Nucleation can play an important role during the formation of silicides, especially when the difference in Gibbs free energy ΔG between the existing and newly formed phase is small. In this work, it is shown that the addition of elements that form a solid solution with either the existing or nucleating phase influences the entropy of mixing and thus changes ΔG. In this way, the height of the nucleation barrier may be controlled, thus controlling the nucleation temperature. The influence of mixing entropy on silicide nucleation is illustrated by experiments for two ternary systems: Co–Mn–Si and Ni–Pd–Si. It is shown that the nucleation temperature of CoSi2 is increased by the addition of Mn, the nucleation temperature of MnSi1.7 is increased by the presence of Co, the nucleation temperature of NiSi2 is increased by the addition of Pd, and the nucleation temperature of PdSi is decreased by the addition of Ni. In all four cases, the effect of the alloying element on the nucleation temperature can be explained by a model on the basis of the concept of mixing entropy.

The silicide formation for Ni/Pd and Pd/Ni bilayers on Si(100) substrates was investigated. X-ray diffraction and photoelectron spectroscopy (XPS) depth profiling have been applied to study the phase formation of the silicide. We found that with addition of Pd into Ni/Si, a uniform layer of ternary Ni1−xPdxSi layer formed and kept stable for a wide temperature range. The lattice parameter of Ni1−xPdxSi as a function of Pd addition was calculated. The nucleation temperature of NiSi2 was delayed due to the addition of Pd. The higher the Pd addition, the larger the increase in NiSi2 nucleation temperature. We also studied the effect on the addition of Ni to the Pd/Si reaction. For pure Pd/Si reaction PdSi nucleated from Pd2Si at 750°C or above. For Ni/Pd/Si reaction, Pd2Si changed to Ni1−xPdxSi at temperature lower than 750°C due to the incorporation of Ni. The phenomena were explained by classic nucleation theory taking into account the effect of mixing entropy effect.

Ultra-thin epitaxial CoSi2 films formed by Co(3∼5nm)/Ti(1 nm)/Si(100) and Co(3∼5nm)/Si(lnm)/Ti(Inm)/Si are studied. The multilayers are deposited by ion-beam sputtering. Rapid thermal annealing (RTA) is used for silicidation. XRD, RBS, TEM, AFM, four-point probe, I-V and C-V measurements are carried out for characterization. The XRD spectra show the CoSi2 film formed by Co/Ti/Si or Co/Si/Ti/Si solid phase epitaxy has, epitaxial characteristic. XTEM shows that the film is continuous. RBS/Channeling shows that the formed CoSi2 has sharp interface with a minimum channeling yield of Co signal of 40%. AFM shows that the surface of ultra-thin CoSi2 film is smooth with a roughness of nearly 0.7 nm. The Rs∼T relationship shows that the CoSi2 films formed by Co/Si/Ti/Si reaction have the best thermal stability (stable up to 900°C). Those formed by Co/Ti/Si reaction are stable up to 850°C, while those formed by Co/Si reaction are only stable up to 750°C. By fitting the experimental I-V and C-V curves of the epitaxial CoSi2/Si Schottky diodes, barrier heights of around 0.6 eV and close to unity ideality factors are obtained.

Ballistic electron emission microscopy (BEEM) and deep level transient spectroscopy (DLTS) have been used to study the effects of substrate damage introduced by an ion-milling process in PtSi/n-Si Schottky contacts. Argon ions with well-defined energies of 300, 500, 700, 1000, 1500 eV were used to sputter n-type Si substrates in an ion beam sputtering system before metal deposition and silicide formation. Histograms of the PtSi/n-Si Schottky barrier height (SBH) measured by BEEM show that the mean SBH decreases with increasing ion energy, which can be explained as a result of donor-like defects that are introduced by the ion milling treatment. From DLTS measurements, we found direct evidence for the presence of such defects.

In this work, we will show that a reactive Ti capping layer can reduce oxide layers that are present at the cobalt-silicon interface. We have used a thin, chemically grown oxide to have a well-controlled form of interfacial oxide layer. To study the silicidation reaction, isochronal annealing was done at various temperatures. Different sets of samples were made in order to investigate the influence of the thickness of the Co layer and its Ti cap. Titanium capping strongly influenced the silicidation reaction. We have found that already at moderate temperatures, Ti can diffuse towards the Co/Si interface, and can reduce the interfacial oxide there present, enabling CoSi2 formation. The CoSi2 thus formed has a preferential epitaxial orientation, and the process by which this epitaxy is attained may be explained by a combination of OME (Oxide Mediated Epitaxy) and TIME (Titanium Mediated Epitaxy).

The formation of ultrathin (≤20 nm) and smooth CoSi2 layers on c–Si substrates has been studied by using a one- and a two-step RTP silicidation method. Pinhole-free silicide layers with a thickness down to ∼10–12 nm were formed on n−, n+, and p+ crystalline Si substrates in the one-step RTP process by sputtering of Co films as thin as 4 nm and subsequent silicidation at 750 °C for 5 or 30 s. The two-step RTP silicidation method is based on the consumption of only a small fraction of a thick sputtered Co film to form Co2Si or CoSi during a first RTP step at 400–500 °C. A selective etch follows to remove the unreacted Co film. During a second, higher temperature, RTP step CoSi2 is formed. Pinhole-free and smooth CoSi2 films with a thickness down to 20 nm were formed in this way on both n+ and p+ monocrystalline Si substrates.

In this paper the electrical properties of epitaxial CoSi2 on Si obtained by solid-state reaction of a Ti/Co bimetallic layer are investigated. Low temperature resistivity, magnetoresistance and Hall data are presented. The CoSi2ISi Schottky diodes are characterised by current - voltage and capacitance - voltage measurements at temperatures varying between - 100°C and 60°C.