High Precision Plasma Etch for Pattern Transfer: Towards Fluorocarbon Based Atomic Layer Etching

A basic requirement of a plasma etching process is fidelity of the patterned organic materials. In photolithography, a He plasma pretreatment (PPT) based on high ultraviolet and vacuum ultraviolet (UV/VUV) exposure was shown to be successful for roughness reduction of 193nm photoresist (PR). Typical multilayer masks consist of many other organic masking materials in addition to 193nm PR. These materials vary significantly in UV/VUV sensitivity and show, therefore, a different response to the He PPT. A delamination of the nanometer-thin, ion-induced dense amorphous carbon (DAC) layer was observed. Extensive He PPT exposure produces volatile species through UV/VUV induced scissioning. These species are trapped underneath the DAC layer in a subsequent plasma etch (PE), causing a loss of adhesion. Next to stabilizing organic materials, the major goals of this work included to establish and evaluate a cyclic fluorocarbon (FC) based approach for atomic layer etching (ALE) of SiO2 and Si; to characterize the mechanisms involved; and to evaluate the impact of processing parameters. Periodic, short precursor injections allow precise deposition of thin FC films. These films limit the amount of available chemical etchant during subsequent low energy, plasma-based Ar+ ion bombardment, resulting in strongly time-dependent etch rates. In situ ellipsometry showcased the self-limited etching. X-ray photoelectron spectroscopy (XPS) confirms FC film deposition and mixing with the substrate. The cyclic ALE approach is also able to precisely etch Si substrates. A reduced time-dependent etching is seen for Si, likely based on a lower physical sputtering energy threshold. A fluorinated, oxidized surface layer is present during ALE of Si and greatly influences the etch behavior. A reaction of the precursor with the fluorinated substrate upon precursor injection was observed and characterized. The cyclic ALE approach is transferred to a manufacturing scale reactor at IBM Research. Ensuring the transferability to industrial device patterning is crucial for the application of ALE. In addition to device patterning, the cyclic ALE process is employed for oxide removal from Si and SiGe surfaces with the goal of minimal substrate damage and surface residues. The ALE process developed for SiO2 and Si etching did not remove native oxide at the level required. Optimizing the process enabled strong O removal from the surface. Subsequent 90% H2/Ar plasma allow for removal of C and F residues.

Influência das espécies do plasma de N2 + O2 nas propriedades físicoquímicas das superfícies do pet

This work reports the influence of the poly (ethylene terephthalate) textile and films surface modification by plasmas of O2 and mixtures (N2 + O2), on their physical and chemical properties. The plasma surface polymeric modification has been used for many researchs, because it does not affect the environment with toxic agents, the alterations remains only at nanometric layers and this technique shows expressive results. Then, due to its good acceptance, the treatment was carried out in a vacuum chamber. Some parameters remained constant during all treatment, such as: Voltage 470 V; Pressure 1,250 Mbar; Current: 0, 10 A and gas flow: 10 cm3/min, using oxygen plasma alternating the treatment time 10 to 60 min with an increase of 10 min to each subsequent treatment. Also, the samples were treated with a gas mixture (nitrogen + oxygen) which was varied only the gas composition from 0 to 100% leaving the treatment time remaining constant to all treatment (10 min). The plasma treatment was characterized in-situ with Optics Emission Spectroscopy (OES), and the samples was characterized by contact angle, surface tension, Through Capillary tests, Raman spectroscopy, Infrared attenuated total reflection (IR-ATR) and atomic force microscopy, scanning electronic Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). The results showed that oxygen treated fabrics presented high wettability, due to the hydrophilic groups incorporation onto the surface formed through spputering of carbon atoms. For the nitrogen atmosphere, there is the a film deposition of amine groups. Treatment with small oxygen concentration in the mixture with nitrogen has a higher spputered species of the samples

Estudo da viabilidade técnica para obtenção de superfície duplex em aço inoxidável martensítico AISI 410 através do processo de deposição a plasma por gaiola catódica

The technique of plasma nitriding by the cathode cage mainly stands out for its ability to produce uniform layers, even on parts with complex geometries. In this study, it was investigated the efficiency of this technique for obtaining duplex surface, when used, simultaneously, to nitriding treatment and thin film deposition at temperatures below 500°C. For this, were used samples of AISI 41 0 Martensitic Stainless Steel and performed plasma treatment, combining nitriding and deposition of thin films of Ti and/or TiN in a plasma atmosphere containing N2-H2. It was used a cathodic cage of titanium pure grade II, cylindrical with 70 mm diameter and 34 mm height. Samples were treated at temperature 420ºC for 2 and 12 hours in different working pressures. Optical Microscopy (OM), Scanning Electron Microscopy (SEM) with micro-analysis by Energy Dispersive Spectroscopy (EDS), X-Ray Diffraction (XRD), Atomic Force Microscopy (AFM) and analysis of Vickers Microhardness were used to investigate coating properties such as homogeneity and surface topography, chemical composition, layer thickness, crystalline phase, roughness and surface microhardness. The results showed there is a direct proportionality between the presence of H2 in plasma atmosphere and the quantity of titanium in surface chemical composition. It was also observed that the plasma treatment at lowpressure is more effective in formation of TiN thin film

Construção de um aparato experimental para monitoramento in situ da deposição de filmes finos de titânio por magnetron sputtering

The technique of surface coating using magnetron sputtering is one of the most widely used in the surface engineering, for its versatility in obtaining different films as well as in the micro / nanometric thickness control. Among the various process parameters, those related to the active species of the plasma are of the most fundamental importance in the mechanism and kinetics of deposition. In order to identify the active species of the plasma, parameters such as gas flow, pressure and density of electric power were varied during titanium coating on glass substrate. By flowing argon gas of 10, 20, 30, 40 and 50 sccm (cubic centimeters per minute) for each gas flow a sequential scan of the electric current of 0.10, 0.20, 0.30, 0.40 , 0.50 A. The maximum value of 0.50 A was chosen based both on literature data and on limitations of the equipment. The monitoring of plasma species present during the deposition was carried out in situ by the technique of optical emission spectroscopy (OES) through the spectrometer Ocean Optics USB2000 Series. For this purpose, an apparatus was developed to adapt the OES inside the plasma reactor to stay positioned closest to the target. The radiations emitted by the species were detected by an optical fiber placed behind the glass substrate and their intensities as a function of wavelength were, displayed on a monitor screen. The acquisition time for each condition of the plain parameters was related to the minima of spectral lines intensities due to the film formed on the substrate. The intensities of different emission lines of argon and titanium were then analyzed as a function of time, to determine the active species and estimate the thickness of the deposited films. After the deposition, the coated glasses thin films were characterized by optical transmittance through an infrared laser. It was found that the thickness and deposition rate determined by in situ analysis were consistent with the results obtained by laser transmittance

Efeito antibacteriano de tecidos têxteis revestidos por prata através da técnica de deposição por plasma

In this study, it has been investigated the influence of silver film deposition onto 100% polyester woven and non-woven, on the survival of Escherichia coli and Staphylococcus aureus in contact with these surfaces. The treatment was performedin a chamber containing the working gas at low pressure (~ 10-2 mbar). Some process parameters such as as voltage: 470 V; pressure: 10-2 mbar; current : 0.40 A and gas flow: 6 and 10 cm3/min were kept constant. For the treatments with purêargon plasma using a flow of 6 and 10 cm3/min, different treatment times were evaluated, such as, 10 , 20, 30, 40, 50 and 60 minutes. Contact angle (sessile drop), measurements were used to determine the surface tension of the treated fabrics and its influence on the bacteria grow as weel as the possibilities of a biofilm formation. The formation of a silver film, as well as the amount of this element was verified byEDX technique. The topography was observed through scanning electron microscopy (SEM) to determine the size of silver grains formed on the surfaces of the fabric and assess homogeneity of treatment. The X-ray diffraction (XRD) was used to analyze the structure of silver film deposition. The woven fabric treatments enabled the formation of silver particulate films with particle size larger than the non-woven fabrics. With respect to bacterial growth, all fabrics were shown to be bactericidal for Staphylococcus aureus (S. aureus), while for the Escherichia coli (E. coli), the best results were found for the non-woven fabric (TNT) treated with a flow of 10 cm3/min to both bacteria

Étude sur les propriétés physicochimiques et électrochimiques des liquides ioniques redox et leur application en tant qu’électrolyte dans les supercapaciteurs

Ce mémoire porte sur les recherches et les développements dans le domaine des électrolytes à base de liquide ionique redox. Une nouvelle famille de liquide ionique redox basée sur le ferrocenylsulfonyl(trifluoromethylsulfonyl) (FcNTf) a été développée et étudiée pour la première fois afin de démontrer le potentiel de ces liquides ioniques dans les dispositifs de stockage d’énergie. En premier lieu, les liquides ioniques redox (RILs) composés de l’anion électroactif et du cation d’alkylimidazolium sont synthétisés et caractérisés. L’impact de la variation des chaînes alkyles du cation sur les propriétés physicochimiques et électrochimiques du RIL a été étudié. À une faible concentration en solution, l’impact du cation a peu d’influence sur l’ensemble des propriétés. Cependant, à haute concentration (>50 % massique) et sans électrolyte de support, la formation de films en oxydation a été observée à l'électrode positive. Ce point est intéressant pour les futures recherches et développements dans le domaine, puisque la variation des chaînes alkyles du cation des liquides ioniques redox et la formation de films lors de l’oxydation du FcNTf est peu connue et comprise en littérature. De plus, l’optimisation des conditions de solution d'électrolyte RIL dans les supercapaciteurs est aussi présentée. En deuxième lieu, la mise en application des RILs dans les supercapaciteurs a été testée. La performance énergétique et le mécanisme d’autodécharge ont été ciblés dans cette étude. En présence de l’électrolyte redox, la contribution des réactions faradaiques permet d'accomplir un gain énergique de 287 % versus les systèmes purement capacitifs. À cause de la formation de film à l’électrode, l’électrolyte redox FcNTf joue un rôle primordial dans la prévention de l’autodécharge versus les liquides ioniques qui étaient connus jusqu’à présent. Finalement, ce mémoire a permis de mieux comprendre les effets structure-propriétés relative aux modifications du cation chez les liquides ioniques redox.

Étude sur les propriétés physicochimiques et électrochimiques des liquides ioniques redox et leur application en tant qu’électrolyte dans les supercapaciteurs

Ce mémoire porte sur les recherches et les développements dans le domaine des électrolytes à base de liquide ionique redox. Une nouvelle famille de liquide ionique redox basée sur le ferrocenylsulfonyl(trifluoromethylsulfonyl) (FcNTf) a été développée et étudiée pour la première fois afin de démontrer le potentiel de ces liquides ioniques dans les dispositifs de stockage d’énergie. En premier lieu, les liquides ioniques redox (RILs) composés de l’anion électroactif et du cation d’alkylimidazolium sont synthétisés et caractérisés. L’impact de la variation des chaînes alkyles du cation sur les propriétés physicochimiques et électrochimiques du RIL a été étudié. À une faible concentration en solution, l’impact du cation a peu d’influence sur l’ensemble des propriétés. Cependant, à haute concentration (>50 % massique) et sans électrolyte de support, la formation de films en oxydation a été observée à l'électrode positive. Ce point est intéressant pour les futures recherches et développements dans le domaine, puisque la variation des chaînes alkyles du cation des liquides ioniques redox et la formation de films lors de l’oxydation du FcNTf est peu connue et comprise en littérature. De plus, l’optimisation des conditions de solution d'électrolyte RIL dans les supercapaciteurs est aussi présentée. En deuxième lieu, la mise en application des RILs dans les supercapaciteurs a été testée. La performance énergétique et le mécanisme d’autodécharge ont été ciblés dans cette étude. En présence de l’électrolyte redox, la contribution des réactions faradaiques permet d'accomplir un gain énergique de 287 % versus les systèmes purement capacitifs. À cause de la formation de film à l’électrode, l’électrolyte redox FcNTf joue un rôle primordial dans la prévention de l’autodécharge versus les liquides ioniques qui étaient connus jusqu’à présent. Finalement, ce mémoire a permis de mieux comprendre les effets structure-propriétés relative aux modifications du cation chez les liquides ioniques redox.

Thermal diffusion in molecular dynamics simulations of thin film diamond deposition

Molecular dynamics simulations of carbon atom depositions are used to investigate energy diffusion from the impact zone. A modified Stillinger-Weber potential models the carbon interactions for both sp2 and sp3 bonding. Simulations were performed on 50 eV carbon atom depositions onto the (111) surface of a 3.8 x 3.4 x 1.0 nm diamond slab containing 2816 atoms in 11 layers of 256 atoms each. The bottom layer was thermostated to 300 K. At every 100th simulation time step (27 fs), the average local kinetic energy, and hence local temperature, is calculated. To do this the substrate is divided into a set of 15 concentric hemispherical zones, each of thickness one atomic diameter (0.14 nm) and centered on the impact point. A 50-eV incident atom heats the local impact zone above 10 000 K. After the initial large transient (200 fs) the impact zone has cooled below 3000 K, then near 1000 K by 1 ps. Thereafter the temperature profile decays approximately as described by diffusion theory, perturbed by atomic scale fluctuations. A continuum model of classical energy transfer is provided by the traditional thermal diffusion equation. The results show that continuum diffusion theory describes well energy diffusion in low energy atomic deposition processes, at distance and time scales larger than 1.5 nm and 1-2 ps, beyond which the energy decays essentially exponentially. (C) 1998 Published by Elsevier Science S.A. All rights reserved.

Influence of the deposition pressure on the properties of transparent and conductive ZnO: Ga thin-film produced by r.f. sputtering at room temperature

Thin Solid Films, vol. 427, nº 1-2

Amorphous silicon thin film solar cells deposited entirely by Hot-Wire Chemical Vapour Deposition at low temperature (<150 ºC)

Amorphous silicon n-i-p solar cells have been fabricated entirely by Hot-Wire Chemical Vapour Deposition (HW-CVD) at low process temperature < 150 °C. A textured-Ag/ZnO back reflector deposited on Corning 1737F by rf magnetron sputtering was used as the substrate. Doped layers with very good conductivity and a very less defective intrinsic a-Si:H layer were used for the cell fabrication. A double n-layer (μc-Si:H/a-Si:H) and μc-Si:H p-layer were used for the cell. In this paper, we report the characterization of these layers and the integration of these layers in a solar cell fabricated at low temperature. An initial efficiency of 4.62% has been achieved for the n-i-p cell deposited at temperatures below 150 °C over glass/Ag/ZnO textured back reflector.

Highly conductive and transparent ZnO thin film using Chemical Spray Pyrolysis technique: Effect of doping and deposition parameters

In the present work we report the preparation details studies on ZnO thin films. ZnO thin films are prepared using cost effective deposition technique viz., Chemical Spray Pyrolysis (CSP). The method is very effective for large area preparation of the ZnO thin film. A new post-deposition process could also be developed to avoid the adsorption of oxygen that usually occurs after the spraying process i.e., while cooling. Studies were done by changing the various deposition parameters for optimizing the properties of ZnO thin film. Moreover, different methods of doping using various elements are also tried to enhance the conductivity and transparency of the film to make these suitable for various optoelectronic applications.

Oblique Angle Deposition of Germanium Film on Silicon Substrate

The effect of flux angle, substrate temperature and deposition rate on obliquely deposited germanium (Ge) films has been investigated. By carrying out deposition with the vapor flux inclined at 87° to the substrate normal at substrate temperatures of 250°C or 300°C, it may be possible to obtain isolated Ge nanowires. The Ge nanowires are crystalline as shown by Raman Spectroscopy.

Electrochemical deposition of praseodymium oxide on tin-doped indium oxide as a thin sensing film

Fabrication of a thin praseodymium oxide film is of great technological interest in sensor, semiconducting, and ceramic industries. It is shown for the first time that an ultrathin layer of praseodymium oxide can be deposited on tin-doped indium oxide surface (ITO) by applying a negative sweeping voltage (cathodic electrodeposition) to the aqueous solution containing Pr(NO3)(3) and H2O2 using cyclic voltammetry, followed by annealing the film at 500 S C for 1 h. X-ray diffraction suggested that the predominant phase of the film is Pr6O11 and atomic force microscopy and scanning electron microscopy characterizations indicated that this film is assembled with a monolayer coverage of spherical praseodymium oxide nanoparticles packed closely on the ITO surface. AC impedance measurements of the thin Pr6O11 film on ITO also revealed that the composite material displays a much higher electrical conductivity compared to the pure ITO. As a result, the material could suitably be used as a new chemical sensor. (c) 2006 The Electrochemical Society.

The improvement of thin polymer film properties through plasma immersion ion implantation and deposition technique

Thin polymer films were deposited from acetylene and argon mixtures by plasma immersion ion implantation and deposition. The effect of the pulse frequency, v, on molecular structure, optical gap, contact angle and hardness of the films was investigated. It was observed progressive dehydrogenation of the samples and increment in the concentration of unsaturated carbon bonds as the pulse frequency was increased. Film hardness and contact angle increased and optical gap decreased with v. These results are interpreted in terms of the chain unsaturation and crosslinking.

Si-based thin film coating on Y-TZP: Influence of deposition parameters on adhesion of resin cement

This study evaluated the influence of deposition parameters for Si-based thin films using magnetron sputtering for coating zirconia and subsequent adhesion of resin cement. Zirconia ceramic blocks were randomly divided into 8 groups and specimens were either ground finished and polished or conditioned using air-abrasion with alumina particles coated with silica. In the remaining groups, the polished specimens were coated with Si-based film coating with argon/oxygen magnetron discharge at 8:1 or 20:1 flux. In one group, Si-based film coating was performed on air-abraded surfaces. After application of bonding agent, resin cement was bonded. Profilometry, goniometry, Energy Dispersive X-ray Spectroscopy and Rutherford Backscattering Spectroscopy analysis were performed on the conditioned zirconia surfaces. Adhesion of resin cement to zirconia was tested using shear bond test and debonded surfaces were examined using Scanning Electron Microscopy. Si-based film coating applied on air-abraded rough zirconia surfaces increased the adhesion of the resin cement (22.78 ± 5.2 MPa) compared to those of other methods (0-14.62 MPa) (p = 0.05). Mixed type of failures were more frequent in Si film coated groups on either polished or air-abraded groups. Si-based thin films increased wettability compared to the control group but did not change the roughness, considering the parameters evaluated. Deposition parameters of Si-based thin film and after application of air-abrasion influenced the initial adhesion of resin cement to zirconia. © 2013 Elsevier B.V. All rights reserved.