance. In solar physics, ML mirrors have proved to be key elements for both imaging and spectroscopy space instruments, as they allow to make observations of EUV solar plasma emissions with spatial and spectral resolutions never reached before. ML-based instruments have been used in many of the major solar satellites and have flown in numerous sounding rocket experiments; moreover, in the last two decades many studies were performed in order to develop ML structures with increasingly better performance for future solar missions. In this paper, a review of the most promising ML nanostructures developed so far and applied to the observation of solar plasma emission lines is presented. After a brief recall of ML theory, a detailed discussion of the most promising material pairs and layer stack structures proposed and applied to past and current space missions will be presented; in particular, the review will focus on the ML structures having high efficiency in the 6 nm-35 nm wavelength range. Finally, the ML stability to low energy ion bombardment will be discussed.

Corrosion Damage Mechanism of TiN/ZrN Nanoscale Multilayer Anti-Erosion Coating

TiN/ZrN multilayers can effectively improve the erosion resistance of metals, particularly titanium alloys employed in aero engines. To explore the corrosion damage mechanism of TiN/ZrN nanoscale multilayers (nanolaminate), a novel [TiN/ZrN]100 nanolaminate coating was deposited on Ti-6Al-4V alloys by multi-arc ion plating method. Salt spray corrosion tests and hot corrosion experiment were carried out to evaluate the corrosion resistance of the coating. The corrosion and damage mechanisms were explored with the help of detailed microstructure, phase composition and element distribution characterizations. The salt spray corrosion tests showed that the [TiN/ZrN]100 nanolaminate coating possessed good corrosion resistance, which protected substrate against the corrosion. The low temperature hot corrosion tests showed that the oxidation occurred on the surface of the coating, which improved the oxidation resistance of the sample. However, the oxidized droplets squeezed the coating, and destroyed the oxidized layers. As a result, the coating was peeled off from the substrate. The research highlights the corrosion resistance of the novel TiN/ZrN nanolaminate coating and offers a support for their application in engine compressor blade.

Structural and Magnetic Properties of Ni0.8Fe0.2/Ti Nanoscale Multilayers.

The influence of the thickness of the Ni0.8Fe0.2 (Permalloy, Py) layers on the structural and magnetic properties of magnetron sputtered Py/Ti multilayers was studied. The thickness of the Py layers was varied in the interval of 8 to 30 Å. X-ray reflectivity scans evidence the existence of a well-defined layered structure in all the samples considered, but also the presence of a complex intermixed interface. The shape of both the temperature dependence of magnetization and the hysteresis loops of the multilayered structures depends strongly on Py thickness. Magnetic and reflectivity measurements were comparatively analyzed in order to better understand the structure of the samples, and specifically, their interfaces. In particular, the presence of small superparamagnetic Py at the interfaces of the samples, especially evident in the samples with the thinnest Py layers, seems confirmed by the magnetic measurements, agreeing well with the reflectivity results.

Kossel diffraction observed with X-ray color camera during PIXE of nano-scale periodic multilayer

By combining Kossel diffraction with particle induced X-ray emission, we have developed a new methodology to analyze nano-scale thin films. We report the Kossel diffraction generated by irradiating Pd/Y based nano-scale periodic multilayers with 2 MeV protons. The intensity of characteristic Pd Lα X-ray emission is measured as a function of the detection angle (grazing exit). An oscillation of its intensity is observed when the detection angle varies around the Bragg angle, which corresponds to the energy of the emission and the period of the multilayer. Use of the X-ray color camera enables the whole setup to be fixed so that no angular scan is required, greatly simplifying the experimental condition. From the features of the Kossel curves, we are able to deduce that nitrided Pd/Y multilayers exhibit much less layer intermixing than the non-nitrided multilayers. The experimental results show that it is possible to distinguish by the shape of Kossel curves of multilayers with B4C barrier layers located in different interfaces. This demonstrates that Kossel diffraction is structural sensitive.

Competing mechanisms on the strength of ion-irradiated Zr/Nb nanoscale multilayers: Interface strength versus radiation hardening

The structural stability and mechanical properties of sputter-deposited Zr/Nb nanoscale multilayers subjected to Si-ion irradiation were investigated in relation to the individual layer thickness. The interface density distribution played a major role on the nature and amount of accumulated radiation damage. The multilayer with a smaller periodicity experienced a significantly higher atomic-scale disorder and radiation hardening compared to the multilayer with thicker individual layers. In the latter case, an enhanced radiation damage tolerance was achieved due to the balance between competing deformation mechanisms.

Exothermic Reaction Kinetics in High Energy Density Al-Ni with Nanoscale Multilayers Synthesized by Cryomilling

The Al-Ni system is known as a high energy density materials (HEDM) because of its highly exothermic nature during intermetallic compound (IMC) formation. In this study, elemental Al and Ni powder were milled to explore the effect of cryomilling atmosphere on the microstructure and exothermic behavior. Scanning electron microscope (SEM) observations show continuous structural refinement up to 8 h of cryomilling. No IMC phase was detected in the X-ray diffraction (XRD) spectrum. Differential thermal analyzer (DTA) results show two exothermic peaks for 8 h cryomilled powder as compared to that of powder milled for 1 h. The ignition temperature of prepared powder mixture also decreased due to gradual structural refinement. The activation energy was also calculated and correlated with the DTA and SEM results. The cryomilled Al-Ni powder is composed of fine Al-Ni metastable junctions which improve the reactivity at a lower exothermic reaction temperature.

A Robust in situ TEM Experiment for Characterizing the Fracture Toughness of the Interface in Nanoscale Multilayers

A novel in situ transmission electron microscopy (TEM) bending method using a nano-cantilever specimen that includes a naturally sharp pre-crack at the interface between a 500 nm-thick SiN layer and a 200 nm-thick Cu layer on a Si substrate is developed in order to precisely characterize the fracture toughness of the interface in nanoscale multilayers. By fabricating a perpendicular nanoscale notch in the SiN layer close to the horizontal Cu/SiN interface, a sharp pre-crack is successfully introduced at the Cu/SiN interface. In addition, by changing the relative position of the notch with respect to the fixed end of the specimen, both the instant and continuous interface crack propagation behaviors could be in situ observed using TEM. Finite element analysis shows that the crack propagation from the sharp pre-crack is dominated by a singular stress field within a region 100 nm from the crack tip under a mixed-mode state in all specimens. On the other hand, the fracture toughness represented by the critical energy release rate for the start of crack propagation along the Cu/SiN interface in all specimens is determined through a compliance method and shows good agreement with an average value of 7.1 J/m2. This indicates the robust reliability and high precision for characterizing the fracture toughness of the interface in nanoscale multilayers.

Inkjet Printing Based Layer‐by‐Layer Assembly Capable of Composite Patterning of Multilayered Nanofilms

AbstractSurface modification involves developing a versatile thin film by combining the physical, chemical, or biological characteristics of the functional materials and can facilitate controlling material for desirable aims. Layer‐by‐layer (LbL) assembly can be used to create materials with controlled thicknesses and morphologies, diverse functionalities, and unique structures on any surface. However, despite the advantages of the LbL fabrication technique, there are limits to its application because it is a time‐consuming process and has difficulty controlling the shape of nanofilms. In addition, controlling the lateral organization is difficult because the preparation methods are based on one‐pot self‐assembly. In this study, a multilayered fabrication system is developed for the high‐throughput LbL assembly of nanofilms through inkjet printing. With various types of materials from synthetic polymer to graphene oxide to natural polymer and protein, the approach can tune the preparation of nanoscale multilayers with desired structures and shapes for specific applications on various substrates, including a silicon wafer, quartz glass, and cellulose‐based paper.

Structure and tribological behavior of Pb-Ti/MoS2 nanoscaled multilayer films deposited by magnetron sputtering method

The Pb-Ti/MoS2 nanoscaled multilayer films with different bilayer period were deposited by unbalanced magnetron sputtering system. The morphology, microstructure, mechanical and tribological properties of the films were investigated. It was found that the film changed from multilayer structure to composite structure as the bilayer period decreased from 25nm to 6nm, due to the diffusion effect. The multilayer film showed a pronounced (002) diffraction peak, the growth of the MoS2 platelets below the interface were affected by Pb and Ti, and the c-axis of MoS2 platelets were inclined to the substrate at an angle of −30° to 30°. The hardness of the film ranged from 5.9 to 7.2GPa depending on the bilayer period. The tribological behavior of the films was performed under vacuum, and the friction coefficient were typically below 0.25. Furthermore, the nanoscale multilayer film with a bilayer period of 20nm exhibits much better mechanical and tribological properties than pure MoS2. The result indicates that the nanoscale multilayer is a design methodology for developing high basal plane oriented and vacuum solid lubricating MoS2 based materials.

Effect of layer thickness on the mechanical behaviour of oxidation-strengthened Zr/Nb nanoscale multilayers

The mechanical behaviour and deformation mechanisms of magnetron-sputtered Zr/Nb nanoscale multilayers were analysed as a function of the periodicity (L = 10 and 75 nm) and annealing time at 350C (2-336 hrs). The strength of the as-deposited multilayers was independent of the layer thickness and it was controlled by the co-deformation of the Zr and Nb layers. Annealing led to transformation of the Zr layers into ZrO2 after a few hours, while the Nb layers oxidised at a much slower rate. The volumetric expansion associated with the oxidation led to the formation of cracks at the interfaces and within the ZrO2 layers for the multilayers with L = 75 nm but not in the case of L = 10 nm. The nanoindentation hardness increased significantly after annealing due to the contribution of the residual stresses associated with the volume increase due to oxidation and to the higher strength of the oxides. The strength increase after annealing, as measured by micropillar compression tests, was smaller than that measured by nanoindentation, as it did not include the contribution of the residual stresses, which were relieved during micropillar fabrication. The nanolaminate with L = 10 nm presented the highest strength and toughness as damage during oxidation was suppressed, and a deformation mechanism controlled by the formation of shear bands.

Thermal stability and oxidation resistance of ZrSiN nanocomposite and ZrN/SiNx multilayered coatings: A comparative study

In the present work we comparatively study the thermal stability and oxidation resistance of ~300nm thick Zr-Si-N coatings with either 2D or 3D interface geometry: 1) Zr-Si-N nanocomposites and 2) ZrN/SiNx nanoscale multilayers. Both types of films were prepared by reactive magnetron sputter-deposition on Si wafers under Ar+N2 plasma discharges. Zr-Si-N films were deposited by co-sputtering from Zr and Si targets at substrate temperature Tdep of 600°C, with Si content ranging from 0 to 22.1at.%, while ZrN/SiNx multilayers with ZrN (resp. SiNx) layer thickness varying from 2 to 40nm (resp. 0.4 to 20nm) were synthesized by sequential sputtering from elemental Zr and Si3N4 targets at Tdep=300°C. According to transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis the microstructure of Zr-Si-N films changes from dual-phase nanocomposite structure, consisting of ZrN nanograins (4–7nm) surrounded by an amorphous tissue, towards X-ray amorphous with increasing Si content. The multilayered films consist of nanocrystalline (002)-oriented ZrN and amorphous SiNx layers. The structural evolution has been investigated by XRD after vacuum annealing at 1000°C, while the oxidation resistance under air was studied using in situ XRD in the temperature range from 400 to 950°C, as well as by scanning electron microscopy (SEM) and wavelength dispersive X-ray spectrometry (WDS) after air annealing procedure. While the reference ZrN film starts to oxidize at Tox.=550°C, a much higher oxidation resistance is found for multilayered films, till Tox.=860–950°C for ZrN/SiNx coatings with the elementary layer thickness ratio of 5nm/10nm, 3nm/5nm and 2nm/5nm. ZrSiN nanocomposites exhibit an improved oxidation resistance with increasing Si content compared to binary ZrN compound, but their stability is worst comparatively to the multilayers case.

보론/티타늄 나노박막다층 내 이종금속간 화학반응 전파특성 해석연구

빠른 반응성 및 자체전파특성을 가지는 보론/티타늄 나노 다층박막구조를 대상으로 박막층 수평방향으로의 이종금속간 화학반응 및 화염 전파현상 해석 모델링을 수립하였다. 이종금속간 화학반응은 Arrhenius 반응식을 가정하여 모델링하였으며, 열 및 화학종 확산, 발열 화학반응에 따른 화염 자체전파 현상에 대하여 2차원적 전산해석을 수행하였다. 보론 및 티타늄 박막층의 두께 및 두께비 등 나노구조 형상의 영향을 비롯하여 접촉층 예혼합 정도가 화염 자체전파속도에 미치는 영향을 분석하였다. The analytical modeling has been established on the self-propagation of intermetallic reaction in the spanwise direction of highly reactive boron and titanium nanoscale multilayers. Assuming that the reaction obeys Arrhenius kinetics, two-dimensional computations are carried out for heat and atomic species diffusion with exothermic reaction model in order to simulate the self-propagation of intermetallic reaction. The effects of bimetallic layer thickness and thickness ratio on the reaction propagation speed are tested and discussed in addition to the assessment of pre-mixing zone effects.

Analysis of self-propagating intermetallic reaction in nanoscale multilayers of binary metals

Nanoscale multilayers of two different metals could exhibit super-fast intermetallic reaction wave that accompanies high level of exothermic heat release, while additional advantage is a very small ignition delay. They could be a promising candidate for the core technology in realizing micron-sized initiation device for explosives detonation or propellants ignition in various defense and civilian applications. This numerical investigation focuses on the numerical modeling and computations of the ignition and self-propagating reaction behaviors in nanoscale intermetallic multilayer structures made of alternating binary metal layers of boron and titanium. Due to thin film nature of metallic multilayers, intermetallic reaction propagation across the repeating bimetallic multilayers is approximated to the one-dimensional transient model of thermal diffusion and atomic species diffusion, and the intermetallic reaction between two metal species is assumed to follow Arrhenius dependence on temperature. The computational results show the details of ignition and propagation characteristics of intermetallic reaction wave by evaluating and discussing the effects of key parameters, such as multilayer thickness, excess of one metal species, and presence of atomic premixing at interface of boron and titanium layers, on ignition delay and propagation speed of self-sustaining reaction wave.

Layer-by-layer self-assembled multilayers on PEEK implants improve osseointegration in an osteoporosis rabbit model

This study aims to fabricate and deposit nanoscale multilayers on polyetheretherketone (PEEK) to improve cell adhesion and osseointegration. Bio-activated PEEK constructs were designed with prepared surface of different layers of polystyrene sulfonate (PSS) and polyallylamine hydrochloride (PAH) multilayers. Irregular morphology was found on the 5 and 10-layer PEEK surfaces, while “island-like” clusters were observed for 20-layer (20 L) multilayers. Besides, the 20 L PEEK showed more hydrophilic feature than native PEEK, and the surface contact angle reduced from 39.7° to 21.7° as layers increased from 5 to 20. In vitro, modified PEEK allowed excellent adhesion and proliferation of bone marrow stromal cells, and induced higher cell growth rate and alkaline phosphatase level. In vivo, this bio-active PEEK exhibited significantly enhanced integration with bone tissue in an osteoporosis rabbit model. This work highlights layer-by-layer self-assembly as a practical method to construct bio-active PEEK implants for enhanced osseointegration.

Selective oxidation-induced strengthening of Zr/Nb nanoscale multilayers

The paper presents a new approach, based on controlled oxidation of nanoscale metallic multilayers, to produce strong and hard oxide/metal nanocomposite coatings with high strength and good thermal stability. The approach is demonstrated by performing long term annealing on sputtered Zr/Nb nanoscale metallic multilayers and investigating the evolution of their microstructure and mechanical properties by combining analytical transmission electron microscopy, nano-mechanical tests and finite element models. As-deposited multilayers were annealed at 350 °C in air for times ranging between 1 and 336 h. The elastic modulus increased by ∼20% and the hardness by ∼42% after 15 h of annealing. Longer annealing times did not lead to changes in hardness, although the elastic modulus increased up to 35% after 336 h. The hcp Zr layers were rapidly transformed into monoclinic ZrO2 (in the first 15 h), while the Nb layers were progressively oxidised, from top surface down towards the substrate, to form an amorphous oxide phase at a much lower rate. The sequential oxidation of Zr and Nb layers was key for the oxidation to take place without rupture of the multi-layered structure and without coating spallation, as the plastic deformation of the metallic Nb layers allowed for the partial relieve of the residual stresses developed as a result of the volumetric expansion of the Zr layers upon oxidation. Moreover, the development of residual stresses induced further changes in mechanical properties in relation to the annealing time, as revealed by finite element simulations.

Interface structure in nanoscale multilayers near continuous-to-discontinuous regime

Interfacial atomic diffusion, reaction, and formation of microstructure in nanoscale level are investigated in W/B4C multilayer (ML) system as functions of thickness in ultrathin limit. Hard x-ray reflectivity (XRR) and x-ray diffuse scattering in conjunction with x-ray absorption near edge spectroscopy (XANES) in soft x-ray and hard x-ray regimes and depth profiling x-ray photoelectron spectroscopy (XPS) have been used to precisely evaluate detailed interfacial structure by systematically varying the individual layer thickness from continuous-to-discontinuous regime. It is observed that the interfacial morphology undergoes an unexpected significant modification as the layer thickness varies from continuous-to-discontinuous regime. The interfacial atomic diffusion increases, the physical density of W layer decreases and that of B4C layer increases, and further more interestingly the in-plane correlation length decreases substantially as the layer thickness varies from continuous-to-discontinuous regime. This is corroborated using combined XRR and x-ray diffused scattering analysis. XANES and XPS results show formation of more and more tungsten compounds at the interfaces as the layer thickness decreases below the percolation threshold due to increase in the contact area between the elements. The formation of compound enhances to minimize certain degree of disorder at the interfaces in the discontinuous region that enables to maintain the periodic structure in ML. The degree of interfacial atomic diffusion, interlayer interaction, and microstructure is correlated as a function of layer thickness during early stage of film growth.

Reactions in Electrodeposited Cu/Sn and Cu/Ni/Sn Nanoscale Multilayers for Interconnects.

Miniaturization of electronic devices has led to the development of 3D IC packages which require ultra-small-scale interconnections. Such small interconnects can be completely converted into Cu-Sn based intermetallic compounds (IMCs) after reflow. In an effort to improve IMC based interconnects, an attempt is made to add Ni to Cu-Sn-based IMCs. Multilayer interconnects consisting of stacks of Cu/Sn/Cu/Sn/Cu or Cu/Ni/Sn/Ni/Sn/Cu/Ni/Sn/Ni/Cu with Ni = 35 nm, 70 nm, and 150 nm were electrodeposited sequentially using copper pyrophosphate, tin methanesulfonic, and nickel Watts baths, respectively. These multilayer interconnects were investigated under room temperature aging conditions and for solid-liquid reactions, where the samples were subjected to 250 °C reflow for 60 s and also 300 °C for 3600 s. The progress of the reaction in the multilayers was monitored by using X-ray Diffraction, Scanning Electron Microscope, and Energy dispersive X-ray Spectroscopy. FIB-milled samples were also prepared for investigation under room temperature aging conditions. Results show that by inserting a 70 nanometres thick Ni layer between copper and tin, premature reaction between Cu and Sn at room temperature can be avoided. During short reflow, the addition of Ni suppresses formation of Cu3Sn IMC. With increasing Ni thickness, Cu consumption is decreased and Ni starts acting as a barrier layer. On the other hand, during long reflow, two types of IMC were found in the Cu/Ni/Sn samples which are the (Cu,Ni)6Sn5 and (Cu,Ni)3Sn, respectively. Details of the reaction sequence and mechanisms are discussed.