Recrystallization of Electrodeposited Copper Thin Films During Annealing

Alshwawreh, Nidal; Militzer, Matthias; Bizzotto, Dan

doi:10.1007/s11664-010-1342-x

Cited by 7 publications

(4 citation statements)

References 19 publications

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“…Kalu reported the activation energy for vacancy migration to be 20 kJ/mol in drawn oxygen-free high thermal conductivity Cu 52 . In electrodeposited Cu, recrystallization was reported to occur at temperatures as low as ambience, and the recrystallization activity energy was estimated to be 86 kJ/mol 17 . Gangulee 53 determined the activation energy for recovery (28 kJ/mol) and recrystallization (57 kJ/mol), in electroplated Cu.…”

Section: Discussionmentioning

confidence: 99%

“…We speculate that a high density of HABs and TJs would disturb the thermal stability of any CTBs in the vicinity. Few investigations have been conducted on the kinetics of recovery and recrystallization in NT Cu, though some work has been carried out on the HAG Cu 17 18 19 20 21 22 . This paper reports our studies of the kinetics of recovery and recrystallization of NT Cu.…”

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confidence: 99%

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Influence of grain boundary characteristics on thermal stability in nanotwinned copper

Niu

Han

et al. 2016

Sci Rep

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High density grain boundaries provide high strength, but may introduce undesirable features, such as high Fermi levels and instability. We investigated the kinetics of recovery and recrystallization of Cu that was manufactured to include both nanotwins (NT) and high-angle columnar boundaries. We used the isothermal Johnson-Mehl-Avrami-Kolmogorov (JMAK) model to estimate activation energy values for recovery and recrystallization and compared those to values derived using the non-isothermal Kissinger equation. The JMAK model hinges on an exponent that expresses the growth mechanism of a material. The exponent for this Cu was close to 0.5, indicating low-dimensional microstructure evolution, which is associated with anisotropic twin coarsening, heterogeneous recrystallization, and high stability. Since this Cu was of high purity, there was a negligible impurity-drag-effect on boundaries. The twin coarsening and heterogeneous recrystallization resulted from migration of high-angle columnar boundaries with their triple junctions in one direction, assisted by the presence of high concentration vacancies at boundaries. Analyses performed by electron energy loss spectroscopy of atomic columns at twin boundaries (TBs) and in the interior showed similar plasma peak shapes and L3 edge positions. This implies that values for conductivity and Fermi level are equal for atoms at TBs and in the interior.

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Section: Discussionmentioning

confidence: 99%

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confidence: 99%

Influence of grain boundary characteristics on thermal stability in nanotwinned copper

Niu

Han

et al. 2016

Sci Rep

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“…This formalism is often employed in the literature to model the reverse-sigmoidal shaped decay in film resistivity during recrystallization. 26,33 For this purpose, the fraction recrystallized at any given time, s, during the recrystallization process, s 0 s s 1 , is defined in terms of the normalized resistivity drop f q ðsÞ ¼ qðs 0 Þ À qðsÞ qðs 0 Þ À qðs 1 Þ :…”

Section: Transformation Kinetics Analysismentioning

confidence: 99%

Characterization of room temperature recrystallization kinetics in electroplated copper thin films with concurrent x-ray diffraction and electrical resistivity measurements

Treger

Witt

Cabral³

et al. 2013

Journal of Applied Physics

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Concurrent in-situ four-point probe resistivity and high resolution synchrotron x-ray diffraction measurements were used to characterize room temperature recrystallization in electroplated Cu thin films. The x-ray data were used to obtain the variation with time of the integrated intensities and the peak-breadth from the Cu 111 and 200 reflections of the transforming grains. The variation of the integrated intensity and resistivity data with time was analyzed using the Johnson-Mehl-Avrami-Kolmogorov (JMAK) model. For both 111-textured and non-textured electroplated Cu films, four-point probe resistivity measurements yielded shorter transformation times than the values obtained from the integrated intensities of the corresponding Cu 111 reflections. In addition, the JMAK exponents fitted to the resistivity data were significantly smaller. These discrepancies could be explained by considering the different material volumes from which resistivity and diffraction signals originated, and the physical processes which linked these signals to the changes in the evolving microstructure. Based on these issues, calibration of the resistivity analysis with direct structural characterization techniques is recommended. V C 2013 AIP Publishing LLC.

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“…4,6 Rigorous control of copper growth can be difficult: the surface energy of copper is high and the atomic diffusion rate is significant, so that dewetting often occurs during growth or subsequent annealing. [7][8][9][10][11][12] Thin films of copper can be deposited by a wide variety of techniques including wet chemical growth, physical vapor deposition, chemical vapor deposition (CVD) and atomic layer deposition (ALD). To deposit copper conformally in substrate architectures such as trenches and vias that have re-entrant or high aspect ratio features, ALD and CVD are preferred techniques because of the ability of the precursor molecules to diffuse throughout the structure.…”

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confidence: 99%

Chemical Vapor Deposition of Copper: Use of a Molecular Inhibitor to Afford Uniform Nanoislands or Smooth Films

Babar

Davis

Zhang

et al. 2014

ECS J. Solid State Sci. Technol.

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We report a method to control the surface morphology of thin copper films during growth by chemical vapor deposition from the precursor Cu(hfac)VTMS. A molecular inhibitor -an additive that modifies the surface attachment kinetics but does not decompose and contribute impurity atoms to the film -is added during the nucleation and/or growth stages of the film. Here we show that the reaction by-product VTMS can serve as such an inhibitor. If the inhibitor is added during the nucleation stage, when bare substrate surface is still exposed, the inhibitor greatly reduces the rate of coalescence and promotes the formation of a large density of uniformly-sized copper islands. Alternatively, if the film is allowed to nucleate in the absence of the inhibitor, subsequent addition of the inhibitor leads to a continuous copper film that is remarkably smooth on the nm scale. © 2014 The Electrochemical Society. [DOI: 10.1149/2.009405jss] All rights reserved.Manuscript submitted January 14, 2014; revised manuscript received February 27, 2014. Published March 11, 2014 Copper is used in many advanced nanoscale technologies due to its high electrical and thermal conductivity, and its strong surface plasmon resonance when in the form of nanoparticles.1-5 For continuous films, such as those used as the seed layer for electrodeposition in integrated circuits, the film must be less than 10 nm thick, pinholefree, and extremely smooth, with an rms roughness of less than 1 nm. For optical devices based on copper nanoparticles, it is important to control the nanoparticle size and morphology. 4,6 Rigorous control of copper growth can be difficult: the surface energy of copper is high and the atomic diffusion rate is significant, so that dewetting often occurs during growth or subsequent annealing. 7-12Thin films of copper can be deposited by a wide variety of techniques including wet chemical growth, physical vapor deposition, chemical vapor deposition (CVD) and atomic layer deposition (ALD). To deposit copper conformally in substrate architectures such as trenches and vias that have re-entrant or high aspect ratio features, ALD and CVD are preferred techniques because of the ability of the precursor molecules to diffuse throughout the structure.13-17 A general difficulty arises when the substrate is relatively unreactive, such as an oxide surface: the resulting films tend to be rough owing to a combination of sparse nucleation and the tendency of the deposited material to agglomerate. 18 Once surface roughness on the length scale of the island separation is formed, it cannot be eliminated by the overgrowth of more material. 18The use of additives to enhance film smoothness is well established in the electrochemical deposition of copper 19,20 but is not common in CVD. For CVD, the morphology of copper films can sometimes be improved by adding a second component to the growth gas. For example, addition of H 2 O to a flux of Cu(hfac)VTMS (hfac = hexafluoroacetylacetonate and VTMS = vinyltrimethylsilane) enhances the wettability of the surfac...

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Recrystallization of Electrodeposited Copper Thin Films During Annealing

Cited by 7 publications

References 19 publications

Influence of grain boundary characteristics on thermal stability in nanotwinned copper

Influence of grain boundary characteristics on thermal stability in nanotwinned copper

Characterization of room temperature recrystallization kinetics in electroplated copper thin films with concurrent x-ray diffraction and electrical resistivity measurements

Chemical Vapor Deposition of Copper: Use of a Molecular Inhibitor to Afford Uniform Nanoislands or Smooth Films

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