Optische und mechanische Eigenschaften von RLVIP HfO2‐Schichten

Optical and mechanical properties of RLVIP HfO₂ films In this paper HfO₂‐films were deposited on unheated fused silica, borosilicate glass, and silicon wafer substrates by reactive low voltage ion plating (RLVIP). Optical film properties, i. e. refractive index and absorption as well as mechanical properties, particularly film stress, were investigated. Their dependence on deposition parameters, i. e. arc current and oxygen partial pressure was studied. The film refractive index was calculated from spectrophotometric measurements. The low absorption was determined by photothermal deflection spectrometry. Stress measurements were performed by bending disc method with uncoated and coated silicon wafer substrates.     

Significant Capacity and Cycle‐Life Improvement of Lithium‐Ion Batteries through Ultrathin Conductive Film Stabilized Cathode Particles

Atomic layer deposition (ALD), as a thin film deposition technique, has been explored as a viable path to improve the performance of lithium‐ion batteries. However, a trade‐off between the species transport (capacity) and protection (lifetime), resulting from the insulating properties of ALD films, is the key challenge in ALD technology. Here we report a breakthrough to overcome this trade‐off by coating an ultrathin conformal cerium dioxide (CeO₂) film on the surfaces of LiMn₂O₄ particles. The optimized CeO₂ film (≈3 nm) coated particles exhibit a significant improvement in capacity and cycling performance compared to uncoated (UC), Al₂O₃ coated, and ZrO₂ coated samples at room temperature and 55 °C for long cycling numbers. The initial capacity of the 3 nm CeO₂‐coated sample shows 24% increment compared to the capacity of the uncoated one, and 96% and 95% of the initial capacity is retained after 1000 cycles with 1C rate at room temperature and 55 °C, respectively. The detailed electrochemical data reveal that the suppression of the impedance rise and the facile transport of the species are the main contributors to the success.     

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.     

Characterization of nanocrystalline indium tin oxide thin films prepared by ion beam sputter deposition method

Indium tin oxide (ITO) thin films were deposited on glass substrates by ion beam sputter deposition method in three different deposition conditions [(i) oxygen (O₂) flow rate varied from 0.05 to 0.20 sccm at a fixed argon (1.65 sccm) flow rate, (ii) Ar flow rate changed from 1.00 to 1.65 sccm at a fixed O₂ (0.05 sccm) flow rate, and (iii) the variable parameter was the deposition time at fixed Ar (1.65 sccm) and O₂ (0.05 sccm) flow rates]. (i) The X-ray diffraction (XRD) patterns show that the ITO films have a preferred orientation along (400) plane; the orientation of ITO film changes from (400) to (222) direction as the O₂ flow rate is increased from 0.05 to 0.20 sccm. The optical transmittance in the visible region increases with increasing O₂ flow rate. The sheet resistance (R_s) of ITO films also increases with increasing O₂ flow rate; it is attributed to the decrease of oxygen vacancies in the ITO film. (ii) The XRD patterns show that the ITO film has a strong preferred orientation along (222) direction. The optical transmittance in the visible spectral region increases with an increase in Ar flow rate. The R_s of ITO films increases with increasing Ar flow rate; it is attributed to the decrease of grain size in the films. (iii) A change in the preferred orientations of ITO films from (400) to (222) was observed with increasing film thickness from 314 to 661 nm. The optical transmittance in the visible spectral region increases after annealing at 200 °C. The R_s of ITO film decreases with the increase of film thickness.     

Material properties and growth control of undoped and Sn-doped In2O3 thin films prepared by using ion beam technologies

Undoped (IO) and Sn-doped In₂O₃ (ITO) films have been deposited on glass and polymer substrates by an advanced ion beam technologies including ion-assisted deposition (IAD), hybrid ion beam, ion beam sputter deposition (IBSD), and ion-assisted reaction (IAR). Physical and chemical properties of the oxide films and adhesion between films and substrates were improved significantly by these technologies. By using the IAD method, non-stoichiometry and microstructure of the films were controlled by changing assisted oxygen ion energy and arrival ratio of assisted oxygen ion to evaporated atoms. Relationships between structural and electrical properties in ITO films on glass substrates were intensively investigated by using the IBSD method with changing ion energy, reactive gas environment, and substrate temperature. Smooth-surface ITO films (R_rms ≤ 1 nm and R_p-v ≤ 10 nm) for organic light-emitting diodes were developed with a combination of deposition conditions with controlling microstructure of a seed layer on glass. IAR surface treatment enormously enhanced the adhesion of oxide films to polymer substrate. The different dependence of IO and ITO films' properties on the experimental parameters, such as ion energy and oxygen gas environment, will be intensively discussed.     

Crystallization process and electro-optical properties of In2O3 and ITO thin films

Amorphous indium oxide (In₂O₃) and 10-wt% SnO₂ doped In₂O₃ (ITO) thin films were prepared by pulsed-laser deposition. These films were crystallized upon heating in vacuum at an effective heating rate of 0.00847 °C/s, while the evolution of the structure was observed by in situ X-ray diffraction measurements. Fast crystallization of the films is observed in the temperature ranges 165–210 °C and 185–230 °C for the In₂O₃ and ITO films, respectively. The crystallization kinetics is described by a reaction equation, with activation energies of 2.31 ± 0.06 eV and 2.41 eV and order of reactions of 0.75 ± 0.07 and 0.75 for the In₂O₃ and ITO films, respectively. The structures of the films observed here during heating are compared with those obtained upon film growth at different temperatures. The resistivity of the films depends on the evolution of the structure, the oxygen content and the activation of tin dopants in the films. A low resistivity of 5.5 × 10⁻⁴ Ω cm was obtained for the In₂O₃ and ITO films at room temperature, after annealing to 250 °C the resistivity of the ITO film reduces to 1.2 × 10⁻⁴ Ω cm.     

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.     

Optical and electrical characterization of r.f. sputtered ITO films developed as art protection coatings

Transparent and conductive tin-doped indium oxide (ITO) films have been prepared by r.f. plasma sputtering technique in Ar and Ar + O₂ gas mixture. The influence of the deposition conditions, film thickness, and substrate heating, as well as the post-annealing treatment on the optical and electrical properties of the ITO films has been investigated.The present study has extended the optical behaviour characterization of the ITO films in a wide UV-VIS-IR spectral region in addition to the comprehensive optical studies of this material at shorter wavelengths.The optical constants: refractive index (n), extinction (k) and absorption (α) coefficient, and the optical band gap (E_go) have been calculated for the ITO films in the spectral range between 350 and 2500 nm. A combination of several well-known theoretical models has been applied to describe precisely the complex optical behaviour of ITO films in separate spectral parts. In this approach, a good overlapping between the experimental and the simulated spectra in the whole investigated spectral region has been achieved.The deposition conditions and the optical and electrical properties of the ITO films have been optimized with respect to the requirements for their applications in art protection coatings.     

Coating material innovation in conjunction with optimized deposition technologies

Concentrating on physical vapour deposition methods several examples of recently developed coating materials for optical applications were studied for film deposition with optimized coating technologies: mixed evaporation materials for ion assisted deposition with modern plasma ion sources, planar metal and oxide sputter targets for Direct Current (DC) and Mid-Frequency (MF) pulsed sputter deposition and planar and rotatable sputter targets of transparent conductive oxides (TCO) for large-area sputter deposition.Films from specially designed titania based mixed evaporation materials deposited with new plasma ion sources and possible operation with pure oxygen showed extended ranges of the ratio between refractive index and structural film stress, hence there is an increased potential for the reduction of the total coating stress in High-Low alternating stacks and for coating plastics.DC and MF-pulsed sputtering of niobium metal and suboxide targets for optical coatings yielded essential benefits of the suboxide targets in a range of practical coating conditions (for absent in-situ post-oxidation ability): higher refractive index and deposition rate, better reproducibility and easier process control, and the potential for co-deposition of several targets.Technological progress in the manufacture of rotatable indium tin oxide (ITO) targets with regard to higher wall-thickness and density was shown to be reflected in higher material stock and coater up-time, economical deposition rates and stable process behaviour. Both for the rotatable ITO targets and higher-dense aluminum-doped zinc oxide (AZO) planar targets values of film transmittance and resistivity were in the range of the best values industrially achieved for films from the respective planar targets. The results for the rotatable ITO and planar AZO targets point to equally optimized process and film properties for the optimized rotatable AZO targets currently in testing.     

Low temperature synthesis of GaN films on ITO substrates by ECR-PEMOCVD

GaN films were deposited on indium tin oxide (ITO) coated glass substrates at various deposition temperatures using an electron cyclotron resonance plasma enhanced metal organic chemical vapor deposition (ECR-PEMOCVD). The TMGa and N₂ are applied as precursors of Ga and N, respectively. The crystalline quality and photoluminescence properties of as-grown GaN films are systematically investigated as a function of deposition temperature by means of X-ray diffraction analysis (XRD), reflection high energy electron diffraction (RHEED), atomic force microscopy (AFM), and room temperature photoluminescence (PL). The results show that the dense and uniformed GaN films with highly c-axis preferred orientation are successfully achieved on ITO glass substrates under optimized deposition temperature of 430 °C, and the room temperature PL spectra of the optimized GaN film show an intense near-band-edge luminescence located at 360 nm. The obtained GaN/ITO/glass structure was especially attractive for transparent optoelectronics applications with inexpensive ITO/glass substrate.     

Effect of V<Subscript>2</Subscript>O<Subscript>5</Subscript> content on the optical,structural and electrochromic properties of TiO<Subscript>2</Subscript> and ZrO<Subscript>2</Subscript> thin films

Vanadium oxide (V₂O₅) mixed titanium oxide (TiO₂) and zirconium oxide (ZrO₂) thin films were fabricated on glass substrates (corning 2947) and on indium tin oxide (ITO) coated glass substrates by sol gel spin coating process. Their optical, structural and electrochromic properties were investigated. The results were compared with pure TiO₂ and ZrO₂ thin films. Mixture of V₂O₅ with both types of film reduces the transmittance at the higher wavelengths. The refractive index of the V₂O₅ mixed TiO₂ and ZrO₂ films increases when compared with pure TiO₂ and ZrO₂ films. AFM images demonstrate no significant topographical changes for V₂O₅ mixed TiO₂ whereas for V₂O₅ mixed ZrO₂ films a topographical change is observed. V₂O₅ mixed TiO₂ showed slight increase in their charge capacity.     

Ion bombardment-induced enhancement of the properties of indium tin oxide films prepared by plasma-assisted reactive magnetron sputtering

Research on tin doped indium oxide (ITO) has for many years been stimulated by the need to simultaneously optimize the electrical, optical and mechanical properties, and by new challenges related to the deposition of transparent conducting oxides on flexible plastic substrates. In the present work, we investigate the growth and optical, electrical, and mechanical (hardness, elastic modulus and stress) properties of ITO films deposited by plasma assisted reactive magnetron sputtering (PARMS) from an indium-tin alloy target. PARMS achieves an effective control of bombardment by reactive species (e.g., O₂⁺, O⁺) on the surface of the growing film by varying the bias voltage, V_B, induced by a radiofrequency power applied to the substrate. Stress-free films possessing high transparency (> 80% — film on glass) and low resistivity (4 × 10^− 4 Ω cm) can be deposited by PARMS under conditions of intense ion bombardment (≤ 600 eV).     

Template Engineering of CuBi2O4 Single‐Crystal Thin Film Photocathodes

To develop strategies for efficient photo‐electrochemical water‐splitting, it is important to understand the fundamental properties of oxide photoelectrodes by synthesizing and investigating their single‐crystal thin films. However, it is challenging to synthesize high‐quality single‐crystal thin films from copper‐based oxide photoelectrodes due to the occurrence of significant defects such as copper or oxygen vacancies and grains. Here, the CuBi₂O₄ (CBO) single‐crystal thin film photocathode is achieved using a NiO template layer grown on single‐crystal SrTiO₃ (STO) (001) substrate via pulsed laser deposition. The NiO template layer plays a role as a buffer layer of large lattice mismatch between CBO and STO (001) substrate through domain‐matching epitaxy, and forms a type‐II band alignment with CBO, which prohibits the transfer of photogenerated electrons toward bottom electrode. The photocurrent densities of the CBO single‐crystal thin film photocathode demonstrate ?0.4 and ?0.7 mA cm^?2 at even 0 V_RHE with no severe dark current under illumination in a 0.1 m potassium phosphate buffer solution without and with H₂O₂ as an electron scavenger, respectively. The successful synthesis of high‐quality CBO single‐crystal thin film would be a cornerstone for the in‐depth understanding of the fundamental properties of CBO toward efficient photo‐electrochemical water‐splitting.     

Effects of substrate temperature on tin-doped indium oxide films deposited by dc arc discharge ion plating

Indium tin oxide (ITO) films were deposited on glass substrate at temperatures ranging from room temperature to 120 °C by the dc arc discharge ion plating technique. The electrical properties and crystallinity of ITO films were investigated. The resistivity of ITO films decreased with the increase of the substrate temperature in deposition, mostly due to increase in Hall mobility above 90 °C. The resistivity of ITO film obtained at temperature 120 °C was 1.33×10⁻⁴ Ω cm. The ITO films crystallized at the substrate temperature higher than 90 °C and the grain size estimated from the (2 2 2) peak in the direction parallel to the surface of the substrate became large with the increase of the substrate temperature. That the Hall mobility increased with the increase of the substrate temperature was speculated to be due to the increase of the grain size in the direction parallel to the surface.     

Aqueous Metal Oxide Inks for Modifying Electrode Work Function in Polymer Solar Cells

A method to prepare aqueous metal oxide inks for tuning the work function (WF) of electrodes is demonstrated. Thin films prepared from the metal oxide ink based on vanadium oxide (V₂O₅) nanoparticles are found to increase the WF of an indium‐tin‐oxide (ITO) electrode. ITO substrates modified with V₂O₅ films are applied as a hole selective layer (HSL) in polymer solar cells (PSCs) using a poly(3‐hexylthiophene) and [6,6]‐phenyl‐C61 butyric acid methyl ester blend as a photoactive layer. The PSCs prepared with V₂O₅‐modified ITO show better device performance, achieving a power conversion efficiency of 3.6%, demonstrating 15% enhancement compared to conventional ITO/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT‐PSS) based devices. Furthermore, ITO/V₂O₅‐modified devices exhibit better ambient stability with 60% improvement in device lifetime than those using PEDOT:PSS as an HSL. This solution‐processable and highly stable WF‐modifying metal oxide film can be a potential alternative material for engineering interfaces in optoelectronic devices.     

Epitaxial Lift‐Off of Centimeter‐Scaled Spinel Ferrite Oxide Thin Films for Flexible Electronics

Mechanical flexibility of electronic devices has attracted much attention from research due to the great demand in practical applications and rich commercial value. Integration of functional oxide materials in flexible polymer materials has proven an effective way to achieve flexibility of functional electronic devices. However, the chemical and mechanical incompatibilities at the interfaces of dissimilar materials make it still a big challenge to synthesize high‐quality single‐crystalline oxide thin film directly on flexible polymer substrates. This study reports an improved method that is employed to successfully transfer a centimeter‐scaled single‐crystalline LiFe₅O₈ thin film on polyimide substrate. Structural characterizations show that the transferred films have essentially no difference in comparison with the as‐grown films with respect to the microstructure. In particular, the transferred LiFe₅O₈ films exhibit excellent magnetic properties under various mechanical bending statuses and show excellent fatigue properties during the bending cycle tests. These results demonstrate that the improved transfer method provides an effective way to compose single‐crystalline functional oxide thin films onto flexible substrates for applications in flexible and wearable electronics.     

Atomic‐Layer‐Deposition‐Assisted Formation of Carbon Nanoflakes on Metal Oxides and Energy Storage Application

Nanostructured carbon is widely used in energy storage devices (e.g., Li‐ion and Li‐air batteries and supercapacitors). A new method is developed for the generation of carbon nanoflakes on various metal oxide nanostructures by combining atomic layer deposition (ALD) and glucose carbonization. Various metal oxide@nanoflake carbon (MO@f‐C) core‐branch nanostructures are obtained. For the mechanism, it is proposed that the ALD Al₂O₃ and glucose form a composite layer. Upon thermal annealing, the composite layer becomes fragmented and moves outward, accompanied by carbon deposition on the alumina skeleton. When tested as electrochemical supercapacitor electrode, the hierarchical MO@f‐C nanostructures exhibit better properties compared with the pristine metal oxides or the carbon coating without ALD. The enhancement can be ascribed to increased specific surface areas and electric conductivity due to the carbon flake coating. This peculiar carbon coating method with the unique hierarchical nanostructure may provide a new insight into the preparation of ‘oxides + carbon’ hybrid electrode materials for energy storage applications.     

Characteristics of ITO films with oxygen plasma treatment for thin film solar cell applications

The influence of oxygen plasma treatment on the electro-optical and structural properties of indium-tin-oxide films deposited by radio frequency magnetron sputtering method were investigated. The films were exposed at different O₂ plasma powers and for various durations by using the plasma enhanced chemical vapor deposition (PECVD) system. The resistivity of the ITO films was almost constant, regardless of the plasma treatment conditions. Although the optical transmittance of ITO films was little changed by the plasma power, the prolonged treatment slightly increased the transmittance. The work function of ITO film was changed from 4.67 eV to 5.66 eV at the plasma treatment conditions of 300 W and 60 min.     

Thin film passive solar windows produced by reactive evaporation of In-Sn

The semiconductor indium tin oxide (ITO) when present as a thin film has been shown to be transparent to visible radiation while opaque to IR radiation. Sputtering, chemical vapor deposition and other coating methodologies have been used to prepare ITO thin films. Reactive evaporation is an alternative coating technique, which has as its major advantage technical simplicity. Our prepation of ITO thin films (30–90 nm) for passive solar windows included the reactive evaporation of In-Sn alloys (In-5wt.%Sn, In-10wt.%Sn and In-20wt.%Sn) onto commercial soda-lime glass held between 25 and 300 °C. The reactive evaporation atmosphere consisted of oxygen at partial pressures from 1 × 10^-4 to 1 × 10^-3 Torr in residual nitrogen. In selected instances ultrathin palladium nucleating layers were evaporated onto the glass substrates prior to the deposition of the ITO. This was done in order to minimize initial alloy-glass agglomeration effects, thus decreasing the final overall ITO film thickness while increasing the visible transmission properties. The film's visible and IR spectral transmission properties were examined using ratio recording spectrophotometry. The agglomeration, nucleation and growth phenomena of the films were extensively investigated by transmission electron microscopy. The agglomeration was found to be a function of the film thickness, with increasing agglomeration for thinner films. Surface analysis by scanning Auger microscopy (SAM), electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy and energy-dispersive analysis of X-rays was also extensively carried out to determine our particular film properties. SAM indicated that only indium, tin and oxygen were present. No tungsten from the evaporation filament or elements from the glass were found. ESCA indicated that ITO was indeed present on the surface. Such work definitely indicated that ITO can be prepared by reactive physical vapor deposition and that the resultant films have the properties commonly found in sputtered ITO films.     

Abscheidung superharter Kohlenstoffschichten mittels Laser‐Arco® auf dem Weg vom Labor in die industrielle Serienfertigung

Superhard carbon film deposition by means of Laser‐Arco® on the way from the Laboratory into the industrial series coating Diamond‐like carbon films (DLC) are more and more applied as wear protection coatings for components and tools due to their unique combination of high hardness, low friction and sticking tendency to metallic counter bodies. Up to now applied DLC films are hydrogen containing (a‐C:H) or metal carbon films (Me‐C:H) deposited by a plasma assisted CVD process from carbon‐hydrogen gas mixtures. Their wide industrial effort results from that the can be deposited with slowly modified coating machines for classical hard coating (e.g. TiN or CrN). A new generation DLC films are the hydrogen‐free ta‐C films (ta‐C = tetrahedral bounded amorphous carbon) with a between two and three‐times higher hardness and with a resulting higher wear resistance under extreme condition than classical DLC films. They have excellent emergency running properties at lubrication break down. Their industrial application is more difficult due to that they cannot deposited with modified coating machines for classical hard and DLC coating and a new technology with corresponding equipment was not available up to now. The laser controlled, pulsed arc deposition technology (Laser‐Arco®) of the Fraunhofer IWS Dresden has this potential. In kind of a Laser‐Arc‐Module‐source the ta‐C film deposition can be integrated in every industrial used deposition machine.