Thermal oxidation

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Furnaces used for diffusion and thermal oxidation at LAAS technological facility in Toulouse, France. In microfabrication, thermal oxidation is a way to produce a thin layer of oxide (usually silicon dioxide) on the surface of a wafer. 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 the Deal-Grove model. Thermal oxidation may be applied to different materials, but this article will only consider oxidation of silicon substrates to producesilicon dioxide. Contents [hide] 1 The chemical reaction o 1.1 Deal-Grove model 2 Oxidation technology

3 Oxide quality 4 Other notes 5 References 6 External links

[edit]The chemical reaction Thermal oxidation of silicon is usually performed at a temperature between 800 and 1200C, resulting in so called High Temperature Oxide layer (HTO). It may use either water vapor (usually UHP steam) or molecular oxygen as the oxidant; it is consequently called either wet or dry oxidation. The reaction is one of the following:

The oxidizing ambient may also contain several percent of hydrochloric acid (HCl). The chlorine removes 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, 2.27 unit thicknesses of oxide will appear. [1] Conversely, if a bare silicon surface is oxidized, 44% of the oxide thickness will lie below the original surface, and 56% above it. [edit]Deal-Grove model Main article: Deal-Grove model According to the commonly-used Deal-Grove model, the time t required to grow an oxide of thickness Xo, at a constant temperature, on a bare silicon surface, is:

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 , the time that would have been required to grow the preexisting oxide under current conditions. This term may be found using the equation for t above. Solving the quadratic equation for Xo yields:

[edit]Oxidation technology Most thermal oxidation is performed in furnaces, at temperatures between 800 and 1200C. A single furnace accepts many wafers at the same time, in a specially designed quartz 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. Vertical furnaces stand higher than horizontal furnaces, so they may not fit into some microfabrication facilities. However, they help to prevent dustcontamination. Unlike horizontal furnaces, in which falling dust can contaminate any wafer, vertical furnaces only allow it to fall on the top wafer in the boat. Vertical furnaces also eliminate an issue that plagued horizontal furnaces: non-uniformity of grown oxide across the wafer[citation needed]. Horizontal furnaces typically have convection currents inside the tube which causes 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 causes the top of the wafer to have a thicker oxide 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 dampening 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. [edit]Oxide quality Wet oxidation is preferred to dry oxidation for growing thick oxides, because of the higher growth rate. However, fast oxidation leaves more dangling bonds at the silicon interface, which produce quantum states for electrons and allow current to leak along the interface. (This is called a "dirty" interface.) Wet oxidation also yields a lowerdensity oxide, with lower dielectric 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 (a dry-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. Mobile metal ions can degrade performance of MOSFETs (sodium is of particular concern). However, chlorine can immobilize sodium by forming sodium chloride. Chlorine is often introduced by adding hydrogen chloride or trichloroethylene to the oxidizing medium. Its presence also increases the rate of oxidation.

[edit]Other

notes

Thermal diffusion
Thermal diffusion utilizes the transfer of heat across a thin liquid or gas to accomplish isotope separation. The process exploits the fact that the lighter 235U gas molecules will diffuse toward a hot surface, and the heavier 238U gas molecules will diffuse toward a cold surface. The S-50 plant at Oak Ridge,

Tennesseewas used during World War II to prepare feed material for the EMIS process. It was abandoned in favor of gaseous diffusion.

In order to form a functional MEMS structure on a substrate, it is necessary to etch the thin films previously deposited and/or the substrate itself. In general, there are two classes of etching processes: 1. Wet etching where the material is dissolved when immersed in a chemical solution 2. Dry etching where the material is sputtered or dissolved using reactive ions or a vapor phase etchant In the following, we will briefly discuss the most popular technologies for wet and dry etching. Wet etching This is the simplest etching technology. All it requires is a container with a liquid solution that will dissolve the material in question. Unfortunately, there are complications since usually a mask is desired to selectively etch the material. One must find a mask that will not dissolve or at least etches much slower than the material to be patterned. Secondly, some single crystal materials, such as silicon, exhibit anisotropic etching in certain chemicals. Anisotropic etching in contrast to isotropic etching means different etch rates in different directions in the material. The classic example of this is the <111> crystal plane sidewalls that appear when etching a hole in a <100> silicon wafer in a chemical such as potassium hydroxide (KOH). The result is a pyramid shaped hole instead of a hole with rounded sidewalls with a isotropic etchant. The principle of anisotropic and isotropic wet etching is illustrated in the figure below.

When do I want to use wet etching? This is a simple technology, which will give good results if you can find the combination of etchant and mask material to suit your application. Wet etching works very well for etching thin films on substrates, and can also be used to etch the substrate itself. The problem with substrate etching is that isotropic processes will cause undercutting of the mask layer by the same distance as the etch depth. Anisotropic processes allow the etching to stop on certain crystal planes in the substrate, but still results in a loss of space, since these planes cannot be vertical to the surface when etching holes or cavities. If this is a limitation for you, you should consider dry etching of the substrate instead. However, keep in mind that the cost per wafer will be 1-2 orders of magnitude higher to perform the dry etching If you are making very small features in thin films (comparable to the film thickness), you may also encounter problems with isotropic wet etching, since the undercutting will be at least equal to the film thickness. With dry etching it is possible etch almost straight down without undercutting, which provides much higher resolution.

Figure 1: Difference between anisotropic and isotropic wet etching. Dry etching The dry etching technology can split in three separate classes called reactive ion etching (RIE), sputter etching, and vapor phase etching. In RIE, the substrate is placed inside a reactor in which several gases are introduced. A plasma is struck in the gas mixture using an RF power source, breaking the gas molecules into ions. The ions are accelerated towards, and reacts at, the surface of the material being etched, forming another gaseous material. This is known as the chemical part of reactive ion etching. There is also a physical part which is similar in nature to the sputtering deposition process. If the ions have high enough energy, they can knock atoms out of the material to be etched without a chemical reaction. It is a very complex task to develop dry etch processes that balance chemical and physical etching, since there are many parameters to adjust. By changing the balance it is possible to influence the anisotropy of the etching, since the chemical part is isotropic and the physical part highly anisotropic the combination can form sidewalls that have shapes from rounded to vertical. A schematic of a typical reactive ion etching system is shown in the figure below. A special subclass of RIE which continues to grow rapidly in popularity is deep RIE (DRIE). In this process, etch depths of hundreds of microns can be achieved with almost vertical sidewalls. The primary technology is based on the so-called "Bosch process", named after the German company Robert Bosch which filed the original patent, where two different gas compositions are alternated in the reactor. The first gas composition creates a polymer on the surface of the substrate, and the second gas composition etches the substrate. The polymer is immediately sputtered away by the physical part of the etching, but only on the horizontal surfaces and not the sidewalls. Since the polymer only

dissolves very slowly in the chemical part of the etching, it builds up on the sidewalls and protects them from etching. As a result, etching aspect ratios of 50 to 1 can be achieved. The process can easily be used to etch completely through a silicon substrate, and etch rates are 3-4 times higher than wet etching. Sputter etching is essentially RIE without reactive ions. The systems used are very similar in principle to sputtering deposition systems. The big difference is that substrate is now subjected to the ion bombardment instead of the material target used in sputter deposition. Vapor phase etching is another dry etching method, which can be done with simpler equipment than what RIE requires. In this process the wafer to be etched is placed inside a chamber, in which one or more gases are introduced. The material to be etched is dissolved at the surface in a chemical reaction with the gas molecules. The two most common vapor phase etching technologies are silicon dioxide etching using hydrogen fluoride (HF) and silicon etching using xenon diflouride (XeF2), both of which are isotropic in nature. Usually, care must be taken in the design of a vapor phase process to not have bi-products form in the chemical reaction that condense on the surface and interfere with the etching process. When do I want to use dry etching? The first thing you should note about this technology is that it is expensive to run compared to wet etching. If you are concerned with feature resolution in thin film structures or you need vertical sidewalls for deep etchings in the substrate, you have to consider dry etching. If you are concerned about the price of your process and device, you may want to minimize the use of dry etching. The IC industry has long since adopted dry etching to achieve small features, but in many cases feature

size is not as critical in MEMS. Dry etching is an enabling technology, which comes at a sometimes high cost.

Figure 2: Typical parallel-plate reactive ion etching system.