Effect of electrode potential on the tribocorrosion of tungsten

The tribocorrosion behavior of tungsten sliding against an alumina ball was evaluated in sulfuric acid under applied electrode potential. Surface chemistry of worn and unworn surfaces was evaluated using XPS and AES. Quasi-potentiostatic polarization curves and potential step measurements were performed under mass transport control to assess relevant corrosion factors. It was found that the tribocorrosion rate of tungsten varies with the applied electrode potential and goes through a maximum for a potential of 0.5 V MSE. Different material removal mechanisms were identified. In the wear track, materials deterioration proceeds by cyclic mechanical removal of the passive oxide film followed by anodic oxidation. The removal rate was found to be proportional to the passivation charge density determined in independent electrochemical experiments. At higher potential (1V MSE) a thick WO3 tribolayer forms and by covering the wear track reduces the tribocorrosion damage. Outside the wear track the stirring of the solution induced by the moving alumina ball leads to an enhancement of the dissolution rate of the WO3 passive film and thus to higher material wastage. (C) 2008 Elsevier Ltd. All rights reserved.

Chemical-mechanical polishing of tungsten

Jelena Stojadinovic

The chemical-mechanical polishing process (CMP) is an essential part of the production of integrated circuits. Metal to be polished in the CMP reacts with the oxidants from the aqueous suspension (slurry) and the passive film is formed on the metal surface. Suspended abrasive nano particles from the slurry cause detachment of the formed friable passive films. The CMP represents the tribocorrosion process where material deterioration results from the interaction of wear and corrosion which takes place in tribological contact exposed to an aggressive environment. Due to increasing number of the materials to be polished in the modern integrated circuits it is necessary to gather fundamental understanding of the removal mechanism of each material. The aim of this work is to elucidate the removal mechanisms of tungsten (W), as a typical microelectronic metal (chosen as a model system), under different oxidising conditions (represented by electrochemically imposed potential). Also, we want to evaluate the effect of the slurry composition (chelating agents lactic and phosphoric acid) on material removal. To achieve this electrochemical techniques (chrono amperometry, cyclic voltametry, passivation kinetics measurements under mass transport control), and tribocorrosion techniques (tests on tribometer with electrochemical cell with reciprocating sliding motion of alumina ball) were used. Surface analysis techniques (SEM, XPS, AES) were used to assess worn and unworn surfaces' morphology and chemistry. In addition, electrochemical tests and polishing tests on the CMP machine were performed with technical CMP slurries. The sliding action of the alumina ball on tungsten in the 0.01 M H2SO4 solution was found to cause three distinct wear responses depending on imposed electrode potential. Below the first threshold potential the wear is low due to negligible oxide film formation. In the following wear region, up to the second threshold potential, materials deterioration in the rubbed area proceeds by cyclic mechanical removal of the WO3 passive film followed by repassivation of tungsten. The amount of anodic oxidation corresponds to the overall removed metal volume. Beyond the second threshold potential a compact tribolayer of WO3 (more than 400 nm thick), probably formed by agglomeration of oxide particles detached from the metal surface, forms and covers the wear track. Similar tribocorrosion behavior of tungsten was also observed in the presence of 0.1 M H3PO4. The presence of chelating agents, lactic acid and phosphoric acid, in the 0.01 M H2SO4 solution does not change the volume of material wastage at potentials below the second threshold potential. Beyond this electrode potential, lactic acid promotes WO3 dissolution and thus impedes the third body formation and enhances wear. Electrochemical factors have a strong influence on the tungsten CMP removal rate. It was found that CMP removal rate increases with the open circuit potential (electrode potential) and with passivation charge density. A good correlation of tribocorrosion results and CMP practice was observed. Tribocorrosion models can be successfully applied to the tribocorrosion of tungsten and as well can be fairly used for modelling the material removal in CMP.

EPFL2009

Electrochemically controlled wear transitions in the tribocorrosion of ruthenium

Didier Bouvet, Michel Declercq, Stefano Mischler, Jelena Stojadinovic

This work presents an investigation of the tribocorrosion of ruthenium in sulphuric acid solutions. The study was focused on the effect of the electrode potential on wear of ruthenium during sliding against an inert alumina ball in a reciprocating sliding tribometer fitted with an electrochemical cell. Surface chemical and electrochemical properties were characterized using AES, XPS, SEM and electrochemical corrosion techniques.

2009

Tribocorrosion behavior of beta titanium alloys in physiological solutions containing synovial components

Stefano Mischler

In this work, the tribocorrosion behavior of Ti-12.5Mo, Ti-13Nb-13Zr and Ti-29Nb-13Ta-4.6Zr beta titanium alloys which are candidate biomaterials for joint prostheses is studied against ultra high molecular weight polyethylene in Hank's balanced salt solution. Ti-6Al-4Fe alpha+beta titanium alloy is also tested for comparison. Experiments were carried out at open circuit potential and at a passive applied potential using a pin-on-flat reciprocating sliding tribo-electrochemical apparatus. The potential, anodic current and friction coefficient were measured in situ as a function of time. The beta alloys exhibited a tendency to repassivate during sliding at passive and open circuit potential. The predominant wear mechanism of the metal-polyethylene pairs was 3 body wear, exhibited by the transfer of polyethylene to all titanium alloys. Polyethylene showed a comparatively low wear against beta titanium alloys. The effect of the addition of synovial fluid constituents, namely bovine serum albumin, hyaluronic acid and dipalmitoyphosphatidylcholine on the tribocorrosion of Ti-29Nb-13Ta-4.6Zr alloy was also studied. The presence of additives affected the friction coefficient, induced an increase of the wear volume, and a modification of the dominant wear mechanism which was identified as abrasion without transfer of polyethylene. (C) 2010 Elsevier B.V. All rights reserved.

2011

Chemical-mechanical polishing of tungsten

Jelena Stojadinovic

EPFL2009