8.2 Case Studies

8.2.1 Ni Silicides

We will look in some detail on the system Si - silicide - metal, where many phase boundaries can be observed. The basic experiment consists of depositing a metal (here Ni) on Si (either in a {100} or {111} orientation), and induce some reaction by heating.
Three different Ni-silicides will form consecutively:
 
 
Ni silicide reactions schematically
 
Altogether five different phase boundaries may be encountered, some of which are shown in the picture above:
Si - Ni,
Si - Ni2Si and Ni2Si - Ni,
Si - NiSi and NiSi - Ni2Si,
Si - NiSi2, and NiSi2 - NiSi.
Major findings are:
The interface between Si and Ni does not really exist because immediately after the (room temperature) evaporation, a thin Ni2Si-silicide layer forms between the Si and the Ni.
The Ni2Si layer is polycrystalline; the interface between Si and Ni2Si seems to be incoherent - i.e. if there is any structure it is not observed with "normal" TEM.
The interface between {111} Si and NiSi is epitaxial, however, and thus semicoherent against all expectations:
NiSi is reported to crystallize in an orthorhombic lattice; on {111} Si substrates, however, a hexagonal lattice is observed (which can be cobtained from an orthorhombic lattice by slight adjustments of the lattice parameters).
The misfit is extremely large (ca. 15%) and would require a distance of 0,6 nm for b = a/2<110> misfit dislocations. Such a small spacing is usually considered to be too small to be meaningful - epitaxial relationships thus should not exist. The diffraction pattern, however, indicates a clear epitaxial relationship (with a bit of polycrystallinity as indicated by the rings):

Diffraction from Si - NiSi layer
 
While no structure can be seen in conventional TEM, high-resolution TEM shows pronounced misfit dislocations relieving some of the stress at a spacing of about 1,6 nm. This is one of the densest misfit dislocation networks ever observed. The ending lattice planes are indicated by the edge dislocation symbol somewhat above the actual interface plane.
 
Interface Si -NiSi
 
 The most interesting phase is NiSi2; it is the final product after sufficient annealing at 800 °C.
NiSi2 crystallizes in the cubic CaF2 - structure with a lattice constant that is only 0,3% smaller than that of Si.
We thus can expect an epitaxial relationship with a misfit dislocation network at a spacing
 
p  =  b · b 
(aeam)/am
 =  b
0,003
 
With aSi = 0,54 nm and b = a/2<110> = 0,382 nm we would expect a network with a spacing of about 130 nm.
What we see for an interface on a {111} plane looks like this:
 
Dislocation network inthe Si -Nidisilicide interface
 
This looks rather interesting. We seem to have a simple hexagonal network of dislocations, but we see some additional features: "Blackish" areas and an island with rather coarser structures embedded in a sea of something with a possible hexagonal symmetry.
The reasons for these complications are two peculiarities of this interface, which can also be found in similar systems; in particular in the Si - CoSi2 interface.
First, it "likes" to be on {111}-planes. This leads to heavy facetting if the Ni layer is deposited on a Si {100} plane, but also to some facetting on {111}. This can be seen best in cross-section; an example is given in the illustration. We must expect that the accommodation of steps will introduce irregularities into the network.
Second, the interface is mostly not in a S = 1 relation, i.e. with a direct continuation of the lattices, but in a S = 3 relation. This means that the NiSi2 is twinned with respect to the substrate. An overview picture is shown in the link. This somewhat surprising result can be obtained from a careful contrast analysis of the network with micrographs taken at higher magnifications. The network then looks like this:
 
Network inSi -Nidisilicide interface at high magnification
 
Shown is one of the "islands" in a sea of regular hexagonal dislocations. Its structure looks somewhat familiar: The arrows point to extended stacking fault knots as in the case of the small angle twist grain boundary on {111} in Si.
But in contrast to the network in the small angle twist boundary, all dislocations now are edge dislocations; as expected for misfit dislocations. The distance is also what would be expected for a almost fully relaxed layer of NiSi2.
The question is, of course, why this mix of S = 1 and S = 3 relations? As in the case of the low angle twist boundary encountered before, nobody knows for sure. Obviously, the energy balance is rather similar for the two cases.
Very similar interfaces have been observed in the case of Si - CoSi2 interfaces, which, except for a slightly larger misfit, have essentially the same geometry.
Despite the structural similarity to the small angle grain boundaries, the phase boundaries add new features and open questions. To get more insights, we will now discuss the case of the interface between (cubic) Si and (hex.) Pd2Si.

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© H. Föll (Defects - Script)