Oxidative Dissolution Of Copper Research Articles

Application photometric method definitions with 4-(2-Pyridylazo)resorcinol for quantitative analysis and research on oxidative dissolution of copper in education thiocyanate complexes

Application photometric method definitions with 4-(2-Pyridylazo)resorcinol for quantitative analysis and research on oxidative dissolution of copper in education thiocyanate complexes

Kinetics and mechanism of the reaction of benzyl bromide with copper in dimethylacetamide in the presence of oxygen

The reaction of copper metal with benzyl bromide in dimethylacetamide in the presence of oxygen has been studied. Oxidative dissolution of copper follows the single-electron transfer mechanism with formation of benzaldehyde, benzyl alcohols, and copper(II) coordination compounds. The kinetic and thermodynamic parameters of the process have been determined by resistometry. Intermediately formed species have been identified and quantitated, and the reaction stereochemistry has been studied. The reaction mechanism is discussed.

The Role of Arginine as a Complexing Agent in Copper CMP

AbstractChemical mechanical polishing (CMP) of copper was investigated in hydrogen peroxide and arginine slurries. Arginine was found to be a complexing agent for the copper in peroxide based slurries, in the alkaline region. The copper polish rate was measured in a Struers LaboPol-5 and LaboForce-3 CMP polishing tool. Static etch rate experiments of copper discs (25.4 mm Dia × 10 mm) were carried in 200 ml beakers with different combinations of hydrogen peroxide and arginine concentrations. Peroxide concentration was varied from 0 to 10 vol%, while the arginine concentration was varied from 0 to 1 wt% for both static etch and polish rate experiments. Fumed silica used as the abrasive medium for polishing.The electrochemical processes involved in oxidative dissolution of copper were investigated by the Tafel corrosion plots and OCP measurements, using the Princeton Applied Research potentiostat. Three electrode corrosion flat cell was used for the electrochemical measurements. Corrosion current density and open circuit potentials (OCP) were used to elucidate the oxidative behavior of peroxide and the complexing role of arginine. Surface characteristics of the polished copper surface were analyzed with the Digital Instruments NanoScope AFM. Polishing with these chemicals resulted in smooth finish.These results indicated that the arginine curtails the formation of oxidative layer on the copper surface and the removal rate was increased by forming complex with the copper.

Kinetics and Mechanism of Reaction of Carbon Tetrachloride with Copper(0) in Dimethylformamide

Reaction of copper(0) with carbon tetrachloride in DMF was studied. In the absence of atmospheric oxygen, the oxidative dissolution of copper(0) occurs as one-electron transfer and gives rise to C2Cl2 and copper(I) complexes. Kinetic and thermodynamic parameters of the process are determined, and its mechanism was considered.

Oxidative Dissolution of Copper and Zinc Metal in Carbon Dioxide with tert-Butyl Peracetate and a β-Diketone Chelating Agent

A series of beta-diketone ligands, R(1)COCH(2)COR(2) [tmhdH (R(1) = R(2) = C(CH(3))(3)); tfacH (R(1) = CF(3); R(2) = CH(3)); hfacH (R(1) = R(2) = CF(3))], in combination with tert-butyl peracetate (t-BuPA), have been investigated as etchant solutions for dissolution of copper metal into carbon dioxide solvent. Copper removal in CO(2) increases in the order tfacH < tmhdH < hfacH. A study of the reactions of the hfacH/t-BuPA etchant solution with metallic copper and zinc was conducted in three solvents: scCO(2) (supercrical CO(2)); hexanes; CD(2)Cl(2). The etchant solution/metallic zinc reaction produced a diamagnetic Zn(II) complex, which allowed NMR identification of the t-BuPA decomposition products as tert-butyl alcohol and acetic acid. Gravimetric analysis of the amount of zinc consumed, together with NMR studies, confirmed the 1:1:2 Zn:t-BuPA:hfacH reaction stoichiometry, showing t-BuPA to be an overall two-electron oxidant for Zn(0). The metal-containing products of the copper and zinc reactions were characterized by elemental analysis, IR spectroscopy, and, as appropriate, NMR spectroscopy and single-crystal X-ray diffraction [trans-M(hfac)(2)(H(2)O)(CH(3)CO(2)H) (1, M = Cu; 2, M = Zn)]. On the basis of the experimental results, a working model of the oxidative dissolution reaction is proposed, which delineates the key chemical variables in the etching reaction. These t-BuPA/hfacH etchant solutions may find application in a CO(2)-based chemical mechanical planarization (CMP) process.

The combinatorial effect of complexing agent and inhibitor on chemical–mechanical planarization of copper

Chemical–mechanical planarization (CMP) is a vital process for the fabrication of advanced copper multilevel interconnects schemes. The focus of this investigation was to understand the oxidation, dissolution and surface modification characteristics of Cu in slurries with varying pH. Hydrogen peroxide was used as the oxidizer, glycine as complexing agent and 3-amino-triazol (ATA) as inhibitor in the slurry. The electrochemical process involved in the oxidative dissolution of copper was investigated by potentiodynamic polarization studies. X-ray photoelectron spectroscopy was used to investigate the surface modification of copper and understand the interaction between Cu–H 2O 2–glycine–ATA during CMP. In the absence of glycine and ATA, copper removal rate was found to be high in the slurry with 5% H 2O 2 at pH 2. The removal rate then decreased and reached the minimum at pH 6 and started to increase in alkaline conditions. With the addition of 0.01 M glycine, the removal rates of copper were lowered in acidic slurries, but increased significantly in alkaline slurries. The addition of ATA lowered copper removal rates, however, better surface planarity was achieved. The present investigation provides an insight to the mechanism of Cu removal in the presence of oxidizer, complexing agent and inhibitor.

Chemical-Mechanical Planarization of Copper: The Effect of Inhibitor and Complexing Agent

AbstractThe present investigation was focused on understanding of the oxidation, dissolution and modification of Cu surface in slurries at various pH using hydrogen peroxide as oxidizer, glycine as complexing agent and 3-amino-triazol (ATA) as inhibitor during Cu-CMP. The electrochemical process involved in the oxidative dissolution of copper was investigated by potentiodynamic polarization studies. Surface modification of copper was investigated using Xray photoelectron spectroscopy to understand the interaction of Cu-H2O2-glycine-ATA during CMP. In the absence of glycine and ATA, the copper removal rate is found to be high in a slurry with 5% H2O2 at pH 2, then it decreases with increasing pH and reaches the minimum at pH 6, it continuously increases at alkaline condition. In the presence of 0.01M glycine, the removal rate of copper decreases in acidic slurries while increases significantly in alkaline slurries. With the further addition of ATA, the copper removal rate was reduced. However, better surface planarity was obtained. The present investigation enhanced understanding of the mechanism of Cu CMP in the presence of oxidizer, complexing agent and inhibitor for formulation of a highly effective CMP-slurry.

Kinetics and Mechanism of the Reaction of Carbon Tetrachloride with Copper in Dimethylacetamide

The reaction of copper with carbon tetrachloride in dimethylacetamide was studied. In the absence of atmospheric oxygen, the oxidative dissolution of copper occurred by the mechanism of single-electron transfer with the formation of C2Cl6 and copper(I) complexes. The kinetic and thermodynamic parameters of the reaction were found. The reaction mechanism is discussed.

The Role of Glycine in the Chemical Mechanical Planarization of Copper

Chemical mechanical polishing (CMP) is an essential process in the production of integrated circuits containing copper interconnects. The role of glycine in reactive slurries representative of those that might be used in copper CMP was studied with the aim of improving our understanding of the mechanisms at play. The electrochemical processes involved in the oxidative dissolution of copper were investigated by potentiodynamic polarization studies. To delineate the specific effect of glycine on the dissolution and polishing of copper, electrochemical tests were conducted in aqueous media with and without glycine. Experimentally measured polarization curves agreed well with potential-pH diagrams for the copper-water and copper-water-glycine systems. In situ electrochemical polarization experiments and open-circuit potential measurements were then conducted during polishing using slurries containing either no glycine or M glycine. These tests indicated that glycine curtails the formation of copper oxide films during polishing and hence may improve the CMP process by controlling the oxide thickness. © 2002 The Electrochemical Society. All rights reserved.

Étude électrochimique de l'oxydation de la chalcopyrite en milieu acide chloruré

The oxidative dissolution of copper from chalcopyrite in an acidic medium shows that the dissolution is inhibted as the mineral dissolves. The reaction mechanisms which are responsible for this inhibited phenomena are developed through electrochemical measurements of the reactivity of the mineral itself and its oxidation in a ferric medium. The elementary anodic curve of chalcopyrite in chloride media is characterised by two peaks of oxidation, the first being attributed to adsorption while the second to an oxidation leading to passivation of the solid. The chalcopyrite transforms superficially into a sulfide which is less reactive. Accordingly, the oxidation of the mineral in a ferric medium is under anodic control.

Copper Corrosion: III . Electrochemical Theory of General Corrosion

The oxidative dissolution of copper in acidic, aqueous media is limited in rate by the presence at the metal‐solution interface of a growing film of cuprous oxide. A brief survey of what is known about the nature and modes of growth of such films provides the basis for a “duplex film” model of the corroding copper system. This leads to an interpretation of some features of the observed kinetics of the corrosion reactions reported in the preceding paper, including the constancy of rates of dissolution and film growth following induction periods, the kinetic link between them, the absence of effects due to concentration polarization of dissolved oxygen, and the results of “replacement experiments.” The interpretation is made in terms of the operation of a hypothetical double electrochemical cell, corresponding with the duplex film model, and leaves unresolved problems associated with possible special functions of carbon dioxide and the mechanism of oxygen reduction.