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457

oxygen ions to form pairs of stable nonbridging hydroxyl groups. The reaction is described schematically by
-

process for layers greater than 40 A thickness for dry oxidation, and 1000 A for wet oxidation. The chemistry of oxidation with d w oxygen is relatively straightforward. It is assumed that the species diffusing through the growing layer is molecular oxygen. The chemical reaction at the silicon surface is

The presence of these hydroxyl groups also tends to weaken the silica network and render it more porous to diffusing species. Thus their behavior is similar to that of interstitial impurities. Figure 7.2 shows a schematic representation of fused silica glass together with the various types of defect structures that may be present in it [5]. 7.1.3 Oxide Formation Oxidation of the silicon slice is conveniently carried out by subjecting it to dry oxygen or water vapor, while it is maintained at an elevated temperature. In water vapor, or wet oxidation schemes, an inert gas (or oxygen) is bubbled through water which is usually held at 95C to avoid its excessive depletion. Direct oxidation of the silicon surface results in forming an oxide layer which -ickness of the consumed silicon. The silica is ap layer so formed contains about-2T2 x lon molecuTes ~ m - ~ z - S i O ~ . The process of oxide formation require that the oxidizing species move through the growing oxide layer in order to reach the silicon surface. Thus, growth proceeds at an ever-decreasing rate as the thickness of the intervening oxide layer increases. This diffusion-controlled regime dominates the growth
-

Here one molecule of oxygen results in the formation of one molecule of SiOZ. The overall process of oxidation of silicon with water vapor may also be considered as one in which the oxidizing species diffuses through the oxide and reacts with the silicon surface, so that

Here, however, two molecules of water vapor are used to form one molecule of S O 2 . The hydrogen evolved by this reaction diffuses rapidly through the growing oxide and leaves the system at the gas-oxide interface. The detailed nature of this reaction, although somewhat more complex [6], is assumed to proceed in the following manner: 1. Water vapor reacts with the bridging oxygen ions in the silica structure to form nonbridging hydroxyl groups. This reaction, which results in weakening the silicastructure, may be written as

2. At the oxide-silicon interface, the hydroxyl groups react with the silicon lattice to form silica polyhedra and hydrogen. The reaction is

Bridging oxygen Nonbridging oxygen Silicon

3. Hydrogen is a rapid diffuser in S O 2 , and leaves after being formed by this process. Some of this diffusing hydrogen reacts with bridging oxygen ions in the silica structure to form hydroxyl groups, as'shown by

Network modifier Hydroxyl group Network former

thus - further weakening the silica struct_ure. --

%
Fig. 7.2 Structure of silica glass. Adapted from Revesz [7].

A somewhat more detailed picture of the role of hydrogen in silica is given elsewhere [7]. However, the relatively simple model, outlined above, is suitable for describing the basic mechanism of formation of these films.

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459

7.1.4

Kinetics of Oxide Growth

j = kN1

(7.10)

The kinetics of oxide growth on silicon may be determined [8] with reference to the model of Fig. 7.3. Assume that a silicon slice is brought in contact with the oxidant, with concentration N , in the gas phase, resulting in a surface concentration of N o molecules cmp3 for this species. In typical oxidation systems, the mass transfer coefficient is extremely high, so that the magnitude of N o is essentially the solid solubility of the species at the oxidation temperature. At 1000C the solid solubility of these species is 5.2 x 1016 molecules ~ r n - ~ for dry oxygen and 3x l0l9 molecules cmp3 for water vapor at a pressure of 1 atm. The oxidizing species is assumed to diffuse in molecular form through the silicon dioxide layer, resulting in a concentration N 1 at the surface of the silicon. Transport of the species may occur by both drift and diffusion. Writing D as the diffusivity and ignoring the effects of drift, the flux density of oxidizing species arriving at the gas-oxide interface is given by j , where

where k is the interfacial reaction rate constant. These fluxes must be equal under steady-state diffusion conditions. Combining Eqs. (7. 9) and (7. 10) gives

The reaction of the oxidizing species with the silicon results in the formation of Si02. Writing n as the number of molecules * of the oxidizing impurity that are incorporated into unit volume of the oxide, the rate of change of the oxide layer thickness is given by

Solving this equation, subject to the boundary value that x = 0 at t = 0, gives and x is the thickness of the oxide at a given point in time. This is sometimes referred to as Henry's law. On arrival at the silicon surface the species enters into chemical reaction with it. If it is assumed that this reaction proceeds at a rate proportional to the concentration of the oxidizing species, then

so that

Equation (7.14) reduces to

for small values of t , and to

for large values. Thus in the initial stages of growth, in which the reaction
Fig. 7.3 Model for oxidation kinetics.
*n = 2.2 x ~ r n - ~ dry oxidation, and 4.4 x for

cmp3 for wet oxidation.

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is kinetically controlled, the oxide thickness varies linearly with time. In later stages the reaction is diffusion-limited and the oxide thickness is directly proportional to the square root of time. Equation (7.13) is often written in the more compact form

Using this form, Eqs. (7.15) and (7.16) can be written as

for small values of t , and

for large values. For this reason, the term B/A is referred to as the linear rate constant whereas the parabolic rate constant is given by B. Measured values for these rate constants as a function of temperature are given [9] in Figs. 7.4 = and 7.5 for both dry and wet oxidation (pHZO 640 torr). The data of Fig. 7.4 are shown for both (111) and (100) silicon. This orientation-dependence effect will be considered in Section 7.1.4.2. Mathematical relations, describing the behavior of these rate constants, are given in Table 7. 1 at the end of this chapter. Insight into the physical processes involved during the thermal oxidation of silicon can be gleaned by study of these figures. Thus, Fig. 7.4 shows that the logarithm of the linear rate constant falls inversely with T at a slope of 2 eV/molecule for dry oxygen, and 2.05 eV/molecule for wet oxidation. This is in close agreement with the energy required to break Si-Si bonds, which is 1.83 eV/molecule. The logarithm of the parabolic rate constant (Fig. 7.5) also falls inversely with T, but at a slope of 1.23 eV/molecule for dry oxidation. The comparable activation energy for diffusion of oxygen in fused silica is about 1.18 eV/molecule, as shown in Fig. 7.1. The corresponding value for wet oxidation is 0.78 eV/molecule, which compares favorably with the activation energy of diffusion of H 2 0 in fused silica (0.79 eV/molecule). To an approximation, the linear rate constant varies directly with the concentration of oxidizing species at the surface, and thus with its partial pressure. This has been experimentally verified for both wet and dry oxidation conditions. Finally, the parabolic rate constant for wet oxidation is found to be much larger than that for dry oxidation. This is primarily due to the significantly greater solid solubility of water over oxygen in silica glass (about 3 decades larger), which more than compensates for the slightly lower diffusivity as seen in Fig. 7.1.

Temperature 10001T (K-' )

Fig. 7.4 Linear rate constant versus temperature. From Deal [S]. Reprinted with permission of the publisher, The Electrochemical Society, Inc.

Temperature 1000IT (K-' )

Fig. 7.5 Parabolic rate constant versus temperature. From Deal [S]. Reprinted with permission of the publisher, The Electrochemical Society, Inc.

! ,

'

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7.1.4.1

Initial Growth Phase

The theory for the kinetics of oxide formation has been found to apply very well to growth in wet oxygen and steam. There is consistent evidence, however, to indicate the presence of an extremely rapid initial growth phase with dry oxygen, generally existing for the first 250 A of growth. Considerable effort has been made to explain this rapid growth behavior, since oxides of this type and thickness are critically important for use as gate insulators in MOS devices. A number of theories have been proposed and are briefly summarized here. One set of theories postulates the movement of charge species through the oxide. For example, it has been proposed [lo] that the molecular oxygen, on entering the oxide, dissociates to form a negative-charged 0; or 0,"-,and one o r two holes respectively. The holes have considerably higher mobility than the oxygen ion, and run ahead of it; the result is the formation of a space-charge . region. The resulting field enhances the diffusion of t h e oxygen in the layer, by providing an additional drift component. This enhancement occurs until the oxide thickness exceeds the thickness of the space charge region. This region of high space-charge density is near the gas-oxide interface, with the rest of tlie oxide layer being almost space-charge neutral. Its thickness region is thus on the order of the extrinsic Debye length, and is given by

defect density is some four orders of magnitude larger than that obtained with ~ , dry oxygen (lo2' cm-3 as compared to 1016 ~ m - respectively). Yet another argument is that the basic assumption of Henry's law, as given by Eq. (7.9), only holds for infinitely thick layers, and that the solubility of oxygen in Si02 is greatly increased when the oxide thickness is less than the mean spacing between solute molecules. A third set of theories postulate a two-stream oxidation process, with enhanced growth resulting from the presence of a thin region of material in which excess sites for oxidation are present [12]. Using this model, the experimental data were fitted to the theory by modifying Eq. (7.12) to the form

where E is the relative permittivity of the oxide ( ~ 3 . 9 ) This Debye length is . about 150 A in dry oxygen, but only 5 A for water vapor." In practice, an accelerated oxidation rate is seen for a depth of about 230 f 30 A in dry oxygen processing, but is unnoticed for wet oxygen or steam processing. Equation (7.17) can be rewritten as

where L is a characteristic length, of value 70 f 10 A, for growth in the 800-1000C range. The pre-exponential term C has an Arrhenious type of temperature dependence, with an activation energy of 2.37 and 2.32 eV/molecule for growth on lightly doped (100) and (111) silicon respectively. Dissolved oxygen, due to indiffusion in the very early phase of growth, is yet another possible candidate for the formation of a thin region of rapid oxide ~ growth [13]. The diffusivity of oxygen in silicon is 2 . 8 lo5 A2/s at 1000C, so that indiffusion to a 50-A depth can occur within the first 10 ms of exposure of bare silicon to oxygen. However, its extent falls off with oxide growth because of a rapid reduction in this surface concentration as oxidation proceeds.
7.1.4.2

Doping Dependence Effects

in order to include this rapid oxidation phase. Here, T is a time displacement which can be used to adjust the initial oxide layer (at t = 0). A second set of theories, based on the structure of the oxide during the initial growth phase, have also been proposed [ll]. Transmission electron microscope studies of silica structure have shown the presence of pores, about 10 A in diameter, in very thin oxides grown in dry oxygen. These allow the oxidant to remain in direct contact with the silicon in the early phases of growth. Such pores have not been observed in wet oxides, presumably because their
*This is because the solid solubility of water in silica is three orders of magnitude larger than that of oxygen.

Heavily doped silicon oxidizes at a faster rate than lightly doped material. However, detailed studies of boron- and phosphorus-doped material have shown considerable differences in oxide growth behavior. Thus, during oxidation, boron is preferentially incorporated into the silicon dioxide because of its relatively small segregation coefficient* (= 0.15 to 0.3). This results in a weakening of the bond structure of the silica film, and an increase in the diffusivity of the oxidizing species through it. Consequently, there is an increase in the parabolic rate constant with boron doping concentration, but little change in the linear rate constant [14]. Phosphorus, on the other hand, has a large segregation coefficient (=lo), is only slightly incorporated into the growing oxide, and piles up at the Si-Si02 interface. This causes an increase in the reaction rate, with a corresponding increase in the linear rate constant. On the other hand, the lack of phosphorus
*Defined as the ratio of the equilibrium concentration of the impurity in silicon to its equilibrium concentration in the oxide. See Section 4.8.1.