Roughness and light scattering of ion-beam-sputtered fluoride coatings for 193 nm

Scattering characteristics of multilayer fluoride coatings for 193 nm deposited by ion beam sputtering and the related interfacial roughnesses are investigated. Quarter- and half-wave stacks of MgF2 and LaF3 with increasing thickness are deposited onto CaF2 and fused silica and are systematically characterized. Roughness measurements carried out by atomic force microscopy reveal the evolution of the power spectral densities of the interfaces with coating thickness. Backward-scattering measurements are presented, and the results are compared with theoretical predictions that use different models for the statistical correlation of interfacial roughnesses.

Procedure to characterize microroughness of optical thin films: application to ion-beam-sputtered vacuum-ultraviolet coatings

A method for characterizing the microroughness of samples in optical coating technology is developed. Measurements over different spatial-frequency ranges are composed into a single power spectral density (PSD) covering a large bandwidth. This is followed by the extraction of characteristic parameters through fitting of the PSD to a suitable combination of theoretical models. The method allows us to combine microroughness measurements performed with different techniques, and the fitting procedure can be adapted to any behavior of a combined PSD. The method has been applied to a set of ion-beam-sputtered fluoride vacuum-UV coatings with increasing number of alternative low- and high-index layers. Conclusions about roughness development and microstructural growth are drawn.

Ultraviolet optical and microstructural properties of MgF2 and LaF3 coatings deposited by ion-beam sputtering and boat and electron-beam evaporation

Single layers of MgF2 and LaF3 were deposited upon superpolished fused-silica and CaF2 substrates by ion-beam sputtering (IBS) as well as by boat and electron beam (e-beam) evaporation and were characterized by a variety of complementary analytical techniques. Besides undergoing photometric and ellipsometric inspection, the samples were investigated at 193 and 633 nm by an optical scatter measurement facility. The structural properties were assessed with atomic-force microscopy, x-ray diffraction, TEM techniques that involved conventional thinning methods for the layers. For measurement of mechanical stress in the coatings, special silicon substrates were coated and analyzed. The dispersion behavior of both deposition materials, which was determined on the basis of various independent photometric measurements and data reduction techniques, is in good agreement with that published in the literature and with the bulk properties of the materials. The refractive indices of the MgF2 coatings ranged from 1.415 to 1.440 for the wavelength of the ArF excimer laser (193 nm) and from 1.435 to 1.465 for the wavelength of the F2 excimer laser (157 nm). For single layers of LaF3 the refractive indices extended from 1.67 to 1.70 at 193 nm to ~1.80 at 157 nm. The IBS process achieves the best homogeneity and the lowest surface roughness values (close to 1 nmrms) of the processes compared in the joint experiment. In contrast to MgF2 boat and e-beam evaporated coatings, which exhibit tensile mechanical stress ranging from 300 to 400 MPa, IBS coatings exhibit high compressive stress of as much as 910 MPa. A similar tendency was found for coating stress in LaF3 single layers. Experimental results are discussed with respect to the microstructural and compositional properties as well as to the surface topography of the coatings.

Characterization of nano-oxide layers fabricated by ion beam oxidation

In this paper, a remote O2 ion source is used for the formation of nano-oxide layers. The oxidation efficiency was measured in CoFe-oxide films, and a decrease of the oxide layer with the pan angle and the oxidation pressure is observed. For the same oxidation pressure, the oxidation efficiency depends on the O2 content in the Ar-O2 plasma. These results were applied in optimizing the fabrication of Al2O3 barrier for tunnel junctions. This method was also used to fabricate junctions with Fe-oxide layers inserted at the Al2O3-CoFe interface. TEM and magnetization data indicate that after anneal at 385°C, a homogeneous ferromagnetic Fe-oxide layer (Fe3O4?) is formed.

Ion-beam induced oxidation of GaAs and AlGaAs

The oxidation of GaAs and AlxGa1−xAs targets by oxygen irradiation has been studied in detail. It was found that the oxidation process is characterized by the strong preferential oxidation of Al as compared to Ga, and of Ga as compared to As. This experimental observation, which has been accurately quantified by using x‐ray photoelectron spectroscopy, is connected to the different heats of formation of the corresponding oxides. The oxide grown by ion beam oxidation shows a strong depletion in As and relatively low oxidation of As as well. The depletion can be associated with the preferential sputtering of the As oxide in respect to other compounds whereas the low oxidation is due to the low heat of formation. In contrast Al is rapidly and fully oxidized, turning the outermost layer of the altered layer to a single Al2O3 overlayer, as observed by transmission electron microscopy. The radiation enhanced diffusion of oxygen and aluminum in the altered layer explains the large thickness of these altered layers and the formation of Al oxides on top of the layers. For the case of ion‐beam oxidation of GaAs a simulation program has been developed which describes adequately the various growth mechanisms experimentally observed

Optical and microstructural properties of MgF2 UV coatings grown by ion beam sputtering process

The optical, mechanical, and microstructural properties of MgF2 single layers grown by ion beam sputtering have been investigated by spectrophotometric measurements, film stress characterization, x-ray photoelectron spectroscopy (XPS), x-ray diffraction, and transmission electron microscopy. The deposition conditions, using fluorine reactive gas or not, have been found to greatly influence the optical absorption and the stress of the films as well as their microstructure. The layers grown with fluorine compensation exhibit a regular columnar microstructure and an UV-optical absorption which can be very low, either as deposited or after thermal annealings at very low temperatures. On the contrary, layers grown without fluorine compensation exhibit a less regular microstructure and a high ultraviolet absorption which is particularly hard to cure. On the basis of calculations, it is shown that F centers are responsible for this absorption, whereas all the films were found to be stoichiometric, in the limit of the XPS sensitivity. On the basis of external data taken from literature, our experimental curves are analyzed, so we propose possible diffusion mechanisms which could explain the behaviors of the coatings.

Spray Pyrolysed Zinc Oxide Thin Films : Effects of Doping and Ion Beam Irradiation

In recent years scientists have made rapid and significant advances in the field of semiconductor physics. One of the most important fields of current interest in materials science is the fundamental aspects and applications of conducting transparent oxide thin films (TCO). The characteristic properties of such coatings are low electrical resistivity and high transparency in the visible region. The first semitransparent and electrically conducting CdO film was reported as early as in 1907 [1]. Though early work on these films was performed out of purely scientific interest, substantial technological advances in such films were made after 1940. The technological interest in the study of transparent semiconducting films was generated mainly due to the potential applications of these materials both in industry and research. Such films demonstrated their utility as transparent electrical heaters for windscreens in the aircraft industry. However, during the last decade, these conducting transparent films have been widely used in a variety of other applications such as gas sensors [2], solar cells [3], heat reflectors [4], light emitting devices [5] and laser damage resistant coatings in high power laser technology [6]. Just a few materials dominate the current TCO industry and the two dominant markets for TCO’s are in architectural applications and flat panel displays. The architectural use of TCO is for energy efficient windows. Fluorine doped tin oxide (FTO), deposited using a pyrolysis process is the TCO usually finds maximum application. SnO2 also finds application ad coatings for windows, which are efficient in preventing radiative heat loss, due to low emissivity (0.16). Pyrolitic tin oxide is used in PV modules, touch screens and plasma displays. However indium tin oxide (ITO) is mostly used in the majority of flat panel display (FPD) applications. In FPDs, the basic function of ITO is as transparent electrodes. The volume of FPD’s produced, and hence the volume of ITO coatings produced, continues to grow rapidly. But the current increase in the cost of indium and the scarcity of this material created the difficulty in obtaining low cost TCOs. Hence search for alternative TCO materials has been a topic of active research for the last few decades. This resulted in the development of binary materials like ZnO, SnO2, CdO and ternary materials like II Zn2SnO4, CdSb2O6:Y, ZnSO3, GaInO3 etc. The use of multicomponent oxide materials makes it possible to have TCO films suitable for specialized applications because by altering their chemical compositions, one can control the electrical, optical, chemical and physical properties. But the advantages of using binary materials are the easiness to control the chemical compositions and depositions conditions. Recently, there were reports claiming the deposition of CdO:In films with a resistivity of the order of 10-5 ohm cm for flat panel displays and solar cells. However they find limited use because of Cd-Toxicity. In this regard, ZnO films developed in 1980s, are very useful as these use Zn, an abundant, inexpensive and nontoxic material. Resistivity of this material is still not very low, but can be reduced through doping with group-III elements like In, Al or Ga or with F [6]. Hence there is a great interest in ZnO as an alternative of ITO. In the present study, we prepared and characterized transparent and conducting ZnO thin films, using a cost effective technique viz Chemical Spray Pyrolysis (CSP). This technique is also suitable for large area film deposition. It involves spraying a solution, (usually aqueous) containing soluble salts of the constituents of the desired compound, onto a heated substrate.

Comparative study of Barium Fluoride thin films produced by ion-beam sputtering and thermal evaporation

Coatings and filters for spaceflight far-infrared components require a robust, non-absorptive low-index thin film material to contrast with the typically higher refractive index infrared materials. Barium fluoride is one such material for the 10 to 20µm wavelength infrared region, however its optical and mechanical properties vary depending on the process used to deposit it in thin film form. Thin films of dielectric produced by thermal evaporation are well documented as having a lower packing density and refractive index than bulk material. The porous and columnar micro structure of these films causes possible deterioration of their performance in varied environmental conditions, primarily because of the moisture absorption. Dielectric thin films produced by the more novel technique of ion-beam sputtering are denser with no columnar micro structure and have a packing density and refractive index similar to the bulk material. A comparative study of Barium Fluoride (BaF2) thin films made by conventional thermal evaporation and ion-beam sputtering is reported. Films of similar thicknesses are deposited on Cadmium Telluride and Germanium substrates. The optical and mechanical properties of these films are then examined. The refractive index n of the films is obtained from applying the modified Manifacier's evvelope method to the spectral measurements made on a Perkin Elmer 580 spectrophotometer. An estimate is also made of the value of the extinction coefficient k in the infrared wavelength transparent region of the thin film. In order to study the mechanical properties of the BaF2 films, and evaluate their usefulness in spaceflight infrared filters and coatings, the thin film samples are subjected to MIL-F-48616 environmental tests. Comparisons are made of their performance under these tests.

X-ray photoelectron spectroscopy analysis of zirconium nitride-like films prepared on Si(100) substrates by ion beam assisted deposition

Thin zirconium nitride films were prepared on Si(l 00) substrates at room temperature by ion beam assisted deposition with a 2 keV nitrogen ion beam. Arrival rate ratios ARR(N/Zr) used were 0.19, 0.39, 0.92, and 1.86. The chemical composition and bonding structure of the films were analyzed with X-ray photoelectron spectroscopy (XPS). Deconvolution results for Zr 3d, Zr 3p(3/2), N 1s, O 1s, and C 1s XPS spectra indicated self-consistently the presence of metal Zr-0, nitride ZrN, oxide ZrO2, oxymnide Zr2N2O, and carbide ZrC phases, and the amounts of these compounds were influenced by ARR(N/Zr). The chemical composition ratio N/Zr in the film increased with increasing ARR(N/Zr) until ARR(N/Zr) reached 0.92, reflecting the high reactivity of nitrogen in the ion beam, and stayed almost constant for ARR(N/Zr) >= 1, the excess nitrogen being rejected from the growing film. A considerable incorporation of contaminant oxygen and carbon into the depositing film was attributed to the getter effect of zirconium. (C) 2007 Elsevier B.V. All rights reserved.

Ion beam assisted deposition of an organic light emitting diode electrode

This work presents the electro-optical characterization of metal-organic interfaces prepared by the Ion Beam Assisted Deposition (IBAD) method. IBAD applied in this work combines simultaneously metallic film deposition and bombardment with an independently controlled ion beam, allowing different penetration of the ions and the evaporated metallic elements into the polymer. The result is a hybrid, non-abrupt interface, where polymer, metal and ion coexists. We used an organic light emitting diode, which has a typical vertical-architecture, for the interface characterization: Glass/Indium Tin Oxide (ITO)/Poly[ethylene-dioxythiophene/poly{styrenesulfonicacid}]) (PEDOT:PSS) /Emitting Polymer/Metal. The emitting polymer layer comprised of the Poly[(9,9-dioctyl-2,7-divinylenefluorenylene)-alt-co-{2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene}] (PFO) and the metal layer of aluminum prepared with different Ar(+) ion energies varying in the range from 0 to 1000 eV. Photoluminescence, Current-Voltage and Electroluminescence measurements were used to study the emission and electron injection properties. Changes of these properties were related with the damage caused by the energetic ions and the metal penetration into the polymer. Computer simulations of hybrid interface damage and metal penetration were confronted with experimental data. (C) 2010 Elsevier B.V. All rights reserved.

Infrared analysis of ion beam irradiated polymers

Irradiation with heavy ions can produce several modifications in the chain structure of polymers. These modifications can be related to scissioning and cross-linking of chemical bonds. which depend on the ion fluence and the density of energy deposited in the material. Stacked thin film Makrofol-KG (R) samples were irradiated with 350 MeV Au(26+) ions and FTIR absorption spectroscopy was used to determine the bond changes in the samples. Data on the absorption bands as a function of the fluence indicated a higher probability for simple-bonds scissioning than for double-bonds scissioning and no dependence on the number of double bonds breaking with ion fluence. Since sample irradiation was done in a non-track-overlapping regime, a novel process for double bonds formation is suggested: the excitation of a site in the material by only one incident ion followed by a double bond formation during the de-excitation process. (C) 2009 Elsevier B.V. All rights reserved.

Nanoindentation mechanical properties characterization of glassy polymeric carbon treated with ion beam

Phenolic resins when heat treated in inert atmosphere up to 1000 degreesC become glassy polymeric carbon (GPC), a chemically inert and biocompatible material useful for medical applications, such as in the manufacture of heart valves and prosthetic devices. In earlier work we have shown that ion bombardment can modify the surface of GPC, increasing its roughness. The enhanced roughness, which depends on the species, energy and fluence of the ion beam, can improve the biocompatibility of GPC prosthetic artifacts. In this work, ion bombardment was used to make a layer of implanted ions under the surface to avoid the propagation of microcracks in regions where cardiac valves should have pins for fixation of the leaflets. GPC samples prepared at 700 and 1500 degreesC were bombarded with ions of silicon. carbon, oxygen and gold at energies of 5, 6, 8 and 10 MeV, respectively, and fluences between 1.0 x 10(13) and 1.0 x 10(16) ions/cm(2). Nanoindentation hardness characterization was used to compare bombarded with non-bombarded samples prepared at temperatures up to 2500 degreesC. The results with samples not bombarded showed that the hardness of GPC increases strongly with the heat treatment temperature. Comparison with ion bombarded samples shows that the hardness changes according to the ion used, the energy and fluence. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Effects of ion beam on nanoindentation characteristics of glassy polymeric carbon surface

Glassy polymeric carbon (GPC) is a useful material for medical applications due to its chemical inertness and biocompatible characteristics. Mitral and aortic and hydrocephalic valves are examples of GPC prosthetic devices that have been fabricated and commercialized in Brazil. In this work, ion beam was used to improve the mechanical characteristics of GPC surface and therefore to avoid the propagation of microcracks where the cardiac valves are more fragile. A control group of phenolic resin samples heat-treated at 300, 400, 700, 1000, 1500, and 2500 degrees C was characterized by measuring their hardness and Young's reduced elastic modulus with the depth of indentation. The control group was compared to results obtained with samples heat-treated at 700, 1000, and 1500 degrees C and bombarded with energetic ions of silicon, carbon, oxygen, and gold at energies of 5, 6, 8, and 10 MeV, respectively, with fluences between 10x10(13) and 10x10(16) ions/cm(2). GPC nonbombarded samples showed that hardness depends on the heat treatment temperature (HTT), with a maximum hardness for heat treatment at 1000 degrees C. The comparison between the control group and bombarded group also showed that hardness, after bombardment, had a greater increase for samples prepared at 700 degrees C than for samples prepared at higher temperatures. The Young's elastic modulus presents an exponential relationship with depth. The parameters obtained by fitting depend on the HTT and on the ion used in the bombardment more than on energy and fluence. The hardness results show clearly that bombardment can promote carbonization, increase the linkage between the chains of the polymeric material, and promote recombination of broken bonds in lateral groups that are more numerous for samples heat-treated at 700 degrees C. (c) 2004 Elsevier B.V. All rights reserved.

Ion beam analysis of a-C:H films on alloy steel substrate

An a-C:H thin film deposited by plasma immersion ion implantation and deposition on alloy steel (16MnCr5) was analyzed using a self-consistent ion beam analysis technique.In the self-consistent analysis, the results of each individual technique are combined in a unique model, increasing confidence and reducing simulation errors.Self-consistent analysis, then, is able to improve the regular ion beam analysis since several analyses commonly used to process ion beam data still rely on handling each spectrum independently.The sample was analyzed by particle-induced x-ray emission (for trace elements), elastic backscattering spectrometry (for carbon), forward recoil spectrometry (for hydrogen) and Rutherford backscattering spectrometry (for film morphology).The self-consistent analysis provided reliable chemical information about the film, despite its heavy substrate.As a result, we could determine precisely the H/C ratio, contaminant concentration and some morphological characteristics of the film, such as roughness and discontinuities.© 2013 Elsevier B.V.All rights reserved.