- Deal-Grove model
The Deal-Grove model mathematically describes the growth of an
oxide layer on the surface of a material. In particular, it is used to analyzethermal oxidation ofsilicon insemiconductor device fabrication . The model was first published in1965 by Bruce Deal and Andrew Grove, ofFairchild Semiconductor .Physical assumptions
The model assumes that oxidation reaction occurs at the interface between the oxide and the substrate, rather than between the oxide and the ambient
gas . Thus, it considers three phenomena that the oxidizing species undergoes, in this order:# It diffuses from the bulk of the ambient gas to the surface.
# It diffuses through the existing oxide layer to the oxide-substrate interface.
# It reacts with the substrate.The model assumes that each of these stages proceeds at a rate proportional to the oxidant's concentration. In the first case, this means
Henry's law ; in the second,Fick's law of diffusion ; in the third, afirst-order reaction with respect to the oxidant. It also assumessteady state conditions, i.e. that transient effects do not appear.Results
Given these assumptions, the
flux of oxidant through each of the three phases can be expressed in terms of concentrations, material properties, and temperature. By setting the three fluxes equal to each other, they may each be found. In turn, the growth rate may be found readily from the oxidant reaction flux.In practice, the ambient gas (stage 1) does not limit the reaction rate, so this part of the equation is often dropped. This simplification yields a simple quadratic equation for the oxide thickness. For oxide growing on an initially bare substrate, the thickness "Xo" at time "t" is given by the following equation::where the constants A and B encapsulate the properties of the reaction and the oxide layer, respectively.
If a wafer that already contains oxide is placed in an oxidizing ambient, this equation must be modified by adding a corrective term τ, the time that would have been required to grow the pre-existing oxide under current conditions. This term may be found using the equation for "t" above.
Solving the quadratic equation for "Xo" yields::
The
discriminant of the above equation reveals two main modes of operation:::Because they appear in these equations, the quantities "B" and "B/A" are often called the "quadratic" and "linear reaction rate constants". They depend exponentially on temperature, like this::
where is the
activation energy and is theBoltzmann Constant in eV. differs from one equation to the other. The following table lists the values of the four parameters for single-crystal silicon under conditions typically used in industry (low doping, atmosphericpressure ). The linear rate constant depends on the orientation of the crystal (usually indicated by theMiller indices of the crystal plane facing the surface). The table gives values for <100> and <111> silicon.Validity for silicon
The Deal-Grove model works very well for single-crystal silicon under most conditions. However, experimental data shows that very thin oxides (less than about 25 nano
metre s) grow much more quickly in than the model predicts. This phenomenon is not well understood theoretically, but it can be modeled.If the oxide grown in a particular oxidation step will significantly exceed 25 nm, a simple adjustment accounts for the aberrant growth rate. The model yields accurate results for thick oxides if, instead of assuming zero initial thickness (or any initial thickness less than 25 nm), we assume that 25 nm of oxide exists before oxidation begins. However, for oxides near to or thinner than this threshold, more sophisticated models must be used.
Deal-Grove also fails for polycrystalline silicon ("poly-silicon"). First, the random orientation of the crystal grains makes it difficult to choose a value for the linear rate constant. Second, oxidant molecules diffuse rapidly along grain boundaries, so that poly-silicon oxidizes more rapidly than single-crystal silicon.
Dopant atoms strain the silicon lattice, and make it easier for silicon atoms to bond with incoming oxygen. This effect may be neglected in many cases, but heavily-doped silicon oxidizes significantly faster. The pressure of the ambient gas also affects oxidation rate.References
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*External links
Online Calculator including pressure effects and doping effects: http://www.lelandstanfordjunior.com/thermaloxide.html
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