Combined Electrochemical and Electron Spectroscopic Investigations of the Surface Oxidation of TiAlN HPPMS Hard Coatings

Wiesing, M.; Baben, Moritz to; Schneider, Jochen M.; Arcos, Teresa de los; Grundmeier, Guido

doi:10.1016/j.electacta.2016.05.011

Cited by 20 publications

(20 citation statements)

References 44 publications

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“…Assuming a model of perfectly separated layers, the observed behavior can be explained as a stepwise formation of first a TiAl(O,N) growth region due to inward migration of oxygen and then the establishment of a top layer of fully oxidized Ti(IV). This interpretation is also supported by recent investigation on the electrochemical oxidation of TiAlN, where the electrochemical oxidation of TiAlN could be described by a reactive migration mechanism as well . The relevance of the oxygen inward migration for the oxidation is further highlighted by the Al/Ti ratios reported in Table : though preponderant aluminum outward migration is expected in the case of the high temperature TiAlN oxidation, the Al/Ti ratios remained rather constant and only slight enrichment of aluminum was observed at 800 K …”

Section: Resultssupporting

confidence: 74%

“…The gas pressure inside the chamber was 0.46 Pa and the Ar:N 2 ratio was set to 4:1. The structure of the samples was characterized by X‐Ray Diffraction and a random structure was found . The density of the TiAlN was around 4.8 g cm −3 and the stoichiometry was Ti 0.2 Al 0.3 N 0.5 as determined by an Ar + sputtered sample measured by XPS.…”

Section: Methodsmentioning

confidence: 99%

“…Thin Film Deposition : The HPPMS deposition process was chosen due to the superior quality of the coatings. As described elsewhere, TiAlN thin films with a thickness of 1.2 µm were deposited on boron‐doped (100) Si wafer (1–5 Ω cm) . The deposition chamber (CemeCon CC‐800/9) was equipped with a rectangular magnetron (500 × 88 mm 2 ) and a Ti/Al compound target, which provided a Ti/Al ratio of nearly 1 and was located 80 mm away from the substrates.…”

Section: Methodsmentioning

confidence: 99%

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The Thermal Oxidation of TiAlN High Power Pulsed Magnetron Sputtering Hard Coatings as Revealed by Combined Ion and Electron Spectroscopy

Wiesing

Arcos

Grundmeier

2016

Adv Materials Inter

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injection molding. [5] In this case the TiAlN coating is in contact with an oxygen containing polymer melt at a temperature of 500-700 K. Among the plethora of parameters that govern the development of specific surface-near multilayer structures upon oxidation the stoichiometry and internal structure of the coating previous to oxidation is of central importance. These latter aspects can be tailored up to a certain point through control of the deposition process. In particular, high power pulsed magnetron sputtering (HPPMS) has gained much attraction recently for the deposition of hard coatings with high density and improved properties in terms of adhesion, hardness, and low surface roughness. [6][7][8][9] The reason for the increased quality of HPPMS-deposited films lies in the highly increased fraction of ionized species during deposition, which allows for a higher degree control on the growing film structure. [9] However, independently of the degree of control achievable during the deposition process, a final issue critical for the establishment of a top oxide layer is the way samples react to different ambient conditions once the deposition process is finished. This aspect has been explored both theoretically and experimentally. Music et al., for example, used ab initio molecular dynamics to investigate the interaction of TiAlN surfaces with residual and environmental gases, namely O 2 , H 2 O, and CO 2 . [10] Greczynski et al. showed experimentally how the surface composition of TiN films dramatically changed as function of the conditions in which the venting procedure is performed. [11] In short, in order to achieve specific oxideterminated surfaces, the basic mechanisms by which thermal oxidation proceeds in the medium temperature range need to be better understood.Preliminary experimental investigations of the oxygen chemisorption layer of HPPMS-deposited TiAlN have been already performed, showing that the oxygen chemisorption is self-limited and results into a surface segregated Ti 2 O 3 layer. [12] However, the present work is intended to provide a more accurate microscopic model of the chemisorption layer by using combined in situ X-ray Photoelectron Spectroscopy (XPS) and Low Energy Ion Scattering (LEIS). Based on the results obtained, a microscopic model of the oxidation of TiAlN at medium temperatures which are relevant for polymer processing will be developed. The thermal oxidation of TiAlN hard coatings deposited by High Power PulsedMagnetron Sputtering (HPPMS) is investigated at room temperature and 800 K at oxygen pressures ranging from 10 −6 to 10 −2 Pa by means of in situ X-ray and Ultraviolet Photoelectron Spectroscopy as well as Low Energy Ion Scattering. The spectra reveal that oxygen binds selectively to titanium during the initial chemisorption step and simultaneously some oxygen is dissolved into subsurface layers, which stay metallic. Enhanced oxidation results into continuous formation of a multilayered oxide film including oxynitride TiAl(O,N) as a metastable reaction product buried be...

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Section: Resultssupporting

confidence: 74%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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The Thermal Oxidation of TiAlN High Power Pulsed Magnetron Sputtering Hard Coatings as Revealed by Combined Ion and Electron Spectroscopy

Wiesing

Arcos

Grundmeier

2016

Adv Materials Inter

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“…After deposition of TiAlN by HPPMS, a certain amount of uncontrolled surface oxidation takes place within the reactor and during subsequent exposure to ambient atmosphere . Electrochemical oxidation, on the other hand, leads to controlled oxidation of the near-surface region, as shown by Wiesing et al By means of the electrochemical oxidation of TiAlN, the oxynitridic TiAl(O,N) near-surface region converts into an oxide layer consisting of amorphous TiO 2 and Al 2 O 3 phases. This is due to the irreversible oxidation of Ti(III) to Ti(IV) and the nitridic nitrogen conversion to molecular N 2 .…”

Section: Resultsmentioning

confidence: 99%

“…The oxidation of TiAlN can also be carried out by electrochemical techniques. Wiesing et al showed that electrochemical oxidation of TiAlN leads to the formation of several nanometer-thin semiconducting surface films with a composition of (TiO 2 ) x (Al(OH) 3 ) y . In the process, an irreversible exchange of nitrogen in TiAl(O,N) and inward migration of oxygen occurs, with the subsequent release of nitrogen …”

Section: Introductionmentioning

confidence: 99%

Single-Molecule Desorption Studies of Poly(acrylic acid) at Electrolyte/Oxide/TiAlN Interfaces

et al. 2020

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The presented studies correlate the surface chemistry of electrochemically oxidized TiAlN hard coatings with the desorption forces of poly(acrylic acid) (PAA) at the electrolyte/oxide/TiAlN interface. Atomic force microscopy (AFM)-based single-molecule force spectroscopy (SMFS) was performed at different pH values to investigate surface chemistry-induced changes in desorption force. The chemical state was characterized by Xray photoemission spectroscopy and electrochemical analysis. The results show that the desorption forces continuously decrease with increasing pH in the range from pH 5 to 9. The comparison of the desorption forces on rf-sputtered titanium dioxide and aluminum oxide films shows that the electrochemically oxidized surface of TiAlN, in agreement with the revealed surface composition, shows interfacial adhesive properties in contact with PAA and water that resemble a pure titanium oxide layer. Load rate-dependent measurements were performed to analyze both the free energy barrier and the transition state distance.

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Correlative Theoretical and Experimental Study of the Polycarbonate | X Interfacial Bond Formation (X = AlN, TiN, (Ti,Al)N) During Magnetron Sputtering

Patterer

Ondračka

Bogdanovski

et al. 2023

Adv Materials Inter

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To understand the interfacial bond formation between polycarbonate (PC) and magnetron‐sputtered metal nitride thin films, PC | X interfaces (X = AlN, TiN, (Ti,Al)N) are comparatively investigated by ab initio simulations as well as X‐ray photoelectron spectroscopy. The simulations predict significant differences at the interface as N and Ti form bonds with all functional groups of the polymer, while Al reacts selectively only with the carbonate group of pristine PC. In good agreement with simulations, experimental data reveal that the PC | AlN and the PC | (Ti,Al)N interfaces are mainly defined by interfacial C─N bonds, whereas for PC | TiN, the interface formation is also characterized by numerous C─Ti and (C─O)─Ti bonds. Bond strength calculations combined with the measured interfacial bond density indicate the strongest interface for PC | (Ti,Al)N followed by PC | AlN, whereas the weakest is predicted for PC | TiN due to its lower density of strong interfacial C─N bonds. This study shows that the employed computational strategy enables prediction of the interfacial bond formation between PC and metal nitrides and that it is reasonable to assume that the research strategy proposed herein can be readily adapted to other organic | inorganic interfaces.

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Combined Electrochemical and Electron Spectroscopic Investigations of the Surface Oxidation of TiAlN HPPMS Hard Coatings

Cited by 20 publications

References 44 publications

The Thermal Oxidation of TiAlN High Power Pulsed Magnetron Sputtering Hard Coatings as Revealed by Combined Ion and Electron Spectroscopy

The Thermal Oxidation of TiAlN High Power Pulsed Magnetron Sputtering Hard Coatings as Revealed by Combined Ion and Electron Spectroscopy

Single-Molecule Desorption Studies of Poly(acrylic acid) at Electrolyte/Oxide/TiAlN Interfaces

Correlative Theoretical and Experimental Study of the Polycarbonate | X Interfacial Bond Formation (X = AlN, TiN, (Ti,Al)N) During Magnetron Sputtering

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