Inmicrofabrication,thermal oxidation is a way to produce a thin layer ofoxide (usuallysilicon dioxide) on the surface of awafer. The technique forces an oxidizing agent to diffuse into the wafer at high temperature and react with it. The rate of oxide growth is often predicted by theDeal–Grove model.^[1] Thermal oxidation may be applied to different materials, but most commonly involves the oxidation ofsilicon substrates to producesilicon dioxide.

Thermal oxidation of silicon is usually performed at a temperature between 800 and 1200°C, resulting in a so-calledHigh Temperature Oxide layer (HTO). It may use eitherwater vapor (usuallyUHP steam) or molecularoxygen as the oxidant; it is consequently called eitherwet ordry oxidation. The reaction is one of the following:

${\displaystyle \mathrm{S}\mathrm{i}+2{\mathrm{H}}_2\mathrm{O}\to \mathrm{S}\mathrm{i}{\mathrm{O}}_2+2{\mathrm{H}}_{2(\mathrm{g})}}$

${\displaystyle \mathrm{S}\mathrm{i}+{\mathrm{O}}_2\to \mathrm{S}\mathrm{i}{\mathrm{O}}_2}$

The oxidizing ambient may also contain several percent ofhydrochloric acid (HCl). The chlorine neutralizes metal ions that may occur in the oxide.

Thermal oxide incorporates silicon consumed from the substrate and oxygen supplied from the ambient. Thus, it grows both down into the wafer and up out of it. For every unit thickness of silicon consumed, 2.17 unit thicknesses of oxide will appear.^[2] If a bare silicon surface is oxidized, 46% of the oxide thickness will lie below the original surface, and 54% above it.

According to the commonly used Deal-Grove model, the timeτ required to grow an oxide of thicknessX_o, at a constant temperature, on a bare silicon surface, is:

${\displaystyle \tau =\frac{X_o^2}{B}+\frac{X_o}{(\frac{B}{A})}}$

where the constants A and B relate to properties of the reaction and the oxide layer, respectively. This model has further been adapted to account forself-limiting oxidation processes, as used for the fabrication and morphological design ofSi nanowires and other nanostructures.^[1]

If awafer 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 fort above.

Solving the quadratic equation forX_o yields:

${\displaystyle X_o(t)=A/2\cdot \left[\sqrt{1+\frac{4B}{A^2}(t+\tau )}-1\right]}$

Most thermal oxidation is performed infurnaces, at temperatures between 800 and 1200 °C. A single furnace accepts many wafers at the same time, in a specially designedquartz rack (called a "boat"). Historically, the boat entered the oxidation chamber from the side (this design is called "horizontal"), and held the wafers vertically, beside each other. However, many modern designs hold the wafers horizontally, above and below each other, and load them into the oxidation chamber from below.

Because vertical furnaces stand higher than horizontal furnaces, they may not fit into some microfabrication facilities. They help to preventdust contamination. Unlike horizontal furnaces, in which falling dust can contaminate any wafer, vertical furnaces use enclosed cabinets with air filtration systems to prevent dust from reaching the wafers.

Vertical furnaces also eliminate an issue that plagued horizontal furnaces: non-uniformity of grown oxide across the wafer.^[3] Horizontal furnaces typically have convection currents inside the tube, which cause the bottom of the tube to be slightly colder than the top of the tube. As the wafers lie vertically in the tube, the convection, and the temperature gradient with it, cause the top of the wafer to have a thicker oxide layer than the bottom of the wafer. Vertical furnaces solve this problem by having wafer sitting horizontally and then having the gas flow in the furnace flowing from top to bottom, significantly damping any thermal convections.

Vertical furnaces also allow the use of load locks to purge the wafers with nitrogen before oxidation to limit the growth of native oxide on the Si surface.

Wet oxidation is preferred to dry oxidation for growing thick oxides, because of the higher growth rate. However, fast oxidation leaves moredangling bonds at the silicon interface, which producequantum states for electrons and allow current to leak along the interface. (This is called a "dirty" interface.) Wet oxidation also yields a lower-density oxide, with lowerdielectric strength.

The long time required to grow a thick oxide in dry oxidation makes this process impractical. Thick oxides are usually grown with a long wet oxidation bracketed by short dry ones (adry-wet-dry cycle). The beginning and ending dry oxidations produce films of high-quality oxide at the outer and inner surfaces of the oxide layer, respectively.

Mobilemetalions can degrade performance ofMOSFETs (sodium is of particular concern). However,chlorine can immobilize sodium by formingsodium chloride. Chlorine is often introduced by addinghydrogen chloride ortrichloroethylene to the oxidizing medium. Its presence also increases the rate of oxidation.

Thermal oxidation can be performed on selected areas of a wafer and blocked on others. This process, first developed at Philips,^[4] is commonly referred to as the local oxidation of silicon (LOCOS) process. Areas which are not to be oxidized are covered with a film ofsilicon nitride, which blocks diffusion of oxygen and water vapor due to its oxidation at a much slower rate.^[5] The nitride is removed after oxidation is complete. This process cannot produce sharp features, because lateral (parallel to the surface) diffusion of oxidant molecules under the nitride mask causes the oxide to protrude into the masked area.

Because impuritiesdissolve differently in silicon and oxide, a growing oxide will selectively take up or rejectdopants. This redistribution is governed by the segregation coefficient, which determines how strongly the oxide absorbs or rejects the dopant, and thediffusivity.

The orientation of the siliconcrystal affects oxidation. A <100> wafer (seeMiller indices) oxidizes more slowly than a <111> wafer but produces an electrically cleaner oxide interface.

Thermal oxidation of any variety produces a higher-quality oxide, with a much cleaner interface, thanchemical vapor deposition of oxide resulting in low temperature oxide layer (reaction ofTEOS at about 600 °C). However, the high temperatures required to produce High Temperature Oxide (HTO) restrict its usability. For instance, inMOSFET processes, thermal oxidation is never performed after the doping for the source and drain terminals is performed, because it would disturb the placement of the dopants.

Notes

Wikimedia Commons has media related toThermal oxidation.

Sources

• Jaeger, Richard C. (2001). "Thermal Oxidation of Silicon".Introduction to Microelectronic Fabrication. Upper Saddle River:Prentice Hall.ISBN 978-0-201-44494-0.

• Online calculator including deal grove and massoud oxidation models, with pressure and doping effects at:http://www.lelandstanfordjunior.com/thermaloxide.html

• Semiconductor technology
• Nanomaterials
• Materials
• Microtechnology
• MOSFETs
• Nanoelectronics
• Silicon

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