Reactive Low Voltage Ion Plating (RLVIP). Prozess‐, Plasma‐ und Schichteigenschaften am Beispiel von Ta2O5/SiO2

Reactive Low Voltage Ion Plating (RLVIP) is a process for production of chemical compound films mainly by direct synthesis from the elements. It can be used for deposition of single layer and multilayer oxide coatings onto unheated glass and other unheated substrates. An introduction to the RLVIP process will be given, together with some relevant plasma process data and optical and mechanical film properties of Ta₂O₅ films and Ta₂O₅/SiO₂ multilayers. The process plasma was analysed by plasma monitoring (PPM421), a Langmuir probe system (Smartprobe) and a Faraday Cup System (MIEDA). A correlation between plasma data and optical/mechanical properties will be shown.     

MoS2/ta‐C‐Kombinationsschichten hergestellt durch Laser‐Arc‐Technologie

MoS₂/ta‐C coatings produced by laserarc‐technology A series of MoS₂ and combined MoS₂/ta‐C coatings were prepared by lasercontrolled arc evaporation (Laser‐Arc) in order to study the tribological coating behaviour under vacuum and atmospheric conditions. Very low friction coefficients down to 0.005 were measured under high vacuum. By using a ta‐C underlayer beneath the MoS₂ a increased lifetime up to 5×10⁵ load cycles could be obtained. Also under atmospheric conditions the underlayer had a beneficial effect on coating performance.     

Abscheidung,Charakterisierung und Anwendung von Plasma‐Polymerschichten auf HMDSO‐Basis

Deposition, Characterisation and Application of HMDSO‐based Plasma Polymer Films High quality organosilicone coatings can be produced via plasma enhanced chemical vapor deposition of hexamethyldisiloxane (HMDSO). In this article aspects of deposition, analysis and application of HMDSO/O₂ processes are presented. The coatings’ organic/inorganic character can be adjusted by an appropriate combination of plasma power and gas mixture which is shown by XPS. Particularly multi layer and gradient layer systems can be deposited within the same process. Quantitative chemical depth profiling of such layer systems can be performed by secondary neutral mass spectrometry (SNMS). AFM investigations exhibit that the surface roughness of the coatings is determined by the appearance of hemispherical agglomerates, which is more pronounced, the more glass‐like the coatings are. As an example of use it is shown, that an appropriate HMDSO plasma treatment can distinctly improve the tribological behavior of elastomer devices. The presented work is done within a project of the German Federal Ministry of Education and Research (BMBF) entitled: “nano functionalization of interfaces for data‐, textile‐, building‐, medicine‐, bio‐, and aerospace‐ technology”.     

Substrate treatment and film deposition in ionized and activated gas

Ionized low pressure gases are used for surface cleaning and as part of vacuum deposition processes. Typical conditions in the abnormal glow discharges and r.f. excited plasmas employed in these techniques are discussed. During the cleaning of a dielectric or insulated component immersed in a plasma the bombarded surface develops a small negative floating potential which retards impinging electrons, but if energetic electrons penetrate the plasma by acceleration across a positive sheath their impingement can charge the surface potential to a positive value. Continued electron bombardment of the positively charged body results in polymer film growth when organic molecules are adsorbed on the substrate from contaminants in the gas atmosphere. R.f. plasmas can be used for surface cleaning in inert and oxidizable atmospheres at moderate (～ 10^-3 torr) and rough (～ 1 torr) vacuum pressures. A high partial pressure (> 10^-2 torr) of organic gas in a plasma can allow radical formation by electron impact in the gas phase, with possible polymer growth. Superficial contaminants can be removed from substrates without sputtering or damage by plasma exposure in cold cathode and r.f. discharges. The preparation of boundary lubricant coatings on metal and dielectric bearings after plasma cleaning is discussed as a typical example. Energy liberated by particle impact and ion recombination can with active gas reactions combine to remove organic contaminants. UV irradiation is known to cause crosslinking of adsorbed organic molecules and to result in the removal of polymer coatings in the presence of oxygen. In conclusion, the deposition conditions in ion plating and the reactive evaporation of metal oxides using ionized gas are discussed.     

Schäden wälzbeanspruchter DLC‐Schichten auf Stahlsubstraten unterschiedlicher Härte

Damages of slip‐rolling tested DLC coatings on steel substrates of different hardness Extremely hard diamond coatings on hard SSiC substrates, various hard DLC coatings on 100Cr6 substrates (HRC60) as well as selected DLC coatings on unhardened steel substrates (HRC20) were tested under slip‐rolling conditions. Unadditivated paraffin oil was used as a lubricant. The tests were carried out in an Amsler type twin disc tester at initial maximum pressures of P₀=2.3 GPa according to Hertz. The tests were terminated after n=1.000.000 revolutions (endurance tests: n=10.000.000 revolutions) or if a coherent damaged area of A>1 mm² occurred. The slip‐rolling tests showed that the SSiC had a supportive influence on the diamond coatings which, however, failed due to fractures in the substrate. At least two of the DLC coatings on 100Cr6 substrates (HRC60) withstood the slip‐rolling test for up to n=10.000.000 revolutions with nearly no visible damage. These coatings deposited onto a soft, nitrogen alloyed steel (HRC20) were able to adjust to the deformation of the substrate without major damaged areas (A>1 mm²).     

Properties of Si3N4 and AIN Films Produced by Reactive Ion Plating and Gas Discharge Sputtering

Thin films of Silicon- and Aluminiumnitride were produced by Reactive Low Voltage Ion Plating and low pressure dc-Magnetron Sputtering. The films show excellent adherence, high hardness and abrasion resistance, and are dense and homogeneous. Both processes, applied at optimum conditions, enable the production of films with nearly identical optical properties. Such optimized deposition conditions in both processes yielded a mean refractive index of n₅₅₀ = 2.05 ± 0.03 for Si₃N₄ and of n₅₅₀ = 2.12 ± 0.01 for AIN films. The region of high optical transmission was found to be between 0.23 and 9.5μm (Si₃N₄) and between 0.2 and 12.5 μm (AIN). In the visible range both metal nitride films are free of optical absorption (k <10^?3). These materials, together with their oxynitride phases, offer interesting applications for the deposition of optical multilayer systems with very high spectral stability.     

Laser treatment of optical Nb2O5‐ and HfO2‐films

Optical thin films have to fulfil high quality requirements, which can be achieved for example by reactive low voltage ion plating (RLVIP). But especially for applications in precision optics, additional treatments are necessary to reduce residual optical absorption and compressive stress arising in the coatings, and to enhance the stability of the coatings – specifically for laser applications. In practice, post deposition heat treatment and backside coatings are mostly used to overcome these problems. In order to provide alternative methods to handle the disadvantages of the RLVIP‐process, the idea was to replace the mentioned steps by a laser treatment. This means that a laser beam is directed onto the sample after deposition or even during the coating process. In this study, the influence of a high power CO²‐laser beam on thin Nb²O⁵‐ and HfO²‐films was investigated. The effects on the refractive index and the film thickness are presented for different energy densities of a TEA‐CO²‐laser beam (10.59μm). For Nb²O⁵‐films a thickness increase up to 12.2nm (6.4 %) and a refractive index decrease of 0.074 (3.1 %) were found. In case of HfO² the values were 2.3nm (1.2 %) in thickness and 0.007 (0.3 %) in refractive index. From the observed changes also distinct impacts on the film stress can be expected. One intention of this research was also to call attention to an alternative technique for enhancement of thin film properties.     

Low‐cycle fatigue/high‐cycle fatigue interactions in notched Ti‐6Al‐4V*

Combined low‐cycle fatigue/high‐cycle fatigue (LCF/HCF) loadings were investigated for smooth and circumferentially V‐notched cylindrical Ti–6Al–4V fatigue specimens. Smooth specimens were first cycled under LCF loading conditions for a fraction of the previously established fatigue life. The HCF 10⁷ cycle fatigue limit stress after LCF cycling was established using a step loading technique. Specimens with two notch sizes, both having elastic stress concentration factors of K_t = 2.7, were cycled under LCF loading conditions at a nominal stress ratio of R = 0.1. The subsequent 10⁶ cycle HCF fatigue limit stress at both R = 0.1 and 0.8 was determined. The combined loading LCF/HCF fatigue limit stresses for all specimens were compared to the baseline HCF fatigue limit stresses. After LCF cycling and prior to HCF cycling, the notched specimens were heat tinted, and final fracture surfaces examined for cracks formed during the initial LCF loading. Fatigue test results indicate that the LCF loading, applied for 75% of total LCF life for the smooth specimens and 25% for the notched specimens, resulted in only small reductions in the subsequent HCF fatigue limit stress. Under certain loading conditions, plasticity‐induced stress redistribution at the notch root during LCF cycling appears responsible for an observed increase in HCF fatigue limit stress, in terms of net section stress.     

Tyrosinase‐catalysed grafting of food‐grade gallates to chitosan: surface properties of novel functional coatings

Plasma‐activated biaxially oriented polypropylene (BOPP) films and paper substrate have been coated with functional chitosan solutions. Plasma treatment increased the amount of surface peroxide groups and carboxyl groups on the BOPP films. As a result of plasma activation, the surface energy increased from 30 to 50 dynes/cm. The enzyme tyrosinase catalysed the grafting of octyl gallate and dodecyl gallate to amino groups of chitosan polysaccharide. Resulting coatings exhibited strong antimicrobial activity against Gram‐positive Staphylococcus aureus and Gram‐negative Listeria innocua. After 24 h of incubation, a total reduction in both bacteria cell numbers varied between >4.9 and 1.4 logarithmic units. Grafted dodecyl gallate and octyl gallate at pH 6 were found to have the lowest reduction values of <3 logarithmic units for S. aureus, while 1.4 logarithmic reduction value was obtained for grafted dodecyl gallate at pH 6 against L. innocua. Chitosan coatings were also effective barrier layers against oxygen transmission although the transmission rates clearly increased in high‐humidity conditions. In dry conditions, however, the transmission rate of 2 cm³/(m² · 24 h) was obtained with chitosan‐coated BOPP. Coatings did not have any effects on water vapour transmission. Both gallates were successfully grafted at pH 6. As increased flocculation and colour formation indicated, the tyrosinase‐catalysed grafting was more powerful with octyl gallate. Dodecyl gallate containing chitosan coatings was more hydrophobic as compared to octyl gallate. Total migration of substances into 95% ethanol was ≥5 mg/dm², thus materials may be exploitable in packaging purposes in direct contact with certain foodstuffs. Copyright © 2008 John Wiley & Sons, Ltd.     

Slip‐rolling resistance of ta‐C and a‐C coatings up to 3,000 MPa of maximum Hertzian contact pressure

The slip‐rolling resistances of hard and stiff thin films under high Hertzian contact pressures can be improved by optimizing the “coating/substrate systems”. It is known from former investigations that the so‐called “egg‐shell” effect is no general hindrance for high slip‐rolling resistance of thin hard coatings. The coating stability depends more on specific deposition process and coating/substrate interface design. In this article it is experimentally shown, that pure amorphous carbon thin films with hardness between 15 and 63 GPa can be slip‐rolling resistant several million load cycles under a maximum Hertzian contact pressures of up to 3.0 GPa. Whereas all coatings were stable up to 10 million load cycles in paraffin oil at room temperature, reduced coating lifetime was found in SAE 0W‐30 engine oil at 120°C. It was shown how the coating hardness and the initial coating surface roughness influence the running‐in process and coating lifetime. No clear correlation between coating hardness and coating lifetime could be observed, but friction coefficients seem to be reduced with higher coating hardness. Very low friction down to ?0.03 in unmodified engine oils was found for the hardest ta‐C film.     

ITO‐coatings by reactive low‐voltage ion plating: film properties and plasma analysis

Transparent conductive oxides (TCO) are widely used materials for multifarious applications. According to today's state of knowledge, indium‐tin‐oxide (ITO) still offers the best electrical properties among numerous TCOs. However, ITO films produced by ion plating have only rarely been reported to be investigated. For most coating processes, ITO films need to be deposited under high temperature conditions (some 100 °C substrate heating) or require post‐deposition heat treatment in order to obtain high film quality. In this study, reactive low‐voltage ion plating (RLVIP) was used, which allows ‐ due to plasma assistance during the coating process ‐ deposition of ITO films at temperatures below 100 °C. Essential film properties, i.e. resistivity and optical transmission, were optimised by variation of arc current, gas pressure and deposition rate. These quantities ‐ particularly arc current and gas pressure ‐ have huge influence on the characteristics of the supporting plasma. This was shown by analysing the plasma with a mass‐spectrometric plasma monitoring system and with a Langmuir probe. In comparison with formerly studied coating materials (Ta₂O₅,Nb₂O₅,HfO₂), different plasma compositions regarding the presence of metal oxide ions were determined, which could be attributed to elemental and molecular energy properties (ionisation and binding energies).     

Electrochemical performance and microstructural evolution of laser deposited Al‐Sn coating in acidic environment

Outstanding performance of materials is one of the requirements of modifying the existing materials in order to meet a global demand necessary in technology innovation. Direct laser metal deposition technique due to excellent properties has replaced conventional techniques in modifying the surface of materials. The interplay between melting, fusion and optimised laser parameters are very important factors to be considered when using laser metal deposition technique. ASTM A29 steel property was enhanced through this technique by Al‐Sn reinforcements. A 3‐kW continuous wave ytterbium laser system was employed by this process. This research investigated the microstructure and corrosion properties of fabricated laser metal deposited ASTM A29 steel. The resulting microstructure and content of the inconsequential elements in the coatings fabricated were studied to obtain the results achieved. Observation of the microstructure showed typical phase of acicular α′‐martensite attributed to rapid cooling of the molten pool. The electrochemical behaviour was investigated in 1 M HCl solution at 27 °C via potentiodynamic polarization technique. The fabricated coatings had corrosion rate of 0.03435 mm/yr, current density of 3.95 ? 10^?6 A/cm², and polarization resistance of 7093.4 Ω ? cm². While the control had corrosion rate of 16.308 mm/yr and polarization resistance of 8.0631 Ω ? cm².     

Laser‐Raman and Nuclear Magnetic Resonance (NMR) studies on plasma‐sprayed hydroxylapatite coatings: Influence of bioinert bond coats on phase composition and resorption kinetics in simulated body fluid

The structure and phase composition of HAp coatings deposited onto Ti6Al4V coupons (50x20x2mm) by atmospheric plasma spraying (APS) were studied by laser‐Raman spectroscopy, ³¹P‐ and ¹H‐MAS‐NMR and 2D‐³¹P/¹H HETCOR‐CP‐NMR spectroscopy, and XRD with Rietveld refinement. The samples investigated comprised APS HAp coatings with and without a TiO₂ bond coat as well as coatings incubated for different lengths of time (up to 12 weeks) in simulated body fluid (SBF) under physiological conditions. In APS coatings the presence of a bond coat increased the proportion of well‐ordered crystalline HAp at the expense of distorted apatite‐like structures such as oxyHAp and oxyapatite, and thermal decomposition products such as tricalcium phosphate (TCP) and tetracalcium phosphate (TTCP), and also decreased the amount of amorphous calcium phosphate (ACP). Incubation in SBF further advanced the proportion of crystalline HAp since the disordered structures, the thermal decomposition products, and ACP exhibit substantially higher solubility.     

Configurable Low‐Cost Plotter Device for Fabrication of Multi‐Color Sub‐Cellular Scale Microarrays

The construction and operation of a low‐cost plotter for fabrication of microarrays for multiplexed single‐cell analyses is reported. The printing head consists of polymeric pyramidal pens mounted on a rotation stage installed on an aluminium frame. This construction enables printing of microarrays onto glass substrates mounted on a tilt stage, controlled by a Lab‐View operated user interface. The plotter can be assembled by typical academic workshops from components of less than 15 000 Euro. The functionality of the instrument is demonstrated by printing DNA microarrays on the area of 0.5 cm² using up to three different oligonucleotides. Typical feature sizes are 5 μm diameter with a pitch of 15 μm, leading to densities of up to 10⁴–10⁵ spots/mm². The fabricated DNA microarrays are used to produce sub‐cellular scale arrays of bioactive epidermal growth factor peptides by means of DNA‐directed immobilization. The suitability of these biochips for cell biological studies is demonstrated by specific recruitment, concentration, and activation of EGF receptors within the plasma membrane of adherent living cells. This work illustrates that the presented plotter gives access to bio‐functionalized arrays usable for fundamental research in cell biology, such as the manipulation of signal pathways in living cells at subcellular resolution.     

Optical thin films obtained by plasma-induced chemical vapor deposition

A plasma-aided deposition technique was used to prepare thin oxide coatings by the reaction of volatile chlorides with oxygen. A 13.56 MHz r.f. supply was connected to a circular electrode on which the substrates were supported. A glow discharge was set up at pressures between 5 and 100 m Torr, and a self-bias on the electrode of between ? 100 and ? 1000 V (depending on input power and pressure) creates ion-plating conditions. GeCl₄, SiCl₄, TiCl₄ and SnCl₄ were used to prepare the corresponding dioxides. The deposition conditions (pressure, bias, gas ratios and treatment time) were varied and the resultant films examined in terms of thickness (and coating rate) and their respective indices.The films were generally smooth and highly transparent and were deposited at rates of tens of nanometres per minute. TiO₂ and SiO₂ were produced with refractive index values of 2.2 and 1.45 respectively at rates of 50 nm min^?1; these rates were found to be relatively insensitive to the gas pressure and r.f. bias.In₂O₃ films were similarly prepared from trimethyl indium vapour and O₂. These films could be electrically conducting.In contrast with earlier published work on reactive plasma deposition of oxide films, this work was carried out at ambient temperatures.     

Mechanical properties of CN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> coatings obtained by carbon arc sputtering

Internal stresses σ₀, friction coefficients fand microhardness were measured in diamond-like coatings obtained by vacuum-arc sputtering of carbon target at different nitrogen pressures in a work chamber during deposition on metallic substrates. The dependence of these parameters on nitrogen concentration in coatings can be used in practical deposition of strengthening and friction coatings for improvement of their tribological properties. The correlation between mechanical properties of diamond-like and CN _x coatings was established.     

Low‐Temperature Wafer‐Scale Deposition of Continuous 2D SnS2 Films

Semiconducting 2D materials, such as SnS₂, hold immense potential for many applications ranging from electronics to catalysis. However, deposition of few‐layer SnS₂ films has remained a great challenge. Herein, continuous wafer‐scale 2D SnS₂ films with accurately controlled thickness (2 to 10 monolayers) are realized by combining a new atomic layer deposition process with low‐temperature (250 °C) postdeposition annealing. Uniform coating of large‐area and 3D substrates is demonstrated owing to the unique self‐limiting growth mechanism of atomic layer deposition. Detailed characterization confirms the 1T‐type crystal structure and composition, smoothness, and continuity of the SnS₂ films. A two‐stage deposition process is also introduced to improve the texture of the films. Successful deposition of continuous, high‐quality SnS₂ films at low temperatures constitutes a crucial step toward various applications of 2D semiconductors.     

Organische UV‐Schutzschichten für die Polycarbonatverglasung

Organic UV‐protective coatings for polycarbonate glazing Polycarbonate as glazing material in outdoor applications requires functional UV protective and scratch resistant coatings. The vacuum coating technology offers a wide range of deposition processes to produce such complex coatings. The Fraunhofer IOF developed an effective UV protection by the deposition of organic UV absorbers. Thermal evaporated organic compounds were investigated as single layers and hybrid layers in a SiO₂ matrix. The UV‐stability of such coatings was increased significantly.     

Inkjet‐Printed High‐Q Nanocrystalline Diamond Resonators

Diamond is a highly desirable material for state‐of‐the‐art micro‐electromechanical (MEMS) devices, radio‐frequency filters and mass sensors, due to its extreme properties and robustness. However, the fabrication/integration of diamond structures into Si‐based components remain costly and complex. In this work, a lithography‐free, low‐cost method is introduced to fabricate diamond‐based micro‐resonators: a modified home/office desktop inkjet printer is used to locally deposit nanodiamond ink as ?50–60 µm spots, which are grown into ≈1 µm thick nanocrystalline diamond film disks by chemical vapor deposition, and suspended by reactive ion etching. The frequency response of the fabricated structures is analyzed by laser interferometry, showing resonance frequencies in the range of ≈9–30 MHz, with Q ‐factors exceeding 10⁴, and (f₀ × Q) figure of merit up to ≈2.5 × 10¹¹ Hz in vacuum. Analysis in controlled atmospheres shows a clear dependence of the Q‐factors on gas pressure up until 1 atm, with Q ∝ 1/P. When applied as mass sensors, the inkjet‐printed diamond resonators yield mass responsivities up to 981 Hz fg^?1 after Au deposition, and ultrahigh mass resolution up to 278 ± 48 zg, thus outperforming many similar devices produced by traditional top‐down, lithography‐based techniques. In summary, this work demonstrates the fabrication of functional high‐performance diamond‐based micro‐sensors by direct inkjet printing.     

Deposition Temperature Effect on the Structure and Optical Property of RF‐PACVD‐Derived Hydrogenated SiCNO Film

Amorphous hydrogenated silicon oxocarbonitride (SiCNO:H) films have been deposited by plasma‐assisted chemical vapour deposition (PACVD) using bis(trimethylsilyl)carbodiimide (BTSC) as a single source precursor in a argon (Ar) radio‐frequency plasma. In this work the SiCNO:H films deposited at different deposition temperatures were studied in terms of deposition rate, refractive index, surface roughness, microstructure, and chemical composition including bonding state. The results showed that a higher deposition temperature enhanced the formation of Si‐N bonds, and disfavoured the formation of N=C=N, Si‐NCN, C‐H and Si‐CH₃ bonds. A higher deposition temperature also decreased the deposition rate and increased the refractive index of the resulting SiCNO:H film. With increasing temperature a denser film was formed, indicating a change of the deposition mechanism, i.e., transformation from particle precipitation to heterogeneous surface reaction. Except for the coatings deposited at room temperature, the surface of the films was smooth with a roughness of around 4 nm at the centre in the range of 5 μm x 5 μm area. Moreover, the films contained 8 ～ 16 at.% oxygen bonded to Si, which originated from the remnant H₂O in the deposition chamber.