Implementation of the Chicot–Lesage Composite Hardness Model in a Determination of Absolute Hardness of Copper Coatings Obtained by the Electrodeposition Processes
Abstract
:1. Introduction
2. Materials and Methods
2.1. Production of the Cu Coatings by Electrodeposition
- (a)
- the basic electrolyte: 240 g L−1 CuSO4·5 H2O in 60 g L−1 H2SO4 (electrolyte I), and
- (b)
- the electrolyte with additives: 240 g L−1 CuSO4∙5H2O, 60 g L−1 H2SO4, 0.124 g L−1 NaCl, 1 g L−1 PEG 6000 (polyethylene glycol), 0.0015 g L−1 MPSA (3–Mercapto–1–propanesulfonic acid) (electrolyte II).
2.2. Morphological and Structural Analysis of the Electrolytically Produced Cu Coatings
- (a)
- Scanning electron microscope (SEM): morphology of the electrolytically obtained Cu coatings was examined using JEOL JSM-6610LV (JEOL Ltd., Tokyo, Japan).
- (b)
- Atomic force microscope (AFM): topography of the coatings was monitored in the contact mode using Auto Probe CP Research; TM Microscopes—Veeco Instruments, Santa Barbara, CA, USA. The software SPMLab (SPMLab NT Ver. 6.0.2., Veeco Instruments, Santa Barbara, CA, USA) was used for an estimation of roughness of obtained coatings by the determination of the arithmetic average of the absolute (Ra) roughness parameters, and for generation of histogram of topography.
- (c)
- X-ray diffractometer (XRD): The crystal structure of obtained Cu coatings electrodeposited on Si(111) cathode was analyzed using RIGAKU Ultima IV diffractometer (Rigaku Co. Ltd., Tokyo, Japan) in Bragg–Brentano geometry with CuKα radiation in a 2θ range from 30° to 95°. For an estimation of the preferred orientation of Cu coatings, methodology based on the determination of the “Texture Coefficient“, TC(hkl) and the “Relative Texture Coefficient“, RTC(hkl) was applied. The detailed description of a procedure for the determination of these coefficients is presented in [21,25,26].
2.3. Characterization of the Mechanical Properties of Cu Coatings
3. Results
3.1. Analysis of the Copper Coatings Electrodeposited on the Brass Cathode
3.2. Analysis of the Copper Coatings Electrodeposited on Si(111) Cathode
3.3. Analysis of the Copper Coatings Electrodeposited on the Si(111) Cathode—Influence of Coating Thickness
4. Discussion
5. Conclusions
- (a)
- The Cu coatings obtained from the basic (sulfate) electrolyte were fine-grained with mat appearance. These coatings showed strong (220) preferred orientation. The smooth mirror bright Cu coatings of strong (200) preferred orientation were obtained from the electrolyte with additives for leveling and brightening. The roughness of the fine-grained coatings was considerably larger than the roughness of smooth coatings.
- (b)
- Hardness of the mat Cu coatings was larger than that obtained for mirror bright Cu coatings. This difference can be attributed to numerous boundaries among grains in the fine-grained mat coatings.
- (c)
- The shapes of the dependencies of the coating hardness calculated by the C–L model on the RID differ mutually for the Cu coatings obtained on the brass and the Si(111) cathodes. This indicated the strong effect of cathode hardness on coating hardness.
- (d)
- Irrespective of conditions of electrolysis, the critical or limiting relative indentation depth (RID) of 0.14 was established for all types of the coatings. This value separates the zone in which the composite hardness can be equaled with the coating hardness (negligible effect of the cathode hardness on the composite hardness) and the zone of a necessary application of the C–L model for a determination of the absolute hardness of the Cu coatings (the strong effect of the cathode hardness on the composite hardness).
- (e)
- The established RID value of 0.14 obtained by implementation of the C–L model represents novel criterion for an estimation of the absolute hardness of electrolytically obtained Cu coatings.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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No. | The Type of Electrolyte | The Type of Cathode | The Coating Thickness (δ/µm) |
---|---|---|---|
1. | electrolyte I | brass | 20 |
2. | electrolyte II | brass | 20 |
3. | electrolyte I | Si(111) | 20 |
4. | electrolyte II | Si(111) | 20 |
5. | electrolyte I | Si(111) | 40 |
6. | electrolyte II | Si(111) | 40 |
Plane | R (in %) | Rs | TC | RTC (in %) | |||
---|---|---|---|---|---|---|---|
(hkl) | RI | RII | (in %) | TCI | TCII | RTCI | RTCII |
(111) | 7.9 | 3.31 | 54.6 | 0.145 | 0.061 | 1.71 | 1.47 |
(200) | 3.2 | 92.12 | 25.1 | 0.127 | 3.67 | 1.49 | 88.31 |
(220) | 84.0 | 4.05 | 10.9 | 7.71 | 0.37 | 90.67 | 8.90 |
(311) | 4.9 | 0.52 | 9.4 | 0.521 | 0.055 | 6.13 | 1.32 |
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Mladenović, I.O.; Lamovec, J.S.; Vasiljević-Radović, D.G.; Vasilić, R.; Radojević, V.J.; Nikolić, N.D. Implementation of the Chicot–Lesage Composite Hardness Model in a Determination of Absolute Hardness of Copper Coatings Obtained by the Electrodeposition Processes. Metals 2021, 11, 1807. https://doi.org/10.3390/met11111807
Mladenović IO, Lamovec JS, Vasiljević-Radović DG, Vasilić R, Radojević VJ, Nikolić ND. Implementation of the Chicot–Lesage Composite Hardness Model in a Determination of Absolute Hardness of Copper Coatings Obtained by the Electrodeposition Processes. Metals. 2021; 11(11):1807. https://doi.org/10.3390/met11111807
Chicago/Turabian StyleMladenović, Ivana O., Jelena S. Lamovec, Dana G. Vasiljević-Radović, Rastko Vasilić, Vesna J. Radojević, and Nebojša D. Nikolić. 2021. "Implementation of the Chicot–Lesage Composite Hardness Model in a Determination of Absolute Hardness of Copper Coatings Obtained by the Electrodeposition Processes" Metals 11, no. 11: 1807. https://doi.org/10.3390/met11111807