HiPIMS ‐ Technologie und Anwendungsfelder

HiPIMS‐technology and field of application Starting wi^th the introduction of planar magnetron cathodes in the mid seventies magnetron sputtering has taken nearly all industrial branches, dealing wi^th thin film coatings, which are in assault. Numerous milestones within the last 30 years were set, whereas some of the most important were the development of rotary cathodes (?CMAG”?) and the introduction of pulsed plasmas. H igh P ower I mpulse M agnetron S puttering (HiPIMS) or H igh P ower P ulse M agnetron S puttering (HPPMS) is a further innovative step towards coatings wi^th superior quality. HiPIMS typically uses pulses in the megawatt range, resulting in power densities of 1000 W/cm² and higher (compared to typically 20 – 50 W/cm²). The major benefit of the new technology is a very high degree of ionised target material of 50 – 90%, leading to superior coating properties like high density, very smoo^th surfaces, and high refractive index for optical coatings. Besides the introduction in highly ionised pulse plasmas the potential of this new technology will be demonstrated by recent results of applied research for applications in different industrial branches.     

Reaktive Multischichtsysteme

Reactive Multilayer Systems as tailored heat sources for plastic bondings The use of reactive multilayer systems (RMS) as a heat source for the manufacturing of thermoplastic material bondings makes it possible to completely or partially overcome the limitations of conventional joining techniques, such as gluing or welding. The release of energy, which takes place directly inside the joining zone within milliseconds can be well adapted to the properties of the plastics. Thus undesired changes in the material structure of the joining partners can be avoided. Bonding strengths which are higher than or comparable to those of commercially used joining methods can be achieved. Furthermore, a particular advantage of RMS joining is that no surface pretreatment is required. RMS bondings of thermoplastics achieve high long-term stability for plastics, which themselves are only slightly susceptible to aging.     

In‐Situ‐Charakterisierung optischer Mehrschichtsysteme in Großflächen‐ Produktionsanlagen

The paper discusses approaches to the insitu analysis of optical multi‐layer coating stacks such as mirror coatings, AR coatings or lowE layer stacks on large‐area substrates in production environments. The stable production of complex layer systems requires in‐situ analysis systems that are able to provide spectral information and optical performance data, but also yield thickness information for individual layers and thus aide the operating staff in detailed analyzing deviations from the production target stack. Solutions incorporating in‐situ optical reflectance, transmittance and ellipsometry measurements wi^th optical data being collected not only for the completed layer stack, but also at intermediate coating stages, are discussed and the accuracy, robustness and stability of different measurement systems and computation strategies are compared.     

纳米结构多层膜自蔓延连接技术的研究及其应用

近年来,利用纳米结构多层膜自蔓延反应瞬间放热作为局部热源实现材料连接的方式逐渐受到人们的重视,其具有反应瞬间完成、连接效率高、适用于热敏感材料并且可以避免元器件从高温冷却时产生较大的热应力等特点。介绍了纳米结构多层膜的制备方法及反应机理,并综述和分析了在陶瓷/金属互连、不锈钢器件、非晶材料的连接以及微电子芯片技术方面的应用。     

Transparente Barriereschichten auf flexiblen Polymersubstraten

Transparent permeation barrier layers on flexible polymer substrates This paper reviews different vacuum based technologies for manufacturing transparent permeation barrier layers and layer stacks on flexible polymer substrates. With plasma assisted reactive evaporation, a cost‐efficient, highly productive process for food packaging applications is presented. Reactive dual magnetron sputtering is a technology for the deposition of oxide layers with a very low water vapor and oxygen transmission rate at a reasonable deposition rate. Many groups suggest multilayer stacks for the encapsulation of flexible electronic devices. In this paper, an all‐in‐vacuum inline concept for manufacturing such multilayers is presented. It is based on the combination of reactively sputtered barrier layers with interlayers grown by using a magnetron based PECVD process (Magnetron‐PECVD). Both, process parameters, such as deposition rate and process pressure, and important layer properties, such as morphology and the water vapor and oxygen transmission rate are compared for the different single and multi layer technologies.     

Stacked Ge nanocrystals with ultrathin SiO₂ separation layers

The aim of this work is the tailored growth of Ge nanocrystals (NCs) in (GeO(x)/SiO(2)) multilayers (ML) for photovoltaic applications. For this purpose the fabrication of regularly stacked Ge NCs separated by ultrathin SiO(2) layers is essential to enable charge carrier transport by direct tunnelling. In this paper we report on the fabrication of (GeO(x)/SiO(2))(50) multilayer stacks via reactive dc magnetron sputtering and Ge NCs formation after subsequent annealing. It is shown that magnetron sputtering allows us to deposit very regular ML stacks with a total thickness of about 300 nm, characterized by ultrathin (down to 1 nm) and very smooth (roughness ～ 0.6 nm) SiO(2) separation layers. A main challenge is to keep these properties for a thermal budget necessary to form Ge NCs. For this reason, the temperature dependence of phase separation. Ge crystallization and ML morphology was investigated by Rutherford backscattering, x-ray scattering, Raman spectroscopy and electron microscopy. The formation of size confined Ge NCs of about 5 nm after annealing of only 550?°C is confirmed. This low thermal budget ensures the suppression of GeO emanation and multilayer stability. Spectroscopic ellipsometry was applied to determine the optical Ge NC bandgap to (1.65 ± 0.5) eV.     

Effects of interfacial Al oxide layers: Control of reaction behavior in micrometer-scale Al/Ni multilayers

Exothermic reaction behaviors of compression-bonded Al–Ni multilayers are investigated through controlling the interfacial layers of the multilayers. The native interfacial Al oxide layers between the Al/Ni bilayers are intentionally preserved to induce a thermal explosion (TE) during slow heating with up to a few tens of K/min. In contrast, the thermal annealing (TA) occurs in the highly shear-deformed multilayers with many broken Ni layers because the ductile Al fills the gaps in the broken Ni layers to form reactive Al/Ni interfaces. Increased onset temperatures of 865–893 K and activation energies, 470 kJ/mol, are measured in the multilayers exhibiting the TE. The onset temperature is increased by 60–80 K over that of the multilayers exhibiting the TA. The influences of the interfacial native Al oxide layers that are preserved in order to delay the Al/Ni inter-diffusion on the exothermic reaction behavior of the compression-bonded multilayers are discussed.     

Diversity in Addressing Reaction Mechanisms of Nano‐Thermite Composites with a Layer by Layer Structure

The reaction mechanisms and microstructures of various layered nano‐thermite composites are investigated through characterization of their energetic properties. Migration of reactive components across the reaction zone is analyzed, which plays an important role in determining the process initiation, reaction propagation, and chemical stability at low temperatures. Distinct types of nanoparticles are deposited onto filter paper in a sequence, using the vacuum filtration method, which promotes intimate contact between neighboring reactive layers. Scanning Electron Microscopy (SEM) images demonstrate a well‐defined contact region between the two layers in the Al/CuO or Al/NiO composites. Differential Scanning Calorimetry (DSC) data shows that the thermite reaction occurs below the melting temperature of Al, resulting in rapid heat release, and improves reaction initiation. Elemental mapping results reveal the migration of Al, Ni/Cu, and oxygen before and after the thermite reaction, which is arranged during thermogravimetric analysis (TGA). This analysis indicates the dominant pathway of the thermite reaction in each composite, through either decomposition of the CuO nanoparticles in the Al/CuO composite or through direct migration of reactive components across the conducting surface within the Al/NiO composite.

     

Organic Field‐Effect Transistor Memory Devices Using Discrete Ferritin Nanoparticle‐Based Gate Dielectrics

Organic field‐effect transistor (OFET) memory devices made using highly stable iron‐storage protein nanoparticle (NP) multilayers and pentacene semiconductor materials are introduced. These transistor memory devices have nonvolatile memory properties that cause reversible shifts in the threshold voltage (V_th) as a result of charge trapping and detrapping in the protein NP (i.e., the ferritin NP with a ferrihydrite phosphate core) gate dielectric layers rather than the metallic NP layers employed in conventional OFET memory devices. The protein NP‐based OFET memory devices exhibit good programmable memory properties, namely, large memory window ΔV_th (greater than 20 V), a fast switching speed (10 μs), high ON/OFF current ratio (above 10⁴), and good electrical reliability. The memory performance of the devices is significantly enhanced by molecular‐level manipulation of the protein NP layers, and various biomaterials with heme Fe^III/Fe^II redox couples similar to a ferrihydrite phosphate core are also employed as charge storage dielectrics. Furthermore, when these protein NP multilayers are deposited onto poly(ethylene naphthalate) substrates coated with an indium tin oxide gate electrode and a 50‐nm‐thick high‐k Al₂O₃ gate dielectric layer, the approach is effectively extended to flexible protein transistor memory devices that have good electrical performance within a range of low operating voltages (<10 V) and reliable mechanical bending stability.     

Influence of substrate temperature on the materials properties of reactive DC magnetron sputtered Ti/TiN multilayered thin films

Ti/TiN multilayers were deposited by DC reactive magnetron sputtering method using a titanium target and an Ar-N₂ mixture discharge gas. XRD technique was employed to study the structure of the coatings and to observe the variations of structural parameters with substrate temperatures. An increase in grain size with increase of substrate temperature was observed. The components of Ti 2p doublet, related to TiN, TiON and TiO₂, were observed in the core-level spectra of the deposited multilayer films from XPS analysis. A microhardness value of 25.5 GPa was observed for Ti/TiN multilayers prepared at 400 °C. Electrical properties were found to depend on substrate temperature.     

Production and performance of multilayer-coated conical x-ray mirrors

A method of fabricating replica figured x-ray optics with integral multilayer coatings is presented. With the intact electroforming multilayer process (IEMP) technique, we sputter multilayers onto a reusable superpolished mandrel, electroform nickel over the multilayers, and remove the multilayer-coated nickel shell intact from the mandrel. This approach offers advantages over more traditional, original, and segmented-replica fabrication techniques, including low cost; compatibility with a wide range of mirror designs, diameters, and focal lengths; simple integration with multilayer sputtering processes; and the ability to produce complete shells of revolution. The fabrication of W/Si multilayer-coated 10-cm-diameter conical x-ray mirrors is described, as are reflectivity measurements at 10 and 30 keV. The measured reflectivity of the IEMP multilayers at the 10-keV primary Bragg peak was 17%. Measurements of multiple points on the cone showed multilayer uniformity to within a few percent around the mirror.     

Multifunctional lipid multilayer stamping

Nanostructured lipid multilayers on surfaces are a promising biofunctional nanomaterial. For example, surface-supported lipid multilayer diffraction gratings with optical properties that depend on the microscale spacing of the grating lines and the nanometer thickness of the lipid multilayers have been fabricated previously by dip-pen nanolithography (DPN), with immediate applications as label-free biosensors. The innate biocompatibility of such gratings makes them promising as biological sensor elements, model cellular systems, and construction materials for nanotechnology. Here a method is described that combines the lateral patterning capabilities and scalability of microcontact printing with the topographical control of nanoimprint lithography and the multimaterial integration aspects of dip-pen nanolithography in order to create nanostructured lipid multilayer arrays. This approach is denoted multilayer stamping. The distinguishing characteristic of this method is that it allows control of the lipid multilayer thickness, which is a crucial nanoscale dimension that determines the optical properties of lipid multilayer nanostructures. The ability to integrate multiple lipid materials on the same surface is also demonstrated by multi-ink spotting onto a polydimethoxysilane stamp, as well as higher-throughput patterning (on the order of 2 cm(2) s(-1) for grating fabrication) and the ability to pattern lipid materials that could not previously be patterned with high resolution by lipid DPN, for example, the gel-phase phospholipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) or the steroid cholesterol.     

Layer-by-layer design method for multilayers with barrier layers: application to Si/Mo multilayers for extreme-ultraviolet lithography

A previous layer-by-layer multilayer design method [J. Opt. Soc. Am. A 19, 385 (2002)] is completed by adding the possibility of alternating layers with fixed thicknesses along with layers whose thicknesses are optimized for the largest possible reflectance at a desired wavelength. The previous algorithm did not allow for layers with fixed thicknesses. The current formalism is particularly suited for a multilayer design in which barrier layers of given thicknesses are used to prevent diffusion and/or reaction between the multilayer constituents. The design method is also useful both when intermixing zones develop at multilayer interfaces and when capping layers are used. The algorithm allows the design of multilayers with complex barrier layers with any number of layers of any optical constants. The optimization can be performed either for normal incidence or for nonnormal incidence with either s- or p-polarized radiation. The completed method provides a fast and accurate procedure for multilayer optimization regardless of the number of different materials used in the multilayer. The optimum layer thickness is determined by means of functions suitable for implementation in a computer code. The performance of the current algorithm is exemplified through the design of Si/Mo multilayers with intermixing layers or with barrier layers that are optimized for the largest reflectance at 13.4 nm. The use of specific barrier layers on each multilayer interface is also discussed.     

R.F. sputtering system for the preparation of multilayer optical filters

Thin film multilayer optical filters are usually prepared by vacuum evaporation of successive layers. The deposition of thin films by sputtering has many advantages over the vacuum evaporation technique and hence it is employed for the fabrication of better quality optical filters. However, the filters may be more time consuming to prepare if a single-target sputtering system is used because two different materials are required for alternate layers. For the preparation of multilayer optical filters, a special r.f. sputtering jig arrangement with two target holders is fabricated. Using this the successive layers can be deposited in one pumpdown. A simple coupling arrangement used to match the r.f. generator output impedance to the load is explained. With all the sputtering parameters such as the pressure, the temperature and the power maintained constant except the time, control of the thickness of the multilayers is achieved. A calibration chart of sputtering time versus thickness of the materials to be deposited is prepared for TiO₂ and SiO₂ for the above purpose. Using this calibration chart, the deposition time of different layers of any optical filters based on these dielectric materials can be fixed to obtain optical filters of acceptable quality and reproducibility.     

Structure, hardness and thermal stability of TiAlN and nanolayered TiAlN/CrN multilayer films

TiAlN films were deposited on silicon (1 1 1) substrates from a TiAl target using a reactive DC magnetron sputtering process in Ar+N₂ plasma. Films were prepared at various nitrogen flow rates and TiAl target compositions. Similarly, CrN films were prepared from the reactive sputtering of Cr target. Subsequently, nanolayered TiAlN/CrN multilayer films were deposited at various modulation wavelengths (Λ). X-ray diffraction (XRD), energy dispersive X-ray analysis, nanoindentation and atomic force microscopy were used to characterize the films. The XRD confirmed the formation of superlattice structure at low modulation wavelengths. The maximum hardness of TiAlN/CrN multilayers was 3900 kg/mm², whereas TiAlN and CrN films exhibited maximum hardnesses of 3850 and 1000 kg/mm², respectively. Thermal stability of TiAlN and TiAlN/CrN multilayer films was studied by heating the films in air in the temperature range (T_A) of 500-900 °C for 30 min. The XRD spectra revealed that TiAlN/CrN multilayers were stable up to 800 °C and got oxidized substantially at 900 °C. On the other hand, the TiAlN films were stable up to 700 °C and got completely oxidized at 800 °C. Nanoindentation measurements performed on the films after heat treatment showed that TiAlN retained a hardness of 2200 kg/mm² at T_A=700 °C and TiAlN/CrN multilayers retained hardness as high as 2600 kg/mm² upon annealing at 800° C.     

Diffusion bonding of TiAl using Ni/Al multilayers

With the stimulus of temperature and pressure Ni and Al can quickly react and produce the intermetallic compound NiAl. This reaction is highly exothermic and high temperatures can be attained in the surroundings. These characteristics make Ni/Al multilayers very attractive to technological applications as localised heat sources. In this study, Ni/Al multilayer thin films are used to promote bonding between TiAl intermetallic alloys. Ni and Al alternated nanolayers were deposited by d.c. magnetron sputtering onto TiAl samples, with periods of 5, 14 and 30 nm. Joining experiments were performed at 900 °C for 60 or 30 min, in a vertical furnace with a vacuum level better than 10⁻² Pa. Applied pressures of 5 MPa were tested. The microstructure of the cross-sections of the bond interface was analysed by energy dispersive X-ray spectroscopy and characterised by scanning electron microscopy. The observation of the microstructure for 14 and 30 nm period multilayers revealed sound bonding, while for 5 nm period porosity and cracks within the interlayer thin film were observed. The interface is divided into three distinct zones: one with columnar grains, another with very small equiaxed grains and the third with larger equiaxed grains. The joining process appears to depend on the diffusion of Ni and Ti across the interface and is assisted by the nucleation of nanometric grains at the interface. The mechanical strength of the joints was evaluated by shear tests. The bonds produced at 900 °C/5 MPa/60 min/14 nm exhibited the highest shear strength of 314 MPa.     

Interfacial properties and characterization of Sc/Si multilayers

We investigate the intermixing of layers in Sc/Si and Sc/B₄C/Si/B₄C multilayers using electron and synchrotron excited soft X-ray emission and absorption spectroscopy. The multilayers are annealed at 100, 200, 300, 400 and 500 °C after preparation by magnetron sputtering. Silicon K_β emission and reflectivity measurements verify that the non-annealed multilayer systems are composed of distinct layers with only a minor interdiffusion in Sc/Si samples whereas annealing Sc/Si multilayers at 400 °C leads to a degradation of the multilayer structure and the formation of intermittent scandium silicide, ScSi. The presence of B₄C barriers in Sc/B₄C/Si/B₄C hinders this degradation from developing for the entire temperature range considered. The barrier layers continue to be effective for the entire temperature range even after an extended shelf-life.     

Microstructure and Vickers hardness of Co/Cu multilayers fabricated by electrodeposition

In order to investigate thermal stability of Co/Cu multilayers fabricated by electrodeposition, Vickers hardness tests and microstructure observations were conducted on both as-deposited and annealed Co/Cu multilayers having a layer thickness of 100 nm. The multilayers were annealed at temperatures ranging from 473 to 1,273 K for 1 h. It is confirmed that even after the annealing at 1,023 K, the multilayer maintained the high hardness (Hv231) which was comparative to that of the as-deposited Co/Cu multilayer. When the annealing temperature was higher than 1,073 K, the hardness decreased rapidly with increasing temperature. Scanning electron microscopy (SEM) observation revealed that the multilayered structures were still maintained without any layer damages after the annealing at the temperatures less than 873 K. At the cross sections of the Co/Cu multilayers annealed at T > 923 K, several copper layers were fragmented. The layered structure finally disappeared by the annealing at 1,273 K. The rapid decrease in the hardness at T > 1,073 K is simply understood from the annihilation of the Co/Cu interfaces.     

Thermal and stress studies of normal incidence Mo/B4C multilayers for a 6.7 nm wavelength

Wavelength, reflectance, and stress stability of Mo/B(4)C multilayers were studied as a function of postdeposition annealing up to 900 °C. These multilayers are of interest as normal incidence coatings for wavelengths above the boron K-absorption edge. Mo/B(4)C multilayers deposited at low sputtering pressure have high compressive stress. Zero stress can be achieved at 360 °C-370 °C, but annealing at <200 °C is sufficient to reduce stress by ～40%. This stress relaxation is accompanied with a multilayer period expansion of ～0.02 nm and a <0.5% decrease in normal incidence reflectivity. The multilayer period remains stable up to ～600 °C, while intrinsic stress changes from compressive to tensile. A four-layer model with amorphous molybdenum and boron carbide layers separated by amorphous layers of molybdenum borides (Mo(x)B(y)) is presented. These interlayers are present already in the as-deposited state and continue to grow with increasing temperature. Their presence lowers the optical contrast and the achievable reflectivity. However, they also increase multilayer thermal stability. At temperatures >600 °C, a noticeable decrease in reflectivity associated with the phase transition from amorphous to crystalline molybdenum boride is observed. This is accompanied with an increase in interface and surface roughness and a change in stress as a function of temperature.