In situ Absorbance Spectroscopy for Characterizing the Low Temperature Oxidation Kinetics of Sputtered Copper Films

Rice, Katherine P.; Han, Junsu; Campbell, Ian P.; Stoykovich, Mark P.

doi:10.1007/s11085-014-9508-1

Cited by 8 publications

(5 citation statements)

References 23 publications

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“…Previous studies on the oxidation kinetics of Cu performed above 350°C report that the oxidation kinetics typically follows the parabolic rate law with Cu 2 O as the predominant oxide phase. 5 On the contrary, different growth laws, such as the cubic rate law, 32 the parabolic rate law, 17,19 the inverse logarithmic law, 32 and the linear rate law 15,20,32 have been reported for the oxidation of Cu films below 300°C. The different growth laws for the oxidation kinetics of Cu films, as reported in the literature, are summarized in Table I.…”

Section: Introductionmentioning

confidence: 99%

In situ oxidation studies of Cu thin films: Growth kinetics and oxide phase evolution

Unutulmazsoy

Cancellieri

Chiodi

et al. 2020

Journal of Applied Physics

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A comprehensive understanding of the oxidation of Cu thin films in the low-temperature regime is of fundamental interest and particularly relevant for applications in the fields of micro-and nanoelectronics, sensors, catalysis, and solar cells. The current study reports on the oxidation kinetics of PVD grown Cu thin films (20-150 nm thick) and the oxide phase evolution from Cu 2 O to CuO upon thermal oxidation in the temperature range of 100-450°C. XRD investigations in the laboratory and at the synchrotron show that the oxide phase formation critically depends on the oxidation conditions such as temperature and oxygen partial pressure. The real-time synchrotron XRD measurements reveal that the formation of the CuO phase only starts after complete oxidation of the Cu films to Cu 2 O films. In situ resistance measurements were performed to follow the oxide growth rate of Cu 2 O on Cu films in the temperature range of 100-300°C in air and in 10 mbar pO 2 . It is found that the oxidation kinetics of Cu films to Cu 2 O films follows the linear rate law, which is attributed to surface reaction controlled oxidation. The oxygen dissociation rate at the gas-solid interface is the rate-limiting process. A dramatic decrease in the linear oxidation rate is observed at low oxygen partial pressures. The fundamental differences between the oxidation rate-limiting processes of Cu as compared to other transition metal films are discussed.

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Section: Introductionmentioning

confidence: 99%

In situ oxidation studies of Cu thin films: Growth kinetics and oxide phase evolution

Unutulmazsoy

Cancellieri

Chiodi

et al. 2020

Journal of Applied Physics

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“…At low temperatures, parabolic, logarithmic, inverse logarithmic, power law, and linear kinetics have been reported. According to Pinnel et al [8], Zhong et al [10], Ramanandan et al [11], and Rice et al [12], the oxidation kinetics follow the parabolic rate law, which suggests a diffusion-controlling oxidation mechanism, at temperature intervals 50-150 • C [8], 80-260 • C [10], 120-150 • C [11], and 250-350 • C [12]. According to Ramanandan et al [11], the oxide film reached a thickness of 30 nm in tens of minutes at 140 • C and 150 • C, in an hour at 130 • C, and in a few hours at 120 • C. After that, the oxide layer did not grow further.…”

Section: Introductionmentioning

confidence: 99%

“…Copper oxides have potential applications in solar cells, semiconductors, gas sensors, catalysts, etc. Many researchers have studied the oxidation behavior of bulk copper metal [5][6][7][8] and copper thin films [9][10][11][12][13][14] at elevated temperatures in air. The main outcome of these studies indicated that copper oxidation products, Cu 2 O (cuprous oxide) and CuO (cupric oxide), are formed on the surface of copper at various temperatures and exposure times, and the growth of these oxide layers follows most frequently the parabolic law, indicating that the growth rate decreases with time and some maximum thickness range is expected.…”

Section: Introductionmentioning

confidence: 99%

The Oxidation of Copper in Air at Temperatures up to 100 °C

Aromaa

Kekkonen

Mousapour

et al. 2021

CMD

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The aim of this study was to investigate the oxidation kinetics of copper at low temperatures (60 °C to 100 °C) in air by isothermal thermogravimetric analysis (TGA) and quartz crystal microbalance (QCM). The weight change in thermogravimetric tests showed periodic weight increase and decrease. In thermogravimetric tests the mass of the copper sample increased until the oxidation gradually slowed down and finally started to decrease due to cracking and spalling of the oxide formed on the surface. In QCM tests using electrodeposited copper film, the weight change was rapid at the beginning but slowed to a linear relationship after few minutes. Temperature and exposure time appeared to have a large effect on oxide film thickness and composition. With QCM, oxidation at 60–80 °C produced less than 40 nm films in 10 days. Oxidation at 90–100 °C produced 40 nm thick films in a day and over 100 nm films in a week. Although SEM-EDS analyses in TGA tests indicated that oxygen was adsorbed on the copper surface, neither XRD patterns nor Raman spectroscopy measurements showed any trace of Cu2O or CuO formation on the copper surface. Electrochemical reduction analysis of oxidized massive copper samples indicated that the oxide film is mostly Cu2O, and CuO develops only after several days at 90–100 °C.

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“…On the other hand, the oxidation kinetics of Cu at low temperatures, including RT, are still not completely understood. The oxidation at temperatures below 350 °C has been investigated by various analytical techniques, including ellipsometry, ,,, X-ray diffraction, , X-ray photoelectron spectroscopy, ,, terahertz transmission spectroscopy, absorbance spectroscopy, or resistivity measurements. , In most experiments, the Cu surface was either exposed directly to the air or placed in an oxygen-enriched atmosphere. The thickness of the copper layer after long exposure times can reach a few hundred nanometers, while the oxidation kinetics follow either parabolic − or logarithmic ,, or even linear ,,, growth rates, depending on temperature, oxygen partial pressure, or the morphology and texture of Cu films …”

Section: Introductionmentioning

confidence: 99%

Initial Stages of Oxide Formation on Copper Surfaces during Oxygen Bombardment at Room Temperature

Peter

Petravić

2021

J. Phys. Chem. C

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We have studied the oxidation kinetics of initial stages of oxide formation on clean metallic copper surfaces during low-energy O2 + bombardment at room temperature using X-ray photoelectron spectroscopy around Cu 2p and O 1s core-levels and Auger Cu LMM peaks. Two stages in the oxidation process of Cu were observed. For the lower oxygen doses, a single, Cu2O, phase was formed, while the growth of the second, CuO, phase preferentially forms at higher doses. The relative contributions of Cu2O and CuO phases were determined from the deconvolution of Auger Cu LMM spectra, while the thickness of the oxides was estimated from the intensity of the underlying metallic Cu LMM signal and in-depth profiles obtained by secondary ion mass spectrometry. While the growth of the Cu2O layer follows the linear oxidation kinetics, characteristic of the fast chemical reactions of oxygen with the host atoms around the penetration depth of impinging oxygen atoms, the logarithmic law was found for the CuO growth, consistent with the formation of CuO nuclei within the Cu2O matrix.

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In situ Absorbance Spectroscopy for Characterizing the Low Temperature Oxidation Kinetics of Sputtered Copper Films

Cited by 8 publications

References 23 publications

In situ oxidation studies of Cu thin films: Growth kinetics and oxide phase evolution

In situ oxidation studies of Cu thin films: Growth kinetics and oxide phase evolution

The Oxidation of Copper in Air at Temperatures up to 100 °C

Initial Stages of Oxide Formation on Copper Surfaces during Oxygen Bombardment at Room Temperature

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