Homer Kissinger and the Kissinger equation

Blaine, Roger L.; Kissinger, H. E.

doi:10.1016/j.tca.2012.04.008

Cited by 492 publications

(219 citation statements)

References 23 publications

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“…The samples were annealed in alumina pans from 400 to 800 • C at a heating rate of 10 • C/min under an argon atmosphere. The onset reaction temperature was observed, and the activation energy of the reaction was calculated following the Kissinger method [22]. In order to minimize the effect of particle shape and size, the material was molded into a circular specimen having a thickness and diameter of 50 mm at a load of seven tons (to have 85% relative density after molding).…”

Section: Characterizationmentioning

confidence: 99%

“…In other words, Al and Ni atoms migrate mainly through the volume diffusion, however, as the milling time increases, the surface diffusion becomes easier due to the reduction in activation energy. According to the Kissinger method [22], a solid-state reaction is represented by the following equation:…”

Section: Activation Energy For Exothermic Reactionmentioning

confidence: 99%

“…According to the Kissinger method [22], a solid-state reaction is represented by the following equation:…”

mentioning

confidence: 99%

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Exothermic Reaction Kinetics in High Energy Density Al-Ni with Nanoscale Multilayers Synthesized by Cryomilling

Han

et al. 2018

Metals

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Abstract:The Al-Ni system is known as a high energy density materials (HEDM) because of its highly exothermic nature during intermetallic compound (IMC) formation. In this study, elemental Al and Ni powder were milled to explore the effect of cryomilling atmosphere on the microstructure and exothermic behavior. Scanning electron microscope (SEM) observations show continuous structural refinement up to 8 h of cryomilling. No IMC phase was detected in the X-ray diffraction (XRD) spectrum. Differential thermal analyzer (DTA) results show two exothermic peaks for 8 h cryomilled powder as compared to that of powder milled for 1 h. The ignition temperature of prepared powder mixture also decreased due to gradual structural refinement. The activation energy was also calculated and correlated with the DTA and SEM results. The cryomilled Al-Ni powder is composed of fine Al-Ni metastable junctions which improve the reactivity at a lower exothermic reaction temperature.

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Section: Characterizationmentioning

confidence: 99%

Section: Activation Energy For Exothermic Reactionmentioning

confidence: 99%

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Exothermic Reaction Kinetics in High Energy Density Al-Ni with Nanoscale Multilayers Synthesized by Cryomilling

Han

et al. 2018

Metals

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“…The barrier failure temperature (T c ) was determined based on the onset of Cu 3 Si XRD peaks during the in-situ ramp anneal which is a signature of the reaction between Cu and Si. The kinetics of Cu 3 Si formation was assessed from the T c values determined from the multiple ramp anneal rates and applying the Kissinger equation, [13][14][15] which has been shown to be valid for silicide formation using ramp anneals, 16,17 to determine the effective activation energy (E a ) for silicidation in presence of the Cu diffusion barrier layers. The form of the Kissinger equation used in this study is given as:…”

Section: Methodsmentioning

confidence: 99%

In Situ Ramp Anneal X-ray Diffraction Study of Atomic Layer Deposited Ultrathin TaN and Ta_1-xAl_xN_yFilms for Cu Diffusion Barrier Applications

Consiglio

Dey

et al. 2016

ECS J. Solid State Sci. Technol.

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films with x = 0.21 to 0.88 were deposited by atomic layer deposition (ALD) and evaluated for Cu diffusion barrier effectiveness compared to physical vapor deposition (PVD) grown TaN. Cu diffusion barrier effectiveness was investigated using in-situ ramp anneal synchrotron X-ray diffraction (XRD) on Cu/1.8 nm barrier/Si stacks. A Kissinger-like analysis was used to assess the kinetics of Cu 3 Si formation and determine the effective activation energy (E a ) for Cu silicidation. Compared to the stack with a PVD TaN barrier, the stacks with the ALD films exhibited a higher crystallization temperature (T c ) for Cu silicidation. The E a values of Cu 3 Si formation for stacks with the ALD films were close to the reported value for grain boundary diffusion of Cu whereas the E a of Cu 3 Si formation for the stack with PVD TaN is closer to the reported value for lattice diffusion. For 3 nm films, grazing incidence in-plane XRD showed evidence of nanocrystallites in an amorphous matrix with broad peaks corresponding to high density cubic phase for the ALD grown films and lower density hexagonal phase for the PVD grown film further elucidating the difference in initial failure mechanisms due to differences in barrier crystallinity and associated phase. The continuous scaling of Cu interconnects for sub-10 nm technology nodes calls for development of ultrathin and conformal Cu diffusion barriers. Due to its ability to conformally deposit films with nanoscale thickness control, atomic layer deposition (ALD) is an attractive method for depositing refractory metal nitride diffusion barrier layers, as opposed to a line-of-sight technique such as physical vapor deposition (PVD).1 In this regard, we have previously demonstrated extendability of Cu fill (with Ru seed layer) below 25 nm linewidth (200 nm height) when PVD TaN is replaced with ALD TaN.2 In 40 nm Cu dual damascene structures with 3 nm barrier layers, ALD TaN has also been shown to reduce via resistance by ∼28% compared to PVD TaN in spite of 20x lower blanket resistivity for PVD TaN.3 In order to further improve ALD grown TaN and minimize Cu diffusion through these ultrathin barrier films, it is desirable to avoid forming polycrystalline films with inherent grain boundary diffusion pathways. Accordingly, alloying refractory transition metal nitrides with a third element (as for example Al) may offer a promising method for maintaining metastable amorphous films by interrupting the typical polycrystalline phase formation. 4,5 In this regard, ALD of the ternary compound Ta 1-x Al x N y is of potential interest for Cu barrier applications. Presently there is scarce literature on ALD of this ternary compound which warrants further investigation of film growth and barrier properties. In a recent review of ALD processes for metallization by Li,6 only one publication of ALD of TaAlN-based compounds was reported. In this study by Alén et al.7 Ta-halide precursors were used with trimethylaluminum (TMA) as a reducing agent to deposit Ta(Al)N(C) films and the barrier properties...

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“…The kinetics of thermally driven metal silicidation can be described using the Kissinger equation 39,40 which assumes the diffusion limited growth of the metal silicide phase 41,42 . In this analysis the Arrhenius plot is used in order to determine the reaction rate and effective activation energy of thermally driven processes from time and temperature dependent changes in the system 43 .…”

Section: Kinetics Of Silicide Formation With and Without A Barriermentioning

confidence: 99%

Atomic layer deposited ultrathin metal nitride barrier layers for ruthenium interconnect applications

Dey

Yu²,

Consiglio³

et al. 2017

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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RC-time delay in Cu interconnects is becoming a significant factor requiring further performance improvements in future nanoelectronic devices. Choice of alternate interconnect materials, as for example, refractory metals, and subsequent integration with underlying barrier and liner layers are extremely challenging for the sub-10 nm nodes. The development of conformal deposition processes for alternate interconnects, liner, and barrier materials are crucial in order for implementation of a possible replacement for Cu interconnects for narrow line widths. In this study we report on ultra-thin (~ 3nm) chemical 2 vapor deposition (CVD) grown ruthenium films on 0.5 and 1 nm thick metal nitride (TiN, TaN) barrier layers deposited via atomic layer deposition (ALD). Using scanning electron microscopy, we determined the effect of the underlying barrier layer on the coverage of the ruthenium overlayer. We utilized synchrotron x-ray diffraction with in-situ rapid thermal annealing to investigate the thermal stability of the barrier layers and determine the effective activation energies of barrier failure leading to ruthenium monosilicide formation.For Ru films deposited directly on Si and on 0.5 nm MN (M=Ti, Ta) covered Si substrates, silicide formation proceeds via a two-step crystallization process involving lateral nucleation above ~ 440 °C followed by thickening of the ruthenium monosilicide layer above ~520 °C. This silicidation temperature of ~ 440 °C could be potentially problematic in back-end-of-the-line (BEOL) processing since it is close to the typical thermal budget used. However ~1 nm thick ALD MN (M=Ti, Ta) was found to be adequate to block silicide formation up to ~ 580 °C and ~ 620 °C for TiN and TaN, respectively, and also aided in superior coverage of the CVD ruthenium overlayer (>90%). The results reported here might be useful to ascertain annealing temperature and time for BEOL process and integration optimization without reaching a state where ruthenium silicides start forming.

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Homer Kissinger and the Kissinger equation

Cited by 492 publications

References 23 publications

Exothermic Reaction Kinetics in High Energy Density Al-Ni with Nanoscale Multilayers Synthesized by Cryomilling

Exothermic Reaction Kinetics in High Energy Density Al-Ni with Nanoscale Multilayers Synthesized by Cryomilling

In Situ Ramp Anneal X-ray Diffraction Study of Atomic Layer Deposited Ultrathin TaN and Ta_1-xAl_xN_yFilms for Cu Diffusion Barrier Applications

Atomic layer deposited ultrathin metal nitride barrier layers for ruthenium interconnect applications

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Homer Kissinger and the Kissinger equation

Cited by 492 publications

References 23 publications

Exothermic Reaction Kinetics in High Energy Density Al-Ni with Nanoscale Multilayers Synthesized by Cryomilling

Exothermic Reaction Kinetics in High Energy Density Al-Ni with Nanoscale Multilayers Synthesized by Cryomilling

In Situ Ramp Anneal X-ray Diffraction Study of Atomic Layer Deposited Ultrathin TaN and Ta1-xAlxNyFilms for Cu Diffusion Barrier Applications

Atomic layer deposited ultrathin metal nitride barrier layers for ruthenium interconnect applications

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In Situ Ramp Anneal X-ray Diffraction Study of Atomic Layer Deposited Ultrathin TaN and Ta_1-xAl_xN_yFilms for Cu Diffusion Barrier Applications