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1

Cabral, C., L. A. Clevenger, J. M. E. Harper, F. M. d'Heurle, R. A. Roy, K. L. Saenger, G. L. Miles, and R. W. Mann. "Lowering the formation temperature of the C54-TiSi2 phase using a metallic interfacial layer." Journal of Materials Research 12, no. 2 (February 1997): 304–7. http://dx.doi.org/10.1557/jmr.1997.0040.

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We demonstrate that the formation temperature of the C54 TiSi2 phase from the bilayer reaction of Ti on Si is lowered by approximately 100 °C by placing an interfacial layer of Mo or W between Ti and Si. Upon annealing above 500 °C, the C49 TiSi2 phase forms first, as in the reaction of Ti directly on Si. However, the temperature range over which the C49 phase is stable is decreased by approximately 100 °C, allowing C54 TiSi2 formation below 700 °C. Patterned submicron lines (0.25−1.0 μm wide) fabricated without the Mo layer contain only the C49 TiSi2 phase after annealing to 700 °C for 30 s. With a Mo layer less than 3 nm thick between Ti and Si, however, a mixture of C49 and C54 TiSi2 was formed, resulting in a lower resistivity. The enhanced formation of the C54 TiSi2 is attributed to an increased density of nucleation sites for the C49-C54 phase transformation, arising from a finer grained precursor C49 phase.
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2

Cheng, S. L., J. J. Jou, L. J. Chen, and B. Y. Tsui. "Formation of C54–TiSi2 in titanium on nitrogen-ion-implanted (001)Si with a thin interposing Mo layer." Journal of Materials Research 14, no. 5 (May 1999): 2061–69. http://dx.doi.org/10.1557/jmr.1999.0278.

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Formation of TiSi2 in titanium on nitrogen-implanted (001)Si with a thin interposing Mo layer has been investigated. The presence of a Mo thin interposing layer was found to decrease the formation temperature of C54–TiSi2 by about 100 °C. A ternary (Ti, Mo)Si2 phase was found to distribute in the silicide layer. The ternary compound is conjectured to provide more heterogeneous nucleation sites to enhance the formation of C54–TiSi2. On the other hand, the effect of grain boundary for decreasing transformation temperature was found to be less crucial. For Ti/Mo bilayer on 30 keV BF2+ or As+ + 20 keV, 1 × 1015/cm2 N2+ implanted samples, a continuous C54–TiSi2 layer was found to form in all samples annealed at 650–950 °C. The presence of nitrogen atoms in TiSi2 is thought to lower the silicide/silicon interface energy and/or the silicide surface energy to maintain the integrity of the C54–TiSi2 layer at high temperatures.
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3

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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4

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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5

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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6

Wang, Ming-Jun, Wen-Tai Lin, and F. M. Pan. "Effects of an interposed Cu layer on the enhanced thermal stability of C49 TiSi2." Journal of Materials Research 17, no. 2 (February 2002): 343–47. http://dx.doi.org/10.1557/jmr.2002.0048.

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The effects of an interposed Cu layer and a surface Cu layer on the C49–C54 TiSi2 transformation temperature were studied. For the Ti/Cu/(100)Si samples the interposed Cu layer significantly enhanced the thermal stability of C49 TiSi2. The temperature for complete C49–C54 TiSi2 transformation was raised from 710 to 735 to 750 °C with the thickness of the interposed Cu layer increasing from 0 to 1.5 to 3.5 nm, correspondingly. Cu was insoluble in C54 TiSi2. For the Cu/Ti/(100)Si samples, the surface Cu layer did not at all enhance the thermal stability of the C49 phase. In the present study, the enhanced thermal stability of C49 TiCuxSi2–x can be attributed to its reduced electron/atom ratio and larger grain size relative to those of C49 TiSi2.
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7

Clevenger, L. A., R. A. Roy, C. Cabral, K. L. Saenger, S. Brauer, G. Morales, K. F. Ludwig, et al. "A comparison of C54-TiSi2 formation in blanket and submicron gate structures using in situ x-ray diffraction during rapid thermal annealing." Journal of Materials Research 10, no. 9 (September 1995): 2355–59. http://dx.doi.org/10.1557/jmr.1995.2355.

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We demonstrate the use of a synchrotron radiation source for in situ x-ray diffraction analysis during rapid thermal annealing (RTA) of 0.35 μm Salicide (self-aligned silicide) and 0.4 μm Polycide (silicided polysilicon) TiSi2 Complementary Metal Oxide Semiconductor (CMOS) gate structures. It is shown that the transformation from the C49 to C54 phase of TiSi2 occurs at higher temperatures in submicron gate structures than in unpatterned blanket films. In addition, the C54 that forms in submicron structures is (040) oriented, while the C54 that forms in unpatterned Salicide films is randomly oriented. Although the preferred oreintation of the initial C49 phase was different in the Salicide and Polycide gate structures, the final orientation of the C54 phase formed was the same. An incomplete conversion of C49 into C54-TiSi2 during the RTA of Polycide gate structures was observed and is attributed to the retarding effects of phosphorus on the transition.
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8

Rajan, Krishna. "Twin boundaries in C54-TiSi2." Metallurgical Transactions A 21, no. 9 (September 1990): 2317–22. http://dx.doi.org/10.1007/bf02646978.

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9

Pico, C. A., and M. G. Lagally. "Angular correlation between grains of metastable TiSi2." Proceedings, annual meeting, Electron Microscopy Society of America 46 (1988): 888–89. http://dx.doi.org/10.1017/s0424820100106508.

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TiSi2 is the primary silicide candidate as interconnect material in very largy scale integrated (VLSI) devices because of its low resistivity (15μΩ-cm) and relatively low processing temperature. While formation of TiSi2 from Ti-on-Si reaction couples can be accomplished easily and quickly at anneal temperatures above 550°C, below ∽650°C TiSi2 forms in the metastable C49 (base-centered orthorhombic; a=3.62Å, b=13.76Å, and c=3.605Å) 12-atom-per-unit-cell crystal structure with a characteristic resistivity of 65μΩ-cm. To achieve the low-resistivity C54 (face-centered orthorhombic; a=8.24Å, b=4.78Å, and c=8.54Å) phase, anneals above ∼650°C are required. It has been suggested that the decrease in resistivity of TiSi2 from the C49 phase to the C54 phase is a result of the reduced number of microstructural defects (defect separation changes from ∼30Å to 5μm) associated with the change of crystal structure. An understanding of the arrangement of the microstructural defects in C49 is needed to correlated the electrical properties of C49 and C54 correctly.
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10

Nemanich, R. J., Hyeongtag Jeon, J. W. Honeycutt, C. A. Sukow, and G. A. Rozgonyi. "Interface structure of epitaxial TiSi2 on Si(lll)." Proceedings, annual meeting, Electron Microscopy Society of America 50, no. 2 (August 1992): 1354–55. http://dx.doi.org/10.1017/s0424820100131401.

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Among the transition metal silicides, TiSi2 is considered to be a reasonable choice for VLSI applications because it exhibits low resistivity, high temperature stability and compatibility with current processing steps. Thin film reaction of Ti on Si results in the formation of two different forms of TiSi2 which have been identified as the C49 and the C54 crystal structures. The structures are base centered and face centered orthorhombic, respectively. The C49 phase is metastable (ie. it is not represented in the binary phase diagram), and forms at temperatures of 450 to 600°C. The stable C54 phase forms after high temperature annealing to > 650°C. In this paper the relation of the morphology and interface structures of epitaxial C49 TiSi2 on Si(l11) are described.The TiSi2/Si structures were prepared in a UHV system. The TiSi2 surface morphologies were examined by SEM and plan view TEM, and the interfaces were studied by TEM and HRTEM. The phase identification was obtained from the TEM and with ex situ Raman spectroscopy.
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11

Ottaviani, G., R. Tonini, D. Giubertoni, A. Sabbadini, T. Marangon, G. Queirolo, and F. La Via. "Investigation of C49–C54 TiSi2 transformation kinetics." Microelectronic Engineering 50, no. 1-4 (January 2000): 153–58. http://dx.doi.org/10.1016/s0167-9317(99)00276-2.

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12

Chen, Chih-Yen, Yu-Kai Lin, Chia-Wei Hsu, Chiu-Yen Wang, Yu-Lun Chueh, Lih-Juann Chen, Shen-Chuan Lo, and Li-Jen Chou. "Coaxial Metal-Silicide Ni2Si/C54-TiSi2 Nanowires." Nano Letters 12, no. 5 (April 9, 2012): 2254–59. http://dx.doi.org/10.1021/nl204459z.

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13

Makogon, Yu N., O. P. Pavlova, Sergey I. Sidorenko, G. Beddies, and A. V. Mogilatenko. "Influence of Annealing Environment and Film Thickness on the Phase Formation in the Ti/Si(100) and (Ti +Si)/Si(100) Thin Film Systems." Defect and Diffusion Forum 264 (April 2007): 159–62. http://dx.doi.org/10.4028/www.scientific.net/ddf.264.159.

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Influence of an annealing environment and film thickness on the phase formation in the Ti(30 nm)/Si(100), [(Ti+Si) 200 nm]/Si(100) thin film systems produced by magnetron sputtering and the Ti(200 nm)/Si(100) thin film system produced by electron-beam sputtering were investigated by X-ray and electron diffraction, Auger electron spectroscopy (AES), secondary ion mass-spectrometry (SIMS) and resistivity measurements. Solid-state reactions in the thin film systems under investigation were caused by diffusion processes during annealing in the different gas environments: under vacuum of 10-4 - 10-7 Pa, flow of nitrogen and hydrogen. It is shown that the decrease of Ti layer thickness from 200 to 30 nm in the Ti/Si(100) film system causes the increase of the transition temperature of the metastable C49 TiSi2 phase to the stable C54 TiSi2 phase up to 1070 K at vacuum annealing. During annealing in the nitrogen flow of the Ti(30 nm)/Si(100) thin film system the C49 TiSi2 is the first crystal phase which is formed at 870 K. For annealings of the [(Ti+Si) 200 nm]/Si(100) thin film system by impulse heating method or for furnace annealings in inert gas atmosphere of N2, Ar, H or higher vacuum (10-5 Pa) the crystallization process has two stages: the first metastable C49 TiSi2 phase is formed at 870 K and then at higher temperatures it is transformed to the stable C54 TiSi2 phase.
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14

Mouroux, Aliette, and Shi-Li Zhang. "Alternative pathway for the formation of C54 TiSi2." Journal of Applied Physics 86, no. 1 (July 1999): 704–6. http://dx.doi.org/10.1063/1.370789.

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15

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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16

Thomas, O., F. M. d'Heurle, and S. Delage. "Some titanium germanium and silicon compounds: Reaction and properties." Journal of Materials Research 5, no. 7 (July 1990): 1453–62. http://dx.doi.org/10.1557/jmr.1990.1453.

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Titanium reacts with pure Ge in two different ways: At low temperatures one observes the formation of Ti6Ge5 with some characteristics typical of diffusion-controlled reaction. Upon completion of this first stage Ti6Ge5 reacts with remaining Ge to form TiGe2, isomorphous with C54 TiSi2, in a process which is clearly controlled by nucleation. The same observations apply to reactions with a Ge alloy containing 25 at.% Si. With an alloy containing 50 at.% Si the two stages become merged, so that while remaining identifiable, they are much less distinct than with the previous conditions. The reaction behavior observed with a Ge alloy containing 80 at.% Si resembles that generally obtained with pure Si: there are no easily identifiable steps between the initial Si–Ti sample and the final one, Si–TiSi2. With both the 50-50 and 80-20 Si–Ge alloys the formation of the C54 structure is preceded by that of the C49 structure (ZrSi2 type), as with pure Si. The gradual merging of the diffusion-controlled reaction and that controlled by nucleation as the concentration of Si in the substrate increases implies that nucleation plays a significant role in the formation of TiSi2, even if that role cannot be easily isolated. Effects due to gas impurities on the path of the metal-substrate reaction have been analyzed. The resistivities of several pure and alloyed phases have been measured. Alloy scattering in the system TiSi2–TiGe2 is briefly discussed.
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17

Quintero, A., M. Libera, C. Cabrai, C. Lavoie, and J. M. E. Harper. "Silicide Identification in Rta-Processed Ti Salicide by Analytical Electron Microscopy." Microscopy and Microanalysis 3, S2 (August 1997): 453–54. http://dx.doi.org/10.1017/s1431927600009156.

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Titanium suicides have low resistivity, low contact resistance, and are widely used as interconnects in electronic devices. The most desirable structure is the C54 variant of titanium disilicide (TiSi2). It is typically formed during thermal annealing by a polymorphic transformation from the C49 TiSi2 structure. The C49 to C54 transformation has been studied extensively and there has been substantial effort to devise ways in which to lower the temperature associated with this transformation. This research uses high-resolution imaging (HREM), convergent-beam diffraction (CBED), and energy-dispersive X-ray microanalysis (EDS) to study the development of suicide morphology in response to rapid thermal annealing (RTA). Two sets of specimens have been studied: (i) 32nm Ti thin films on undoped single-crystal Si substrates [Ti/Si] and (ii) 32nm Ti films separated from an undoped single-crystal Si substrate by a 0.12nm thick Mo interlayer [Ti/Mo/Si]. This paper shows structures formed after RTA at a ramp rate 3 °C/sec to 750 °C with a hold of 1 sec
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18

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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19

Cabral, C., L. A. Clevenger, J. M. E. Harper, F. M. d’Heurle, R. A. Roy, C. Lavoie, K. L. Saenger, G. L. Miles, R. W. Mann, and J. S. Nakos. "Low temperature formation of C54–TiSi2 using titanium alloys." Applied Physics Letters 71, no. 24 (December 15, 1997): 3531–33. http://dx.doi.org/10.1063/1.120401.

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20

Amorsolo, A. V., P. D. Funkenbusch, and A. M. Kadin. "A parametric study of titanium silicide formation by rapid thermal processing." Journal of Materials Research 11, no. 2 (February 1996): 412–21. http://dx.doi.org/10.1557/jmr.1996.0050.

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A parametric study of titanium silicide formation by rapid thermal processing was conducted to determine the effects of annealing temperature (650 °C, 750 °C), annealing time (30 s, 60 s), wet etching (no HF dip, with HF dip), sputter etching (no sputter etch, with sputter etch), and annealing ambient (Ar, N2) on the completeness of conversion of 60 nm Ti on (111)-Si to C54–TiSi2 based on sheet resistance and the uniformity of the sheet resistance measurements across the entire wafer. Statistical analysis of the results showed that temperature, annealing ambient, and sputter etching had the greatest influence. Increasing the temperature and using argon gas instead of nitrogen promoted conversion of the film to C54–TiSi2. On the other hand, sputter etching retarded it. The results also indicated significant interactions among these factors. The best uniformity in sheet resistance was obtained by annealing at 750 °C without sputter etching. The different sheet resistance profiles showed gradients that were consistent with expected profile behaviors, arising from temperature variations across the wafer due to the effect of a flowing cold gas and the effects of the wafer edge and flats.
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21

Barmak, K., L. E. Levine, D. A. Smith, and Y. Komemt. "In situ tEM observation of C49 to C54 TiSi2 transformation." Proceedings, annual meeting, Electron Microscopy Society of America 50, no. 2 (August 1992): 1356–57. http://dx.doi.org/10.1017/s0424820100131413.

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The reaction of thin films of Ti with Si results in the formation of the high resistivity (≃150 μΩcm) base-centered orthorhombic C49 phase prior to the low resistivity (≃15-20 μΩcm) face-centered orthorhombic C54 phase. In our experiments, 30 nm of Ti was evaporated onto a < 100 > oriented Si wafer cleaned in a 10:1 H2O:HF solution. The wafer had been previously implanted with As to a dose of 5×l015 cm−2. Mixed C49/C54 phase films were obtained by furnace annealing at 700°C for 10 min. Plan view transmission electron microscopy (TEM) specimens were prepared by dimpling and etching in a 10:6:6 HNO3:HF:CH3COOH solution. The sample was initially studied in a JEOL 4000FX and in situ heating experiments were carried out in a Philips 430 operating at 300 kV. The progress of the transformation was recorded on video tape. The temperature was raised relatively quickly to 700°C and then more slowly to 750°C.
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22

ZHANG, LIN, YONG KEUN LEE, and HUN SUB PARK. "FORMATION ENHANCEMENT OF THE C54-TiSi2 BY A MULTI-CYCLE PRE-COOLING TREATMENT." International Journal of Modern Physics B 16, no. 01n02 (January 20, 2002): 213–18. http://dx.doi.org/10.1142/s0217979202009664.

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This work investigated effects of different processing methods on the transformation of the C49-TiSi 2 phase to the C54-TiSi 2 phase in 20nm IMP Ti/Si thin films. A multi-cycle pre-cooling treatment was added to the titanium silicidation process sequence before the rapid thermal annealing (RTA) step. Compared with the conventional process, this new processing method was found to enhance formation of the low-resistivity C54-TiSi 2 phase. The extent to which the C49 transformed to the C54 phase at 720°C was observed to increase with the number of the pre-cooling cycle. The kinetic mechanisms of the C49 to C54 phase transformation were adopted to explain the experimental results. It is considered that defects at the Si/Ti interface caused by the thermal mismatch between these two layers during the pre-cooling treatment contributed to the increase in the C49 nucleation sites. This supplied more C49 grain boundaries and triple junction sites at which the C54 phase could nucleate. This discovery has a potential of reducing the complexity and cost associated with forming the low-resistivity C54 phase on sub-micron structures.
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23

Xu, Jianguang, Menglan Jin, Xinlu Shi, Qiuyu Li, Chengqiang Gan, and Wei Yao. "Preparation of TiSi2 Powders with Enhanced Lithium-Ion Storage via Chemical Oven Self-Propagating High-Temperature Synthesis." Nanomaterials 11, no. 9 (September 2, 2021): 2279. http://dx.doi.org/10.3390/nano11092279.

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Although silicon has highest specific capacity as anode for lithium-ion battery (LIB), its large volume change during the charge/discharge process becomes a great inevitable hindrance before commercialization. Metal silicides may be an alternative choice because they have the ability to accommodate the volume change by dispersing Si in the metal matrix as well as very good electrical conductivity. Herein we report on the suitability of lithium-ion uptake in C54 TiSi2 prepared by the “chemical oven” self-propagating high-temperature synthesis from the element reactants, which was known as an inactive metal silicide in lithium-ion storage previously. After being wrapped by graphene, the agglomeration of TiSi2 particles has been efficiently prevented, resulting in an enhanced lithium-ion storage performance when using as an anode for LIB. The as-received TiSi2/RGO hybrid exhibits considerable activities in the reversible lithiation and delithiation process, showing a high reversible capacity of 358 mAh/g at a current density of 50 mA/g. Specially, both TiSi2 and TiSi2/RGO electrodes show a remarkable enhanced electrochemical performance along with the cycle number, indicating the promising potential in lithium-ion storage of this silicide. Ex-situ XRD during charge/discharge process reveals alloying reaction may contribute to the capacity of TiSi2. This work suggests that TiSi2 and other inactive transition metal silicides are potential promising anode materials for Li-ion battery and capacitor.
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24

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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25

WANG, TAO, JI-AN CHEN, XING LING, YONG-BING DAI, and QING-YUAN DAI. "PSEUDOPOTENTIAL INVESTIGATION OF ELECTRONIC PROPERTIES OF C54- AND C49-TiSi2." Modern Physics Letters B 20, no. 07 (March 20, 2006): 343–51. http://dx.doi.org/10.1142/s0217984906010639.

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The letter casts some light on the structural, elastic and electronic properties of C49- and C54-TiSi 2, using an ab initio plane-wave ultrasoft pseudopotential method based on generalized gradient approximation (GGA). An intrinsic advantage in the growth stage for C49 phase might explain its kinetically favored phenomena in a solid-state reaction.
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26

Engqvist, Jan, Ulf Jansson, Jun Lu, and Jan‐Otto Carlsson. "C49/C54 phase transformation during chemical vapor deposition of TiSi2." Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films 12, no. 1 (January 1994): 161–68. http://dx.doi.org/10.1116/1.578914.

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27

Wang, T., Y. B. Dai, S. K. Ouyang, H. S. Shen, Q. K. Wang, and J. S. Wu. "Investigation of vacancy in C54 TiSi2 using ab initio method." Materials Letters 59, no. 8-9 (April 2005): 885–88. http://dx.doi.org/10.1016/j.matlet.2004.11.038.

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28

Mann, R. W., and L. A. Clevenger. "The C49 to C54 Phase Transformation in TiSi2 Thin Films." Journal of The Electrochemical Society 141, no. 5 (May 1, 1994): 1347–50. http://dx.doi.org/10.1149/1.2054921.

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29

Mohadjeri, B., K. Maex, R. A. Donaton, and H. Bender. "Ion‐Induced Amorphization and Regrowth of C49 and C54 TiSi2." Journal of The Electrochemical Society 146, no. 3 (March 1, 1999): 1122–29. http://dx.doi.org/10.1149/1.1391732.

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30

Wang, Tao, Soon-Young Oh, Won-Jae Lee, Yong-Jin Kim, and Hi-Deok Lee. "Ab initio comparative study of C54 and C49 TiSi2 surfaces." Applied Surface Science 252, no. 14 (May 2006): 4943–50. http://dx.doi.org/10.1016/j.apsusc.2005.07.029.

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31

Ma, Z., L. H. Allen, and D. D. J. Allman. "Effect of dimension scaling on the nucleation of C54 TiSi2." Thin Solid Films 253, no. 1-2 (December 1994): 451–55. http://dx.doi.org/10.1016/0040-6090(94)90365-4.

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32

Jin, S., M. Aindow, Z. Zhang, and L. J. Chen. "Formation and microstructural development of TiSi2 in (111)Si by Ti ion implantation and annealing at 950 °C." Journal of Materials Research 10, no. 4 (April 1995): 891–99. http://dx.doi.org/10.1557/jmr.1995.0891.

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A transmission electron microscopy study of the microstructural development for (111)Si wafers implanted with Ti ions and annealed subsequently at 950 °C is presented. The as-implanted wafers have a Ti-rich amorphous layer at the surface with embedded silicides, which correspond to a crystalline form of TiSi2 that has not been reported previously. Below this lies a Ti-lean crystalline layer with extensive radiation damage. The annealed layers have large incoherent islands of C54 TiSi2, with a layered microstructure in the Si between them consisting of twins, then topotaxial silicides, then dislocation loops. It is proposed that this microstructure arises from silicide growth prior to epitaxial regrowth, whereas for the continuous epitaxial films observed previously at lower annealing temperatures, epitaxial regrowth precedes silicide development.
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33

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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34

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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35

David Theodore, N., Andre Vantomme, and Peter Crazier. "TEM study of Cosi2 formation via annealing of Co-Ti bilayers on Si." Proceedings, annual meeting, Electron Microscopy Society of America 53 (August 13, 1995): 464–65. http://dx.doi.org/10.1017/s0424820100138695.

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Contact is typically made to source/drain regions of metal-oxide-semiconductor field-effect transistors (MOSFETs) by use of TiSi2 or CoSi2 layers followed by AI(Cu) metal lines. A silicide layer is used to reduce contact resistance. TiSi2 or CoSi2 are chosen for the contact layer because these silicides have low resistivities (~12-15 μΩ-cm for TiSi2 in the C54 phase, and ~10-15 μΩ-cm for CoSi2). CoSi2 has other desirable properties, such as being thermally stable up to >1000°C for surface layers and >1100°C for buried layers, and having a small lattice mismatch with silicon, -1.2% at room temperature. During CoSi2 growth, Co is the diffusing species. Electrode shorts and voids which can arise if Si is the diffusing species are therefore avoided. However, problems can arise due to silicide-Si interface roughness (leading to nonuniformity in film resistance) and thermal instability of the resistance upon further high temperature annealing. These problems can be avoided if the CoSi2 can be grown epitaxially on silicon.
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36

Suh, You-Seok, Dae-Gyu Park, Se-Aug Jang, Sang-Hyeob Lee, Tae-Kyun Kim, In-Seok Yeo, Sam-Dong Kim, and Chung-Tae Kim. "Retarded C54 transformation and suppressed agglomeration by precipitates in TiSi2 films." Journal of Applied Physics 87, no. 6 (March 15, 2000): 2760–64. http://dx.doi.org/10.1063/1.372252.

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37

Inui, H., M. Moriwaki, N. Okamoto, and M. Yamaguchi. "Plastic deformation of single crystals of TiSi2 with the C54 structure." Acta Materialia 51, no. 5 (March 2003): 1409–20. http://dx.doi.org/10.1016/s1359-6454(02)00533-5.

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38

Svilan, V., J. M. E. Harper, C. Cahral, and L. A. Clevengeri. "Stress Evolution During the Formation and Transformation of Titanium Silicide." MRS Proceedings 356 (1994). http://dx.doi.org/10.1557/proc-356-167.

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AbstractThe evolution of stress vs. temperature was measured during the formation of TiSi2 in the reaction of Ti with (100) Si and with polycrystalline Si, and during the phase transformation from C49 to C54 TiSi2. The formation of C49 TiSi2 causes an increase in compressive stress, followed by relaxation before the transformation to C54 TiSi2, which causes no significant stress change. C54 TiSi2 is shown to be elastic in the temperature range of 750–860 °C. This difference in the deformation mechanisms of C49 and C54 TiSi2 affects the morphological stability of TiSi2 in fine line structures.
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39

Cheng, S. L., S. M. Chang, H. Y. Huang, Y. C. Peng, L. J. Chen, B. Y. Tsui, C. J. Tsai, and S. S. Guo. "The Influence Of Stress on The Growth of Titanium Silicide Thin Films on (001) Silicon Substrates." MRS Proceedings 564 (1999). http://dx.doi.org/10.1557/proc-564-9.

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AbstractThe influence of stress on the enhanced formation of C54-TiSi2 phase has been investigated. Tensile stress induced by backside CoSi2 film on the silicon substrate has been found to enhance the growth of C54-TiSi2 on (001)Si. The thickness of amorphous interlayers (a-interlayers) between Ti films and silicon substrates was found to be thicker and thinner in the tensilly and compressively stressed samples, respectively. From auto-correlation function analysis, the thicker a-interlayer was found to consist of a higher density of crystallites. The crystallites provide nucleation sites for C49-TiSi2 and facilitate the formation of C49-TiSi2 of small size. The larger total area of C49-TiSi2 grain boundaries supplies more nucleation sites for the phase transformation of C49- to C54-TiSi2. Therefore, the tensile stress present in the silicon substrate promotes the formation of a-interlayer and decreases the grain size of C49- TiSi2, which increases the nucleation density of the C54-TiSi2 phase. As a result, the transformation of C49- to C54-TiSi2 phase is enhanced.
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40

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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41

Matsubara, Y., K. Noguchi, and K. Okumura. "Activation Energy for the C49-TO-C54 Phase Transition of Polycrystalline TiSi2 Films with under 30nm Thickness." MRS Proceedings 311 (1993). http://dx.doi.org/10.1557/proc-311-263.

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ABSTRACTThe C49–to–C54 transition in TiSi2 was investigated by resistance measurement and x-ray diffraction technique. The resistance measurement showed that the C49–to–C54 transition has an activation energy strongly dependent on the titanium thickness. The energy increased with the thinning of the TiSi2, from 4.6±0.3 eV for TiSi2 formed with 50nm titanium, to 10.5±0.3 eV formed with 20nm titanium. Furthermore, x-ray diffraction result showed that (004)-oriented phase in C54 TiSi2 is responsible for the increase in activation energy. This orientation dependence of the activation energy probably originates from anisotropy in C54 crystal growth during the transition.
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42

Ganapathiraman, Ramanath, S. Koh, Z. Ma, L. H. Allen, and S. Lee. "Formation of TiSi2 During Rapid Thermal Annealing: In Situ Resistance Measurements at Heating Rates From 1°C/S to 100°C/S." MRS Proceedings 303 (1993). http://dx.doi.org/10.1557/proc-303-63.

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ABSTRACTIn VLSI technology, there is interest in monitoring the sequence of phase formation of TiSi2 (c-Ti ⇒ a-TiSi ⇒ C49 TiSi2 ⇒ C54 TiSi2), with the prospect of reducing the temperature of formation of the stable C54 TiSi2 phase. In this study, phase formation characteristics of TiSi2 during rapid thermal annealing(RTA) of Ti-Si bilayers are investigated by means of in situ four point probe resistance measurements. Ex situ X-ray diffraction(XRD) was used for phase identification and characterization. Results indicate that the same multi-step sequence of transformations precede the formation of the C54 TiSi2 phase for heating rates from 1°C/s to 100°C/s. Also, all intermediate and metastable phases which occur at l°C/s also occur at 100°C/s. Temperature dependence and kinetics of the C49 TiSi2 and the C54 TiSi2 phase formation were studied over a wide range of heating rates. Activation energies estimated for the two processes were ∼2eV and ∼5eV respectively. Finally, a new Electrical Thermal Annealing(ETA) technique for heating at rates up to 30000°C/s is introduced. Preliminary in situ resistivity measurement results of TiSi2 formation at these high heating rates are also presented.
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43

Nakamura, T., K. Ikeda, H. Tomita, S. Komiya, and K. Nakajima. "C49-TiSi2 Epitaxial Orientation Dependence of the C49-to-C54 Phase Transformation Rate." MRS Proceedings 514 (1998). http://dx.doi.org/10.1557/proc-514-213.

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ABSTRACTEffects of the C49-TiSi2 epitaxial orientation on the C49-to-C54 phase transformation rate have been studied for samples with different pre-amorphization implantation (PAI) conditions. The C49 epitaxial orientation to the Si(001) substrate is characterized by use of grazing-incidence X-ray diffraction (GIXD) measurements. We found that the PAl treatment suppresses the epitaxial growth of C49-TiSi2 on Si(001) substrates and the poorer orientational alignment of C49-TiSi2 causes a more rapid transformation to C54-TiSi2. We believe this suppression of epitaxial alignment is a possible mechanism to understand the effect of the PAl treatment on the C49-C54 transformation.
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44

Fujii, K., R. T. Tung, D. J. Eaglesham, K. Kikuta, and T. Kikkawa. "Phase Transformation of Titanium Disilicide Induced by High-Temperature Sputtering." MRS Proceedings 402 (1995). http://dx.doi.org/10.1557/proc-402-83.

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AbstractThe reaction between sputtered Ti thin films and heavily arsenic doped Si(100) is studied. The use of an arsenic implantation to pre-amorphize the Si substrate and the choice of the substrate temperature during Ti sputtering are both found to have a significant effect on subsequent TiSi2 reactions. Cross-sectional transmission electron microscopy reveals that an amorphous TiSix layer is formed at the interface between Si and as-sputtered Ti. The thickness of this interfacial layer increases with the sputtering temperature. After rapid thermal anneals in nitrogen, the sheet resistances of TiSi2 thin films grown with the pre-amorphization step and a high sputtering temperature (450°C) are generally lower than films processed under other conditions. This apparent reduction in the temperature for the polymorphic C49 to 54 phase transformation in TiSi2 is shown to originate from a higher nucleation density of the C54-TiSi2 phase. These dependencies of the silicide reaction are ascribed to the interfacial amorphous TiSix layer. In increasing the nucleation density of the C54-TiSi2 phase, the amorphous TiSix layer is speculated to either act as a direct nucleation source for the C54-TiSi2 phase, or lead to more defective C49-TiSi2 structures which facilitate the C54-TiSi2 nucleation.
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45

Roux, M., A. Mouroux, and S. L. Zhang. "The Formation of C54 TiSi2 in The Presence of Implanted or Deposited Molybdenum." MRS Proceedings 564 (1999). http://dx.doi.org/10.1557/proc-564-53.

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AbstractThe presence of Mo, either implanted in Si substrate prior to Ti deposition or deposited at the interface between Ti and Si, leads to the formation of C54 TiSi2 at 600 °C. Without Mo, the C54 TiSi2 does not form below 700 °C. It is shown that the C54 TiSi2 formed with the implanted Mo of a nominal dose of 5x1014 at./cm2 and that formed with the deposited Mo of 0.09 nm average thickness, display similar microstructure properties. The preferential orientation of the C54 TiSi2 is <110> in the samples with implanted Mo or with 0.09 nm Mo interlayer, as well as in the reference sample without any Mo. It becomes <010> when the Mo interlayer is 0.73 nm thick. The silicide surface and Si/silicide interface are appreciably rougher for the silicides formed with 0.09 nm Mo interlayer, with implanted Mo or in the absence of Mo, than for the silicide formed with 0.73 nm Mo interlayer. The experimental results indicate that the enhanced formation of C54 TiSi2 is caused by the same effect, i.e. template mechanism, irrespective of the means of Mo addition to the Ti-Si system.
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46

Jung, Bokhee, Young Do Kim, Woochul Yang, R. J. Nemanich, and Hyeongtag Jeon. "Reduction of The Phase Transition Temperature of TiSi2 on Si(111) Using a Ta Interlayer." MRS Proceedings 564 (1999). http://dx.doi.org/10.1557/proc-564-59.

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AbstractThe effect of a thin Ta interlayer on the C49 to C54 phase transition of TiSi2 on Si(111) was examined. The Ta interlayered samples were prepared by depositing Ta and Ti films sequentially on Si(111) substrates in a UHV system. As control samples, 100Å Ti films were deposited directly on clean Si(111) substrates. The deposited substrates were annealed for 10 min, in-situ, at temperatures between 500°C and 750°C using 50°C increments. The TiSi2, which formed in this UHV process, was analyzed with XRD, AES, SEM, TEM, and four-point probe measurements. The control samples exhibited the C49 to C54 transition at a temperature of 750°C. However, the TiSi2 samples with 5Å and 10Å Ta interlayers displayed a significant reduction of the phase transition temperature. The XRD analysis indicated that the C49 to C54 transition temperature of TiSi2 was lowered by ∼200°C. The sheet resistance measurement showed a low resistivity characteristic of C54. The SEM and TEM micrographs showed that the Ta interlayer also suppressed the surface agglomeration of the C54 TiSi2 film. The AES analysis data indicated that the composition of the titanium silicide showed the expected Ti:Si stoichiometry of 1:2.
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47

Ma, Z., G. Ramanath, and L. H. Allen. "Kinetics and Mechanism of the C49 to C54 Titanium Disilicide Polymorphic Transformation." MRS Proceedings 320 (1993). http://dx.doi.org/10.1557/proc-320-361.

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ABSTRACTThe kinetics and mechanism of the C49 to C54 TiSi2 polymorphic transformation have been investigated in a temperature range from 660 to 720°C using in situ sheet resistance measurement and transmission electron microscopy. The kinetics results were correlated with the microstructural changes during the phase transformation. The main structural characteristics demonstrating the mechanism of the transformation were established by examining the nucleation and growth of the C54-TiSi2 in the polycrystalline C49-TiSi2 thin films. It was found that the C54 nuclei predominantly formed at grain edges (three-grain junctions) of the C49 phase and grew very fast by moving its incoherent interphase boundaries. Preliminary results have not revealed rigorous orientation relationships between the two phases. It is suggested that the C49 to C54 structural transition is massive in nature.
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48

Libera, M., and A. Quintero. "Effect of Boron Doping on the C49 TO C54 Phase Transformation in Ti/Si (100) Bilayers." MRS Proceedings 441 (1996). http://dx.doi.org/10.1557/proc-441-303.

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AbstractWe have demonstrated that the formation of C54 TiSi2 on Boron-doped single crystal silicon substrates, under RTA annealing conditions in a Nitrogen ambient, leads to a thicker TiN capping surface layer, thinner silicide layer, higher C49 to C54 transformation temperature and greater interface roughness compared to C54 TiSi 2 formation on undoped single crystal silicon substrates. Titanium films 32 nm thick were deposited on undoped and boron-doped single crystal silicon substrates. The films were annealed at 3 /C/isn nitrogen to final quenching temperatures between 500 °C and 900 TC. Ex-situ four point probe sheet resistance, cross sectional transmission electron microscopy (XTEM), high resolution transmission electron microscopy (HRTEM) and x-ray diffraction (XRD) were used to analyze the resulting TiN on TiSi2 bilayer. The C49 to C54 transformation occurs circa 760 TC and 810 TC for the undoped and boron-doped cases respectively. HRTEM observations reveal a thick 20 nm TIN layer on the C54 TiSi2 film in the boron-doped case but only fine dispersed TiN particles embedded on the top of the silicide in the undoped case. It was observed that the resultant silicide in the boron-doped case was thinner and the TiSi2 /Si(100) interface is rougher. XRD and TEM analysis show that in the boron doped case, there is a preferred C54 (040) orientation compared to a random orientation for the undoped case.
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49

Clevenger, L. A., C. Cabral, R. A. Roy, C. Lavoie, R. Viswanathan, K. L. Saenger, J. Jordan-Sweet, G. Morales, K. L. Ludwig, and G. B. Stephenson. "In Situ Analysis of the Formation of thin TISI2, (>50 nm) Contacts in Submicron Cmos Structures during Rapid Thermal Annealing." MRS Proceedings 402 (1995). http://dx.doi.org/10.1557/proc-402-257.

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AbstractA detailed in situ study of silicide reactions during rapid thermal annealing of patterned structures was performed to determine the effects of linewidth (0.2 to 1.1 μm), dopants (arsenic, boron or phosphorus) and silicon substrate type (poly-Si or <100>-Si) on the C49 to C54-TiSi2 transformation. A synchrotron x-ray source and a high speed position sensitive detector were used to collect x-ray diffraction patterns of the reacting phases on a millisecond time scale, in situ, during annealing. We demonstrate that most patterned C49-TiSi2 structures (0.2 to 1.1 μm in width, 2 to 4 μm2 in area) will incompletely transform into C54-TiSi2 during rapid thermal annealing. The C49 to C54 transformation ends at about 900°C and further annealing to higher temperatures does not force the remaining C49 to transform into C54. We also observed that the C54 formation temperature increases as the linewidth of the silicide structure decreases. These results are explained by a low density of C54 nuclei in C49 which leads to a one-dimensional growth of C54 grains along the length of the patterned lines. Finally the incorporation of a Mo implant into either poly-Si or <100>-Si before the deposition of titanium is shown to increase the percentage of C49 that transforms into C54 and also to lower the C54 formation temperature.
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50

Ohmi, S., and R. T. Tung. "Facilitated C54-TiSi2 Formation With Elevated Deposition Temperature: A Study of CO-Deposited Layers." MRS Proceedings 564 (1999). http://dx.doi.org/10.1557/proc-564-47.

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AbstractThe effect of co-deposition method on the C49- to C54-TiSi2 phase transformation was investigated. Both the co-deposition ratio of TiSix layers and the deposition temperature were found to have a significant effect on the C54 phase transformation. The optimum composition to form C54 TiSi2 phase was x∼l.5 for room temperature deposition, and x∼2.0 for samples deposited at 400°C. The incorporation of a small amount of Mo had a beneficial effect on the C54 transformation in layers deposited at room temperature, but it had little effect in layers deposited at 400°C.
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