Quasi-blazed type multilayer zone plate for X-rays

In order to attain high diffraction efficiency in high-energy X-ray region, we have developed multilevel-type (6-step) multilayer FZPs with the diameter of 70 μm, which composed of concentric multilayers of alternating high-Z (Cu), low-Z (Al), and four types of composite materials (Cu, Al) layers. Such a multilevel-type FZP with high diffraction efficiency contributes the reduction of the radiation damage to biological specimens, the simplification of the X-ray optical system. Some FZPs are fabricated and their diffraction efficiencies were evaluated at the beamline of SPring-8. For one FZP, the peak efficiency for the 1st-order diffraction of 51% has been obtained at 70 keV. The efficiencies higher than 40% have been achieved in the wide energy range of 70-90 keV. That for the 2nd-order diffraction of 46% has been obtained at 37.5 keV. For another FZP, the peak efficiency for the 1st-order diffraction of 52% has been obtained at 41.3 keV. The efficiencies higher than 45% have been achieved in the wide energy range of 33-49.5 keV.     

Fabrication and testing of sputtered-sliced kinoform style Fresnel zone plate

The Fresnel zone plate (FZP) is a type of lens for focusing X-rays. We have fabricated a kinoform style FZP with a 30-step structure composed of concentric multilayer of alternating Cu layer, Al layer, and 28 composite material (Cu, Al) layers. The multilayer was deposited using a magnetron sputtering apparatus with two DC-sputtering guns. The focusing characteristics were evaluated at the synchrotron radiation beamline of SPring-8, and the focused beam size measured by knife-edge scanning was 0.8 μm at 40 keV. The peak diffraction efficiencies measured using ion chambers for 1st- and 2nd-order diffraction were 42% and 12% at 40 keV and 20 keV, respectively. High-order X-ray diffraction was also examined using the data obtained from a CCD camera.     

Multilevel-type multilayer X-ray lens (Fresnel zone plate) by sputter deposition

We have developed a multilevel-type multilayer X-ray lens (Fresnel zone plate, FZP) using sputter deposition. Such a multilevel-type FZP can attain high diffraction efficiency which results in the reduction of radiation damage to biological specimens and the simplification of the X-ray optical system because unwanted diffraction orders are considerably suppressed. Previously, we have reported the effectiveness (i.e., realizing high diffraction efficiency) of a multilevel multilayer FZP with 4-step structure. This paper presents two experimental results on the FZP: (1) the focusing test of a multilayer FZP with 6-step structure in order to realize higher efficiency and (2) the change over time of the focusing characteristic of the FZP with 4-step structure. For (1), the diffraction efficiency of the 1st order focus and the focused beam size measured by knife-edge scanning were found to be more than 50% and 0.8 μm, respectively, at 41.3 keV, and superior to the previous results. For (2), no significant differences have been observed: it can be said that the multilevel FZP is stable at least for 9 months.     

New approaches to fabrication of multilayer Fresnel zone plate for high-energy synchrotron radiation X-rays

A multilayer (sputtered-sliced) Fresnel zone plate (FZP) is one of the promising focusing optics with high spatial resolution for the high-energy X-ray region. This is because a large “aspect ratio” can be realized easily. In addition, it is important that the kinoform FZP (theoretical diffraction efficiency=100%) can be fabricated by the sputtered-sliced method. This paper presents the experimental results of two new approaches for fabrication of a multilayer FZP for X-rays. (1) To achieve higher diffraction efficiency, a multilevel-type (4-step: quasi-kinoform type) FZP was fabricated. This FZP was composed of concentric multilayers of alternating high-Z, low-Z, and composite materials. The composite material layer was deposited by co-sputtering of high-Z and low-Z materials. (2) To achieve smoother zones (multilayer interfaces) at the conventional-type FZP, each target of a sputtering apparatus with two DC-sputtering guns was surrounded by a cover with an aperture, and Ar gas was supplied inside the cover, which led to the deposition at lower Ar gas pressure. As a result, for the former, the efficiency was improved markedly as compared with conventional FZP, and for the latter, the zone roughness was reduced, which has resulted in the improvement of the spatial resolution of the FZP.     

Observation of kinoform-style multilayer Fresnel zone plate by scanning ion microscopy

We investigated a kinoform-style Fresnel zone plate (FZP) that is a high-efficient optical element for hard X-ray focusing. The Cu/Al kinoform-style FZPs were fabricated with a sputtered-sliced method. The FZP was composed of 450 layers (30 layers, 15 pairs) of Al, Cu/Al composite, and Cu. The microstructure of the Cu/Al composite layer was observed by scanning ion microscopy based on a focused ion beam (FIB). In the Cu/Al composite layer, the SIM images obtained by grain orientation contrast observation indicated that the Cu grains were grown gradually with increasing Cu concentration.     

Microstructure and magnetic properties of electrodeposited Co/Cu multilayer nanowire arrays

Highly uniform Co/Cu multilayer nanowire arrays had been electrodeposited into the nanochannels of porous anodic aluminum oxide template. X-ray diffraction pattern showed that Co and Cu grow in their HCP and FCC structures, respectively. Each nanowire had the same length with 20 μm and the diameter with 50 nm. The thickness of Co was 50 nm and Cu layer was about 5 nm. Magnetic measurements of the nanowire arrays showed that the magnetic coercivity for the applied field parallel to the nanowires is larger than that perpendicular to the anowires. The magnetic coercivity of Co multilayer nanowire arrays is smaller than that of the Co/Cu nanowire arrays and the crystal direction of Co layers were not obviously affected by Cu layer. The Co/Cu nanowire arrays exhibited excellent Giant Magneto Resistive ratio of about 75%.     

Interface stress induced hardness enhancement and superelasticity in polytetrafluoroethylene/metal multilayer thin films

Polytetrafluoroethylene (PTFE)/Al, PTFE/Cu, and PTFE/Ti multilayer thin films have been deposited in order to investigate effects of interface energy on mechanical properties. PTFE, which has a low surface energy of 19.2 mJ/m², was used to introduce a large interface energy into multilayer thin films. PTFE thin film was deposited by rf magnetron sputtering using a PTFE sheet target. Al, Cu, and Ti were deposited by dc magnetron sputtering. The multilayer thin films were fabricated sequentially without breaking vacuum. Substrate used was aluminosilicate glass. The modulation period was changed from 6.7 to 200 nm. The total thickness was about 200 nm for all samples. The internal stress of metal layers changed from tensile to compressive and increased with decreasing modulation period for all of PTFE/Al, PTFE/Cu, and PTFE/Ti. Both hardness enhancement and superelasticity were observed in the results of nanoindentation measurements. The energy dissipated during nanoindentation process (one load and unload cycle) decreased with decreasing modulation period. The minimum value of the ratio of dissipated/loaded energy was < 40%, which is smaller than the values obtained for monolithic PTFE or metal films (about 73% for PTFE and 87% for Al, 72% for Cu, and 71% for Ti, respectively). This meant that the PTFE/metal nano-multilayer thin films became more elastic with decreasing modulation period. The tendency of change in the mechanical properties strongly correlated to internal stress. Mechanisms involved in anomalous behaviors in film hardness and elasticity were discussed based on the relationship to interface energy, interface stress, and internal stress, induced by multilayering of the films. It is concluded that a large compressive stress introduced in the thin films increased the energy needed to deform elastically or plastically the thin film during indentation, resulting in the increase in hardness and elasticity. The nanoindentation analysis of the multilayer thin films emphasized that in PTFE/metal multilayer thin films mechanical properties of the films depend on interface stress induced by the accumulated interface energy, being independent of bulk materials properties composing thin films, resulting in increase in hardness and elasticity.     

Self-forming AlOx layer as Cu diffusion barrier on porous low-k film

The copper diffusion barrier properties of an ultrathin self-forming AlO_x layer on a porous low-k film have been investigated. Cu-3 at.% Al alloy films were directly deposited onto porous low-k films by co-sputtering, followed by annealing at various temperatures. Transmission electron microscopy micrographs showed that a ∼ 5 nm layer self-formed at the interface after annealing. X-ray photoelectron spectroscopy analysis showed that this self-formed layer was Al₂O₃. Sharp declines of the Cu and Si concentrations at the interface indicated a lack of interdiffusion between Cu and the porous low-k film for annealing up to 600 °C for 30 min. The leakage currents from Cu(Al)/porous low-k/Si structures were similar to as-deposited films even after a 700 °C, 5 min anneal while a Cu sample without Al doping failed at lower temperatures. Adding small amounts of Al to bulk Cu is an effective way to self-form copper diffusion layer for advanced copper interconnects.     

ZnO/Cu/ZnO multilayer films: Structure optimization and investigation on photoelectric properties

A series of ZnO/Cu/ZnO multilayer films has been fabricated from zinc and copper metallic targets by simultaneous RF and DC magnetron sputtering. Numerical simulation of the optical properties of the multilayer films has been carried out in order to guide the experimental work. The influences of the ZnO and Cu layer thicknesses, and of O₂/Ar ratio on the photoelectric and structural properties of the films were investigated. The optical and electrical properties of the multilayers were studied by optical spectrometry and four point probe measurements, respectively. The structural properties were investigated using X-ray diffraction. The performance of the multilayers as transparent conducting coatings was compared using a figure of merit. In experiments, the thickness of the ZnO layers was varied between 4 and 70 nm and those of Cu were between 8 and 37 nm. The O₂/Ar ratios range from 1:5 to 2:1. Low sheet resistance and high transmittance were obtained when the film was prepared using an O₂/Ar ratio of 1:4 and a thickness of ZnO (60 nm)/Cu (15 nm)/ZnO (60 nm).     

Characterization of Al/Ni multilayers and their application in diffusion bonding of TiAl to TiC cermet

The Al/Ni multilayers were characterized and diffusion bonding of TiAl intermetallics to TiC cermets was carried out using the multilayers. The microstructure of Al/Ni multilayers and TiAl/TiC cermet joint was investigated. The layered structures consisting of a Ni₃(AlTi) layer, a Ni₂AlTi layer, a (Ni,Al,Ti) layer and a Ni diffusion layer were observed from the interlayer to the TiAl substrate. Only one AlNi₃ layer formed at the multilayer/TiC cermet interface. The reaction behaviour of Al/Ni multilayers was characterized by means of differential scanning calorimeter (DSC) and X-ray diffraction. The initial exothermic peak of the DSC curve was formed due to the formation of Al₃Ni and Al₃Ni₂ phases. The reaction sequence of the Al/Ni multilayers was Al₃Ni → Al₃Ni₂ → AlNi → AlNi₃ and the final products were AlNi and AlNi₃ phases. The shear strength of the joint was tested and the experimental results suggested that the application of Al/Ni multilayers improved the joining quality.     

Effects of the substrate temperature on the Cu seed layer formed using atomic layer deposition

Cu has replaced Al as the main interconnection material in ultra-large integrated circuits, reducing resistance capacitance delay and yielding higher electro-migration reliability. As feature size decreases, however, it has become more difficult to produce reliable Cu wiring. We studied a Cu seed layer deposited using plasma enhanced atomic layer deposition (PEALD). The electrical properties of the PEALD Cu thin film with sub-10 nm thickness were determined by the continuities and morphologies of the films. At a deposition temperature of 150 °C, the resistivity of Cu thin films was 5.2 μΩ-cm and the impurity content was below 5 atomic %. Based on these results, Cu seed layers were deposited on 32-nm Ta/SiO2 trench substrates, and electrochemical plating was performed under conventional conditions. A continuous seed layer was deposited using PEALD, resulting in a perfectly filling of the 32-nm sized trench.     

Annealing effects on microstructure and mechanical properties of sputtered multilayer Cr(1 − x)AlxN films

Multilayer Cr_(1 − x)Al_xN films with a total thickness of 2 μm were deposited on high-speed steel by medium frequency magnetron sputtering from Cr and Al-Cr (70 at.% Al) targets. The samples were annealed in air at 400 °C, 600 °C, 800 °C and 1000 °C for 1 hour. Films were characterized by cross-sectional scanning electron microscopy and X-ray diffraction analysis. The grain size of the as-deposited multilayer films is about 10 nm, increasing with the annealing temperature up to 100 nm. Interfacial reactions have clearly changed at elevated annealing temperatures. As-deposited films' hardness measured by nanoindentation is 22.6 GPa, which increases to 26.7 GPa when the annealing temperature goes up to 400 and 600 °C, but hardness decreases to 21.2 GPa with further annealing temperature increase from 600 to 1000 °C. The multilayer film adhesion was measured by means of the scratch test combined with acoustic emission for detecting the fracture load. The critical normal load decreased from 49.7 N for the as-deposited films to 21.2 N for the films annealed at 1000 °C.     

Conductive Ga doped ZnO/Cu/Ga doped ZnO thin films prepared by magnetron sputtering at room temperature for flexible electronics

Ga doped ZnO(GZO)/Cu/GZO multilayers were deposited by magnetron sputtering on polycarbonate substrates at room temperature. We investigated the structural, electrical, and optical properties of multilayers at various thicknesses of Cu and GZO layers. The lowest resistivity value of 3.3 × 10^− 5 Ω cm with a carrier concentration of 2.9 × 10²² cm^− 3 was obtained at the optimum Cu (10 nm) and GZO (10 nm) layer thickness. The highest value of figure of merit φ_TC is 2.68 × 10^− 3 Ω^− 1 for the GZO (10 nm)/Cu(10 nm)/GZO(10 nm) multilayer. The highest average near infrared reflectivity in the wavelength range 1000-2500 nm is as high as 70% for the GZO(10 nm)/Cu(10 nm)/GZO(10 nm) multilayer.     

High temperature oxidation behavior of CrN/AlN superlattice films

The oxidation behavior of CrN/AlN superlattice films with different bilayer periods (Λ), Al/(Cr + Al) ratios, and crystal structures of the AlN layer was investigated. The films were deposited using a pulsed dc closed field unbalanced magnetron sputtering system. The oxidation tests were carried out in the ambient air at elevated temperatures from 700 to 1100 °C for 1 h. The changes in the crystal phase, microstructure and hardness of the films after the oxidation tests were characterized using X-ray diffraction, scanning electron microscopy and nanoindentation, respectively. When both CrN and AlN layers were in the NaCl cubic structure, the film with Λ = 3.8 nm and an Al/(Cr + Al) ratio of 0.6 exhibited a superior oxidation resistance than the film with Λ = 12.4 nm and an Al/(Cr + Al) ratio of 0.19. The film with Λ = 3.8 nm maintained the nanolayered structure with an oxidation temperature up to 1000 °C by the protection of a thin and dense X-ray amorphous oxide layer. In contrast, when the AlN layers were in the Wurzite hexagonal structure, the film with Λ = 22.5 nm and an Al/(Cr + Al) ratio of 0.67 exhibited poor oxidation resistance. The film lost the superlattice structure at 800 °C and was completely oxidized at 1000 °C due to the formation of a porous crystalline oxide layer on the surface.     

Study of structural, electrical, optical, thermoelectric and photoconductive properties of S and Al co-doped SnO2 semiconductor thin films prepared by spray pyrolysis

In this paper, the effect of S and Al concentrations on the structural, electrical, optical, thermoelectric and photoconductive properties of the films was studied. The [Al]/[Sn] and [S]/[Sn] atomic ratios in the spray solutions were varied from 10 at.% to 40 at.% and 0 to 50 at.%, respectively. X-ray diffraction analysis showed the formation of SnO₂ cassiterite phase as a main phase and the numerous sulfur phases including S, SnS, SnS₂ and Sn₂S₃ in SnO₂:Al films. Scanning electron microscopy studies showed that in the absence of S, increasing the Al content results in a smaller grain size and with the addition of S, the films appear to contain small cracks and nodules. The minimum resistance of 0.175 (kΩ/□) was obtained for S-doped SnO₂:Al (40 at.%) film with 20 at.% S-doping. From the Hall effect measurements, the majority carrier concentration was obtained in order of 10¹⁷-10¹⁸ cm^− 3. The thermoelectric measurements showed that majority carriers change from electrons to holes for S-doping in SnO₂:Al (40 at.%) thin films. The maximum Seebeck coefficient of + 774 μV/K (at T = 370 K) was obtained for S-doped SnO₂:Al (10 at.%) film with 50 at.% S-doping. The band gap values were obtained in the range of 3.8-4.2 eV. The S-doped SnO₂:Al (40 at.%) films have shown considerably photoconductivity more than S-doped SnO₂:Al (10 at.%) with increasing S-doping. The best photoconductive property was obtained for co-doped SnO₂ thin film with 40 at.% Al and 5 at.% S concentration in solution.     

CrN/AlN superlattice coatings synthesized by pulsed closed field unbalanced magnetron sputtering with different CrN layer thicknesses

CrN/AlN superlattice coatings with different CrN layer thicknesses were prepared using a pulsed closed field unbalanced magnetron sputtering system. A decrease in the bilayer period from 12.4 to 3.0 nm and simultaneously an increase in the Al/(Cr + Al) ratio from 19.1 to 68.7 at.% were obtained in the CrN/AlN coatings when the Cr target power was decreased from 1200 to 200 W. The bilayer period and the structure of the coatings were characterized by means of low angle and high angle X-ray diffraction and transmission electron microscopy. The mechanical and tribological properties of the coatings were studied using the nanoindentation and ball-on-disc wear tests. It was found that CrN/AlN superlattice coatings synthesized in the current study exhibited a single phase face-centered cubic structure with well defined interfaces between CrN and AlN nanolayers. Decreases in the residual stress and the lattice parameter were identified with a decrease in the CrN layer thickness. The hardness of the coatings increased with a decrease in the bilayer period and the CrN layer thickness, and reached the highest value of 42 GPa at a bilayer period of 4.1 nm (CrN layer thickness of 1.5 nm, AlN layer thickness of 2.5 nm) and an Al/(Cr + Al) ratio of 59.3 at.% in the coatings. A low coefficient of friction of 0.35 and correspondingly low wear rate of 7 × 10^− 7 mm³N^− 1m^− 1 were also identified in this optimized CrN/AlN coating when sliding against a WC-6%Co ball.     

Dielectric/metal/dielectric structures using copper as metal and MoO3 as dielectric for use as transparent electrode

Transparent conductive oxide/metal/oxide, where the oxide is MoO₃ and the metal is Cu, is realized and characterized. The films are deposited by simple joule effect. It is shown that relatively thick Cu films are necessary for achieving conductive structures, what implies a weak transmission of the light. Such large thicknesses are necessary because Cu diffuses strongly into the MoO₃ films. We show that the Cu diffusion can be strongly limited by sandwiching the Cu layer between two Al ultra-thin films (1.4 nm). The best structures are glass/MoO₃ (20 nm)/Al (1.4 nm)/Cu (18 nm)/Al (1.4 nm)/MoO₃ (35 nm). They exhibit a transmission of 70% at 590 nm and a resistivity of 5.0 · 10^− 4 Ω cm. A first attempt shows that such structures can be used as anode in organic photovoltaic cells.     

Null-ellipsometry investigations of the optical properties and diffusion processes in spin-valve structures based on Co and Cu

The influence of annealing temperature (T_a = 300-900 K) on optical properties of the Au (4 nm)/Co (3 nm)/Cu (6-12 nm)/Co (20 nm)/SiO₂/Si spin-valve structures was studied. The model of Co, Au, and Cu atom interdiffusion was proposed based on the experimental data analysis. The formation of solid solutions at the thin layer interfaces Au/Co and Cu/Co was studied, and as a result the most intensive formation of solid solutions was identified at annealing temperature of T_a = 750 K. The optical parameters of the samples were calculated using the genetic algorithm. The spin-valve systems remain relatively unperturbed until 750 K, but the optical properties change significantly from 750 to 900 K. It can be explained by the formation of the interphase in multilayer thin film systems.     

Deposition of nano-scaled CrTiAlN multilayer coatings with different negative bias voltage on Mg alloy by unbalanced magnetron sputtering

In a magnetron sputtering system, the negative substrate bias voltage has been used as a basic process parameter to modify the deposition structure and properties of coatings. In this paper we report the effect of bias voltage ranging from −40 V to −90 V on nano-scaled CrN/TiN/CrN/AlN (CrTiAlN) multilayer coatings synthesized on a Mg alloy by a closed-field unbalanced magnetron sputtering ion plating system in a gas mixture of Ar + N₂. The technological temperature and atomic concentration in the multilayer coatings were controlled by adjusting the current density of different metal magnetron targets and the plasma optical emission monitor. The composition, crystallographic structure, deposition model and friction coefficient of multilayer coatings were characterized by X-ray photoelectron spectrometry (XPS), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and ball-on-disc testing. The experimental results show that the deposition model and friction coefficient of nano-scaled CrTiAlN multilayer coatings were significantly affected by the negative bias voltage (V_b). The nitride species in multilayer coatings mainly involve CrN, AlN and TiN, and XRD analysis shows that the crystallographic structure was face-centered cubic. Under different bias voltage conditions, the multilayer coating composition shows a fluctuation, and the Al and Cr concentrations respond in the opposite sense to the bias voltage, attaining their greatest values at V_b = −70 V. The surface and cross-sectional morphology shows deposition model change from a columnar model into non-columnar model with the increase in negative bias voltage. The friction coefficient of the nano-scaled multilayer coatings at V_b = −55 V stabilize after 10 000 cycles.     

Structural, optical and electrical properties of AZO/Cu/AZO tri-layer films prepared by radio frequency magnetron sputtering and ion-beam sputtering

Highly conducting tri-layer films consisting of a Cu layer sandwiched between Al-doped ZnO (AZO) layers (AZO/Cu/AZO) were prepared on glass substrates at room temperature by radio frequency (RF) magnetron sputtering of AZO and ion-beam sputtering of Cu. The tri-layer films have superior photoelectric properties compared with the bi-layer films (Cu/AZO, AZO/Cu) and single AZO films. The effect of AZO thickness on the properties of the tri-layer films was discussed. The X-ray diffraction spectra show that all films are polycrystalline consisting of a Cu layer with the cubic structure and two AZO layers with the ZnO hexagonal structure having a preferred orientation of (0 0 2) along the c-axis, and the crystallite size and the surface roughness increase simultaneously with the increase of AZO thickness. When the AZO thickness increases from 20 to 100 nm, the average transmittance increases initially and then decreases. When the fixed Cu thickness is 8 nm and the optimum AZO thickness of 40 nm was found, a resistivity of 7.92 × 10⁻⁵ Ω cm and an average transmittance of 84% in the wavelength range of visible spectrum of tri-layer films have been obtained. The merit figure (F_TC) for revaluing transparent electrodes can reach to 1.94 × 10⁻² Ω⁻¹.