Silicide formation and the interaction of metals with polycrystalline Si

The main factors affecting solid-phase Si-metal interactions are reported in this work. The influence of the orientation of the Si substrates and the presence of impurities in metal films and at the Si-metal interface on the formation of nickel and chromium silicides have been demonstrated. We have observed that the formation and kinetic rate of growth of nickel silicides is strongly dependent on the orientation and crystallinity of the Si substrates; a fact which, up to date, has never been seriously investigated in silicide formation. Impurity contaminations in the Cr film and at the Si-Cr interface are the most dominant influencing factors in the formation and kinetic rate of growth of CrSi₂. The potentiality and use of silicides as a diffusion barrier in metallization on silicon devices were also investigated.

Two phases, Ni₂Si and NiSi, form simultaneously in two distinct sublayers in the reaction of Ni with amorphous Si, while only the former phase was observed on other substrates. On (111) oriented Si substrates the growth rate is about 2 to 3 times less than that on <100> or polycrystalline Si. Transmission electron micrographs establish-·that silicide layers grown on different substrates have different microcrystalline structures. The concept of grain-boundary diffusion is speculated to be an important factor in silicide formation.

The composition and kinetic rate of CrSi₂ formation are not influenced by the underlying Si substrate. While the orientation of the Si substrate does not affect the formation of CrSi₂ , the purity of the Cr film and the state of Si-Cr interface become the predominant factors in the reaction process. With an interposed layer of Pd₂Si between the Cr film and the Si substrate, CrSi₂ starts to form at a much lower temperature (400°C) relative to the Si-Cr system. However, the growth rate of CrSi₂ is observed to be independent of the thickness of the Pd2Si layer. For both Si-Cr and Si-Pd₂Si-Cr samples, the growth rate is linear with time with an activation energy of 1.7 ± 0.1 ev.

A tracer technique using radioactive ³¹Si (T_1/2 = 2.26 h) was used to study the formation of CrSi₂ on Pd₂Si. It is established from this experiment that the growth of CrSi₂ takes place partly by transport of Si directly from the Si substrate and partly by breaking Pd₂Si bonds, making free Si atoms available for the growth process.

The role of CrSi₂ in Pd-Al metallization on Si was studied. It is established that a thin CrSi₂ layer can be used as a diffusion barrier to prevent Al from interacting with Pd₂Si in the Pd-Al metallization on Si.

As a generalization of what has been observed for polycrystalline-Si-Al interaction, the reactions between polycrystalline Si (poly Si) and other metals were studied. The metals investigated include Ni, Cr, Pd, Ag and Au. For Ni, Cr and Pd, annealing results in silicide formation, at temperatures similar to those observed on single crystal Si substrates. For Al, Ag and Au, which form simple eutectics with Si annealing results in erosion of the poly Si layer and growth of Si crystallites in the metal films.

Backscattering spectrometry with 2.0 and 2.3 MeV ⁴He ions was the main analytical tool used in all our investigations. Other experimental techniques include the Read camera glancing angle x-ray diffraction, scanning electron, optical and transmission electron microscopy. Details of these analytical techniques are given in Chapter II.

Progress in the understanding of Ni silicide formation for advanced MOS structures

Metallic silicides have been used as contact materials on source/drain and gate in metal-oxide semiconductor (MOS) structure for 40 years. Since the 65 nm technology node, NiSi is the preferred material for contact in microelectronic due to low resistivity, low thermal budget, and low Si consumption. Ni(Pt)Si with 10 at.% Pt is currently employed in recent technologies since Pt allows to stabilize NiSi at high temperature. The presence of Pt and the very low thickness (<10 nm) needed for the device contacts bring new concerns for actual devices. In this work, in situ techniques [X-ray diffraction (XRD), X-ray reflectivity (XRR), sheet resistance, differential scanning calorimetry (DSC)] were combined with atom probe tomography (APT) to study the formation mechanisms as well as the redistribution of dopants and alloy elements (Pt, Pd.) during the silicide formation. Phenomena like nucleation, lateral growth, interfacial reaction, diffusion, precipitation, and transient phase formation are investigated. The effect of alloy elements (Pt, Pd.) and dopants (As, B.) as well as stress and defects induced by the confinement in devices on the silicide formation mechanism and alloying element redistribution is examined. In particular APT has been performed for the three-dimensional (3D) analysis of MOSFET at the atomic scale. The advances in the understanding of the mechanisms of formation and redistribution are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CERIUM SILICIDE FORMATION IN THIN CE SI MULTILAYER FILMS

Alternating layers of Si(200 angstrom thick) and Ce(200 angstrom thick) up to 26 layers altogether were deposited by electron evaporation under ultrahigh vacuum conditions on Si(100) substrate held at 150-degrees-C. Isothermal, rapid thermal annealing has been used to react these Ce-Si multilayer films. A variety of analytical techniques has been used to study these multilayer films after annealing, and among these are Auger electron spectroscopy, Rutherford backscattering, X-ray diffraction, and high resolution transmission electron microscopy. Intermixing of these thin Ce-Si multilayer films has occurred at temperatures as low as 150-degrees-C for 2 h, when annealed. Increasing the annealing temperature from 150 to 400-degrees-C for 1 h, CeSi2 forms gradually and the completion of reaction occurs at approximately 300-400-degrees-C. During the formation of CeSi2 from 150-400-degrees-C, there is some evidence for small grains in the selected area diffraction patterns, indicating that CeSi2 crystallites were present in some regions. However, we have no conclusive evidence for the formation of epitaxial CeSi2 layers, only polycrystals were formed when reacted in the solid phase even after rapid thermal anneal at 900-degrees-C for 10 s. The formation mechanism has also been discussed in combining the results of the La-Si system.

INFRARED SURFACE-PLASMONS ON PLATINUM SILICIDE

It is shown that surface plasmons (SPs) are supported on thin PtSi films. Using a prism-air gap-sample configuration, p-polarised infra-red light (3.39-mu-m) has been coupled with approximately 95% efficiency to SPs on the silicide electrode of PtSi-Si Schottky barrier structures. Stimulating SPs offers both a means of optically characterising silicide films and of enhancing optical absorption with a view to significantly increasing the Schottky barrier photoresponse.

Characterization of optical properties of PtSi at 3.392 mu m from 300 K to 85 K and relation of morphological effects

PtSi/Si Schottky junctions, fabricated using a conventional technique of Pt deposition with a subsequent thermal anneal, are examined using X-ray diffraction, atomic force microscopy and a novel prism/gap/sample optical coupling system. With the aid of X-ray diffraction and atomic farce microscopy it is shown that a post-anneal etch in aqua regia is essential for the removal of an unreacted, rough surface layer of Pt, to leave a much smoother PtSi film. The prism/gap/sample or Otto coupling rig is mounted in a small UHV chamber and has facilities for remote variation of the gap (by virtue of a piezoactuator system) and variation of the temperature in the range of similar to 300 K - 85 K. The system is used to excite surface plasmon polaritons on the outer surface of the PtSi and thus produce sensitive optical characterisation as a function of temperature. This is performed in order to yield an understanding of the temperature dependence of phonon and interface scattering of carriers in the PtSi.

Three dimensional distributions of arsenic and platinum within NiSi contact and gate of an n-type transistor

Atom probe tomography was used to study the redistribution of platinum and arsenic atoms after Ni(Pt) silicidation of As-doped polycrystalline Si. These measurements were performed on a field-effect transistor and compared with those obtained in unpatterned region submitted to the same process. These results suggest that Pt and As redistribution during silicide formation is only marginally influenced by the confinement in microelectronic devices. On the contrary, there is a clear difference with the redistribution reported in the literature for the blanket wafers. Selective etching used to remove the non-reacted Ni(Pt) film after the first rapid heat treatment may induce this difference. © 2011 American Institute of Physics.

Ni-silicide growth kinetics in Si and Si/SiO2 core/shell nanowires.

A systematic study of the kinetics of axial Ni silicidation of as-grown and oxidized Si nanowires (SiNWs) with different crystallographic orientations and core diameters ranging from ∼ 10 to 100 nm is presented. For temperatures between 300 and 440 °C the length of the total axial silicide intrusion varies with the square root of time, which provides clear evidence that the rate limiting step is diffusion of Ni through the growing silicide phase(s). A retardation of Ni-silicide formation for oxidized SiNWs is found, indicative of a stress induced lowering of the diffusion coefficients. Extrapolated growth constants indicate that the Ni flux through the silicided NW is dominated by surface diffusion, which is consistent with an inverse square root dependence of the silicide length on the NW diameter as observed for (111) orientated SiNWs. In situ TEM silicidation experiments show that NiSi(2) is the first forming phase for as-grown and oxidized SiNWs. The silicide-SiNW interface is thereby atomically abrupt and typically planar. Ni-rich silicide phases subsequently nucleate close to the Ni reservoir, which for as-grown SiNWs can lead to a complete channel break-off for prolonged silicidation due to significant volume expansion and morphological changes.

Tantalum-oxide catalysed chemical vapour deposition of single- and multi-walled carbon nanotubes

Tantalum-oxide thin films are shown to catalyse single- and multi-walled carbon nanotube growth by chemical vapour deposition. A low film thickness, the nature of the support material (best results with SiO2) and an atmospheric process gas pressure are of key importance for successful nanotube nucleation. Strong material interactions, such as silicide formation, inhibit nanotube growth. In situ X-ray photoelectron spectroscopy indicates that no catalyst reduction to Ta-metal or Ta-carbide occurs during our nanotube growth conditions and that the catalytically active phase is the Ta-oxide phase. Such a reduction-free oxide catalyst can be technologically advantageous. © 2013 The Royal Society of Chemistry.

Atom probe tomography for advanced metallization

In microelectronics, the increase in complexity and the reduction of devices dimensions make essential the development of new characterization tools and methodologies. Indeed advanced characterization methods with very high spatial resolution are needed to analyze the redistribution at the nanoscale in devices and interconnections. The atom probe tomography has become an essential analysis to study materials at the nanometer scale. This instrument is the only analytical microscope capable to produce 3D maps of the distribution of the chemical species with an atomic resolution inside a material. This technique has benefit from several instrumental improvements during last years. In particular, the use of laser for the analysis of semiconductors and insulating materials offers new perspectives for characterization. The capability of APT to map out elements at the atomic scale with high sensitivity in devices meets the characterization requirements of semiconductor devices such as the determination of elemental distributions for each device region. In this paper, several examples will show how APT can be used to characterize and understand materials and process for advanced metallization. The possibilities and performances of APT (chemical analysis of all the elements, atomic resolution, planes determination, crystallographic information...) will be described as well as some of its limitations (sample preparation, complex evaporation, detection limit, ...). The examples illustrate different aspect of metallization: dopant profiling and clustering, metallic impurities segregation on dislocation, silicide formation and alloying, high K/metal gate optimization, SiGe quantum dots, as well as analysis of transistors and nanowires. © 2013 Elsevier B.V. All rights reserved.

EFFECTS OF DEEP CENTERS AT PT SI INTERFACES AND HYDROGENATION

Electrical measurements were combined with surface techniques to study the Pt/Si interfaces at various silicide formation temperatures. Effects of deep centers on the Schottky barrier heights were studied. Hydrogen plasma treatment was used to passivate the impurity/defect centers at the interfaces, and the effects of hydrogenation on the Schottky barrier heights were also examined. Combining our previous study on the Pt/Si interfacial reaction, factors influencing the PtSi/Si Schottky barrier diode are discussed.

INTERACTION OF CO WITH SI AND SIO2 DURING RAPID THERMAL ANNEALING

The interaction of Co with Si and SiO2 during rapid thermal annealing has been investigated. Phase sequence, layer morphology, and reaction kinetics were studied by sheet resistance, x-ray diffraction, Auger electron spectroscopy, x-ray photoelectron spectroscopy, and scanning electron microscopy. With increasing annealing temperature, Co film on Si(100) is transformed sequentially into Co2Si, CoSi, and finally CoSi2 which corresponds to the minimum of sheet resistance. No evidence of silicide formation was observed for Co/SiO2 annealed even at the high temperature of 1050-degrees-C.

Modifying germanium nanowires for future devices: an in situ TEM study

Germanium was of great interest in the 1950’s when it was used for the first transistor device. However, due to the water soluble and unstable oxide it was surpassed by silicon. Today, as device dimensions are shrinking the silicon oxide is no longer suitable due to gate leakage and other low-κ dielectrics such as Al2O3 and HfO2 are being used. Germanium (Ge) is a promising material to replace or integrate with silicon (Si) to continue the trend of Moore’s law. Germanium has better intrinsic mobilities than silicon and is also silicon fab compatible so it would be an ideal material choice to integrate into silicon-based technologies. The progression towards nanoelectronics requires a lot of in depth studies. Dynamic TEM studies allow observations of reactions to allow a better understanding of mechanisms and how an external stimulus may affect a material/structure. This thesis details in situ TEM experiments to investigate some essential processes for germanium nanowire (NW) integration into nanoelectronic devices; i.e. doping and Ohmic contact formation. Chapter 1 reviews recent advances in dynamic TEM studies on semiconductor (namely silicon and germanium) nanostructures. The areas included are nanowire/crystal growth, germanide/silicide formation, irradiation, electrical biasing, batteries and strain. Chapter 2 details the study of ion irradiation and the damage incurred in germanium nanowires. An experimental set-up is described to allow for concurrent observation in the TEM of a nanowire following sequential ion implantation steps. Grown nanowires were deposited on a FIB labelled SiN membrane grid which facilitated HRTEM imaging and facile navigation to a specific nanowire. Cross sections of irradiated nanowires were also performed to evaluate the damage across the nanowire diameter. Experiments were conducted at 30 kV and 5 kV ion energies to study the effect of beam energy on nanowires of varied diameters. The results on nanowires were also compared to the damage profile in bulk germanium with both 30 kV and 5 kV ion beam energies. Chapter 3 extends the work from chapter 2 whereby nanowires are annealed post ion irradiation. In situ thermal annealing experiments were conducted to observe the recrystallization of the nanowires. A method to promote solid phase epitaxial growth is investigated by irradiating only small areas of a nanowire to maintain a seed from which the epitaxial growth can initiate. It was also found that strain in the nanowire greatly effects defect formation and random nucleation and growth. To obtain full recovery of the crystal structure of a nanowire, a stable support which reduces strain in the nanowire is essential as well as containing a seed from which solid phase epitaxial growth can initiate. Chapter 4 details the study of nickel germanide formation in germanium nanostructures. Rows of EBL (electron beam lithography) defined Ni-capped germanium nanopillars were extracted in FIB cross sections and annealed in situ to observe the germanide formation. Chapter 5 summarizes the key conclusions of each chapter and discusses an outlook on the future of germanium nanowire studies to facilitate their future incorporation into nanodevices.