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1

Zhang, Z.-B., S.-L. Zhang, D.-Z. Zhu, H.-J. Xu, and Y. Chen. "Different routes to the formation of C54 TiSi2 in the presence of surface and interface molybdenum: A transmission electron microscopy study." Journal of Materials Research 17, no. 4 (April 2002): 784–89. http://dx.doi.org/10.1557/jmr.2002.0115.

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Direct evidence revealing fundamental differences in sequence of phase formation during the growth of TiSi2 in the presence of an ultrathin surface or interface Mo layer is presented. Results of cross-sectional transmission electron microscopy showed that when the Mo layer was present at the interface between Ti films and Si substrates, C40 (Mo,Ti)Si2 formed at the interface, and Ti5Si3 grew on top after annealing at 550 °C. Additionally, both C54 and C40 TiSi2 were found in the close vicinity of the C40 (Mo,Ti)Si2 grains. No C49 grains were detected. Raising the annealing temperature to 600 °C led to the formation of C54 TiSi2 at the expense of Ti5Si3, and the interfacial C40 (Mo,Ti)Si2 also began to transform into C54 (Mo,Ti)Si2 at 600 °C. When the Mo was deposited on top of Ti, the silicide film was almost solely composed of C49 TiSi2 at 600 °C. However, a small amount of (Mo,Ti)5Si3 was still present in the vicinity of the sample surface. Upon annealing at 650 °C, only the C54 phase was found throughout the entire TiSi2 layer with a surface (Mo,Ti)Si2 on top of TiSi2. Hence, it was unambiguously shown that in the presence of surface versus interface Mo, different routes were taken to the formation of C54 TiSi2.
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2

Chen, S. Y., Z. X. Shen, K. Li, A. K. See, and L. H. Chan. "Synthesis and characterization of pure C40 TiSi2." Applied Physics Letters 77, no. 26 (December 25, 2000): 4395–97. http://dx.doi.org/10.1063/1.1329864.

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3

Quintero, A., M. Libera, C. Cabral, C. Lavoie, and J. M. E. Harper. "Mechanisms for enhanced C54–TiSi2 formation in Ti–Ta alloy films on single-crystal Si." Journal of Materials Research 14, no. 12 (December 1999): 4690–700. http://dx.doi.org/10.1557/jmr.1999.0635.

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The mechanisms are studied for enhanced formation of C54–TiSi2 at about 700 °C when rapid thermal annealing at 3 °C/s in N2 is performed on 32-nm-thick codeposited Ti–5.9 at.% Ta on Si(100) single-crystal substrates. The enhancement is related to an increased C54–TiSi2 nucleation rate due to the development of a multilayered microstructure. The multilayer microstructure forms at temperatures below 600 °C with the formation of an amorphous disilicide adjacent to the Si substrate and a M5Si3 (M = Ti, Ta) capping layer. This amorphous disilicide crystallizes at higher temperatures to C49–TiSi2. The multilayer microstructure introduces an additional interface that increases the area available for the heterogeneous nucleation of C54. The capping layer is identified as hexagonal Ti 5Si3 or its isomorphous compound (Ti1–xTax)5Si3. Crystal simulations demonstrate that C54(040) has a lattice mismatch of 6–7% relative to Ti5Si3(300) suggesting that a pseudomorphic epitaxial relationship may lower the interfacial energy between these two phases and reduce the energy barrier for C54 nucleation. A C40 disilicide phase was also observed at temperatures above that required to form C54–TiSi2 suggesting that, in the present experiments, the C40 phase does not play a major role in catalyzing C54 formation.
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4

Li, K., S. Y. Chen, and Z. X. Shen. "Identification of refractory-metal-free C40 TiSi2 for low temperature C54 TiSi2 formation." Applied Physics Letters 78, no. 25 (June 18, 2001): 3989–91. http://dx.doi.org/10.1063/1.1378309.

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5

Yu, T., S. C. Tan, Z. X. Shen, L. W. Chen, J. Y. Lin, and A. K. See. "Structural study of refractory-metal-free C40 TiSi2 and its transformation to C54 TiSi2." Applied Physics Letters 80, no. 13 (April 2002): 2266–68. http://dx.doi.org/10.1063/1.1466521.

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6

Quintero, A., M. Libera, C. Cabral, C. Lavoie, and J. M. Harper. "Templating Effects On C54-Tisi2 Formation In Ternary Reactions." Microscopy and Microanalysis 4, S2 (July 1998): 666–67. http://dx.doi.org/10.1017/s143192760002345x.

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Titanium disilicide (C54-TiSi2) is a low resistivity silicide (15 - 20 μΩ-cm) and is widely used in the device industry. It is formed at about 750-850 °C when thin layers (∽30- lOOnm) of Ti on poly- or single-crystal Si substrates are subjected to rapid thermal annealing (3 °C/sec) in a controlled atmosphere (N2). During the anneal, other Ti silicides such as Ti5Si3, Ti5Si4 ,TiSi and C49-TiSi2 may form prior to the desirable C54-TiSi2.Some attempts have been made to promote low-temperature C54-TiSi2 formation. Depositing a Mo (l-2nm) interlayer between Ti and Si has been reported to decrease the C54 formation temperature by 100 °C.2 Codepositing Ti with Ta, Nb or Mo has successfully decreased the formation temperature by about 150 °C.3 These findings have been interpreted in terms of a template mechanism which facilitates formation of C54 by advantageous lattice matching between similar planes in C54 and a hexagonal ternary (Ti- X-Si, X=Ta, Nb, Mo) C40 precursor phase.
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7

Esposito, L., S. Kerdilès, M. Gregoire, P. Benigni, K. Dabertrand, J. G. Mattei, and D. Mangelinck. "Impact of nanosecond laser energy density on the C40-TiSi2 formation and C54-TiSi2 transformation temperature." Journal of Applied Physics 128, no. 8 (August 2020): 085305. http://dx.doi.org/10.1063/5.0016091.

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8

Wang, R. N., J. Y. Feng, and Y. Huang. "Effects of intermediate phase C40 TiSi2 on the formation temperature of C54 TiSi2 with a Ta interlayer." Journal of Crystal Growth 253, no. 1-4 (June 2003): 280–85. http://dx.doi.org/10.1016/s0022-0248(03)01012-1.

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9

Káňa, T., Mojmír Šob, and V. Vitek. "Transformation Paths in Transition-Metal Disilicides." Key Engineering Materials 465 (January 2011): 61–64. http://dx.doi.org/10.4028/www.scientific.net/kem.465.61.

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We suggest and investigate three possible displacive transformation paths between the ideal C11b, C40 and C54 structures in MoSi2, VSi2 and TiSi2 by calculating ab initio total energies along these paths. An estimate of transition temperatures based on the calculated energy barriers leads to values comparable with the melting temperatures of the disilicides studied. This confirms their high temperature stability and indicates that if a phase transformation between C11b, C40 and C54 structures of the disilicides takes place, then its prevailing mechanism should be diffusional rather than martensitic like. During the transformations studied, atoms come as close together as, for example, in configurations with interstitials. Hence, the present ab initio results can also help in fitting adjustable parameters of semi-empirical interatomic potentials for the transition-metal disilicides, in particular of the repulsion at short separations of atoms.
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10

Via, F. La, F. Mammoliti, and M. G. Grimaldi. "Reaction of the Si/Ta/Ti system: C40 TiSi2 phase formation andin situkinetics." Journal of Applied Physics 91, no. 2 (January 15, 2002): 633–38. http://dx.doi.org/10.1063/1.1421212.

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11

Mammoliti, F., M. G. Grimaldi, and F. La Via. "Electrical resistivity and Hall coefficient of C49, C40, and C54 TiSi2 thin-film phases." Journal of Applied Physics 92, no. 6 (September 15, 2002): 3147–51. http://dx.doi.org/10.1063/1.1500787.

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12

Esposito, L., S. Kerdilès, M. Gregoire, P. Benigni, K. Dabertrand, J. G. Mattei, and D. Mangelinck. "Publisher’s Note: “Impact of nanosecond laser energy density on the C40-TiSi2 formation and C54-TiSi2 transformation temperature” [J. Appl. Phys 128, 085305 (2020)]." Journal of Applied Physics 128, no. 15 (October 21, 2020): 159901. http://dx.doi.org/10.1063/5.0031552.

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13

Niranjan, Manish K. "Anisotropy in elastic properties of TiSi2(C49,C40 andC54), TiSi and Ti5Si3: anab-initiodensity functional study." Materials Research Express 2, no. 9 (September 1, 2015): 096302. http://dx.doi.org/10.1088/2053-1591/2/9/096302.

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14

La Via, F., S. Privitera, F. Mammoliti, and M. G. Grimaldi. "Effects of a Ta interlayer on the titanium silicide reaction: C40 formation and scalability of the TiSi2 process." Microelectronic Engineering 60, no. 1-2 (January 2002): 197–203. http://dx.doi.org/10.1016/s0167-9317(01)00595-0.

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15

La Via, F., F. Mammoliti, G. Corallo, M. G. Grimaldi, D. B. Migas, and Leo Miglio. "Formation of the TiSi2 C40 as an intermediate phase during the reaction of the Si/Ta/Ti system." Applied Physics Letters 78, no. 13 (March 26, 2001): 1864–66. http://dx.doi.org/10.1063/1.1359142.

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16

ZHANG, ZHIBIN, SHILI ZHANG, DEZHANG ZHU, HONGJIE XU, and YI CHEN. "FORMATION OF C54 TiSi2 ON Si(100) USING Ti/Mo AND Mo/Ti BILAYERS." International Journal of Modern Physics B 16, no. 01n02 (January 20, 2002): 205–12. http://dx.doi.org/10.1142/s0217979202009652.

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The effect of Mo on the formation of C54 TiSi 2 on Si (100) substrates is studied using cross-section transmission electron microscopy. For a Ti/Mo bilayer on Si, the interfacial Mo film reacts with Ti and Si to form C40 (Mo,Ti)Si 2 at 550°C. Crystal grains of metastable C40 TiSi 2 and equilibrium C54 TiSi 2 are found in the region near the interfacial (Mo,Ti)Si 2 layer due to the template phenomenon. Increasing the temperature to 600°C leads to the growth of C54 TiSi 2 throughout the film. No C49 grains can be detected. The findings confirm that the usual sequence for the formation of C54 TiSi 2, i.e. the C49 TiSi 2 forms first followed by a phase transition to the C54 TiSi 2, is altered by the interposed Mo layer. For a Mo/Ti bilayer on Si , the surface Mo layer is found to be present sequentially in (Mo,Ti) 5 Si 3 at 550°C, C49 (Mo,Ti)Si 2 at 600°C and C54 (Mo,Ti)Si 2 at 650°C. The bulk Ti beneath forms the C54 TiSi 2 following the usual route through the C49-C54 phase transition. However, this transition is now enhanced, in comparison with the C54 TiSi 2 formation with pure Ti , by the C54 (Mo,Ti)Si 2 atop that plays the role as a template precisely as the interfacial C40 (Mo,Ti)Si 2.
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17

Kappius, L., and R. T. Tung. "On the Template Mechanism of Enhanced C54-TiSi2 Formation." MRS Proceedings 611 (2000). http://dx.doi.org/10.1557/proc-611-c8.2.1.

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ABSTRACTThe enhanced formation of the C54-TiSi2 phase by the addition of small amounts of refractory metal (Tm = Mo, Ta, Nb,..) has often been ascribed to a template mechanism from the C40 TixRm1−xSi2 or the (Ti,Rm)5Si3 phase. Due to lattice matching conditions, the presence of either of these phases is thought to lower the interface energies with certain orientations of the C54-TiSi2 grain and, thereby, possibly lower the nucleation barrier of the C54-TiSi2 phase. These proposed template mechanisms are specifically tested in the present work through a study of the nucleation of TiSi2 phase(s) in contact with a pre-existing C40 Ti0.4Mo0.6Si2 or Ti5Si3 layer. No identifiable enhancement in the C54-TiSi2 nucleation was observed which could be attributed to templates. Instead, the nucleation temperature of the C54-TiSi2 phase appeared to be correlated with the grain size of the C49-TiSi2 layer, independent of whether Rm was present. These results are suggestive that the primary mechanism for the enhanced formation of the C54 phase by refractory metals is a reduction in the grain size of the C49 TiSi2phase, likely due to altered kinetics.
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18

Chen, S. Y., Z. X. Shen, S. Y. Xu, A. K. See, L. H. Chan, and W. S. Li. "Direct Formation of C54 Phase on the Basis of C40 TiSi2 and Its Applications in Deep Sub-Micron Technology." MRS Proceedings 670 (2001). http://dx.doi.org/10.1557/proc-670-k6.4.

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ABSTRACTA simple and novel salicidation process applying pulsed laser annealing as the first annealing step was used to induce TiSi2 formation. Both Raman spectroscopy and transmission electron microscope results confirm the formation of a new phase of Ti disilicide, the pure C40 TiSi2 after laser irradiation. Direct C54 phase growth on the basis of C40 template bypassing the C49 phase is accomplished at the second annealing temperature as low as 600°C. Line width independent formation of the C54 phase was observed on patterned wafers using this salicidation process and “fine line effect” is thus eliminated.
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19

Frankwicz, P. S., and J. H. Perepezko. "Phase Stability and Solidification Pathways in MoSi2 Based Alloys." MRS Proceedings 213 (1990). http://dx.doi.org/10.1557/proc-213-169.

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ABSTRACTThe phase equilibria developed upon substitution of Ti in MoSi2 along the pseudobinary MoSi2-TiSi2 section has been investigated using x-ray diffraction, and electron microscopy. The pseudobinary exhibits orthorhombic (C54), hexagonal (C40), and tetragonal (Cllb) crystalline structures. A hexagonal (C40) ternary silicide (Ti1-xMox)Si2 was observed to exhibit a relatively wide range of solubility with x in the range of 0.50 to 0.75, in contrast to MoSi2 which exhibits limited solubility for Ti. An analysis of the microstructural evolution following solidification reveals that the hexagonal β-(Ti,Mo)Si2 phase forms via a peritectic reaction between liquid and MoSi2 (Cllb). The primary dendritic structure during solidification in (Til-xMo2)Si2, where x z 0.80, has been determined to be tetragonal (Cllb) MoSi2. The results of this study confirm that substitutional alloying on the transition metal sublattice (Mo) is an effective approach to control of the phase stability and crystal structure in intersilicide reactions.
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20

La Via, F., S. Privitera, F. Mammoliti, and M. G. Grimaldi. "Effects of a Ta Interlayer on the Titanium Silicide Reaction: C40 Formation and Higher Scalability of the TiSi2 Process." MRS Proceedings 670 (2001). http://dx.doi.org/10.1557/proc-670-k6.3.

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ABSTRACTWhen a Ta layer is deposited at the Si/Ti interface a new phase has been detected, i.e. theTiSi2C40. The C40-C54 transformation kinetics and the film morphology are consistent with an increase of the nucleation density with respect to the C49-C54 transition. The activation energies for the nucleation rate (4.2±0.3 eV) and the growth velocity (4.0±0.4 eV) have been obtained from the in situ sheet resistance and the Transmission Electron Microscopy results. These results show that the process with a Ta layer at the Ti/Si interface has a greater scalability with respect to the standard TiSi2 process.
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