**2. Kinetics and thermodynamics of g-SiN formation on the Si (111) surface**

#### **2.1 Formation kinetics of silicon nitride**

The Si3N4 film formed on the silicon surface as a rule is amorphous [14–18]. However, at the initial stage of this process, the (8 × 8) structure is formed. The structure (8 × 8) was first discovered by van Bommel and Meyer in 1967 [19]. This structure has been actively studied later. "Modifications" of this structure such as (11/8 × 11/8) and (3/8 × 3/8) have been discovered and described. Models explaining the appearance of (8 × 8) structure by forming a layer of crystalline silicon nitride β-Si3N4 are dominating in the literature [20–24].

In our experiments, the nitridation of the silicon surface is started by the onset of ammonia flux onto the clean Si (111) substrate heated to temperatures above 750°C [25]. Two different stages of the silicon nitridation were distinguished by reflection high energy electron diffraction (RHEED): the first stage is a fast formation of the (8 × 8) structure and the following stage is a slow formation of amorphous Si3N4 phase. The ordered (8 × 8) structure appears within a few seconds under ammonia flux for the all used temperatures. RHEED pattern of (8 × 8) obtained after exposure of the surface during 6 s under ammonia flux FNH3 = 10 sccm at a temperature T = 1050°C is shown in **Figure 1a**. The following bright diffraction spots corresponding to the (8 × 8) structure are clearly observed (**Figure 1a**): (0 -3/8), (0 -5/8), (0 -6/8), (0 -11/8), as well as weaker reflections of (0 -1/8), (0 -2/8), and (0 -7/8) along with the fundamental reflexes (0 0), (0 1), and (0 1) of the Si (111) surface. However, the diffraction spots such as (0 ± 4/8) or (±4/8 ± 4/8) related to the fundamental periodicity of the crystalline phase of β-Si3N4 were not observed. This experimental fact indicates that the structure (8 × 8) does not correspond to the β-Si3N4 phase, in contrast to the dominating interpretation of nature of the structure (8 × 8) [20–24].

Further nitridation at the same conditions (the second stage) results in silicon nitride amorphous phase (a-Si3N4) formation that was accompanied by the total disappearance of all diffraction spots in the RHEED pattern within several minutes. The behavior of intensities of the fractional (0 3/8) diffraction spot as a function of time (i.e., kinetic curves) at different substrate temperatures is shown in **Figure 1b**. **Figure 1b** clearly demonstrates the fast rise of the fractional (0 3/8) spot intensity (the first fast stage) and its further decay of the diffraction spot (the second slow stage). The thickness of a-Si3N4 in our experiments was about 5–30 Å, depending on the duration of nitridation. These data do not confirm the possibility of epitaxial growth of crystalline β-Si3N4 layers, as was supposed in works [22, 23]. We revealed that the diffraction spot intensity decay as function of time is well described by the exponential law *I(t) = I0(*T*) × exp(−k2(*T*)*⋅*t)* at all investigated temperatures T,

**33**

factor of 107

**Figure 1.**

–108

activation barrier [26].

played by mobile silicon adatoms (Si<sup>a</sup>

1/s is found.

*taken at T = 1050°C (gray, solid) by the exponential function (red, dash).*

*Van der Waals and Graphene-Like Layers of Silicon Nitride and Aluminum Nitride*

where *k2* is the rate constant and *t* denotes time, and so this process corresponds to a first-order reaction. As an example, the inset in **Figure 1b** shows approximation of the experimental curve by the exponential law at T = 1050°C. The activation energy of the amorphous silicon nitride phase formation of 2.4 eV and pre-exponential

*(a) RHEED pattern of the structure (8 × 8) appeared on the Si (111) substrate after its exposure to 10 sccm ammonia flux for 6 s at temperature of 1050°C; (b) the behavior of fractional (0 3/8) spot intensities at different substrate temperatures, from [25]. The inset* **Figure 1b** *shows approximation of the kinetic curve* 

**Figure 2a** shows the normalized kinetic curves for the formation of the (8 × 8) structure, measured by the intensity evolution of the (0 3/8) spot. The figure clearly shows that there is a slight decrease in the rate of formation of the structure (8 × 8) with increasing temperature, which indicates the absence of an activation barrier in this process in contrast to a-Si3N4 formation. This fact also does not agree with the formation of a crystalline β-Si3N4 layer, which requires the overcoming of a large

As shown in work [25], at the formation of the structure (8 × 8), the main role is

the silicon crystal at a given temperature, and the heat of the mobile adatoms formation is 1.7 eV. The existence of mobile adatoms is well known, for example, in the

), which are in equilibrium with the surface of

*DOI: http://dx.doi.org/10.5772/intechopen.81775*

*Van der Waals and Graphene-Like Layers of Silicon Nitride and Aluminum Nitride DOI: http://dx.doi.org/10.5772/intechopen.81775*

#### **Figure 1.**

*2D Materials*

**surface**

**2.1 Formation kinetics of silicon nitride**

nitride β-Si3N4 are dominating in the literature [20–24].

Dielectric materials that provide insulation of conductive channels are also necessary for the development of electronic devices. Hexagonal-BN (h-BN), one of the 2D dielectric materials [11, 12], attracts grate attention. However, the fabrication of large area h-BN layers is difficult. AlN is another alternative dielectric material that can be grown epitaxially on large areas. It is also predicted [13] that silicene is stable when encapsulating between two thin graphite-like hexagonal AlN layers. This is especially important, since until now silicene growth has been presented only on metal substrates, which makes it unsuitable for electronic devices. In this chapter, the synthesis and properties of the graphene-like materials and van der Waals layers

of silicon nitride (g-SiN) and aluminum nitride (g-AlN) are reported.

**2. Kinetics and thermodynamics of g-SiN formation on the Si (111)** 

The Si3N4 film formed on the silicon surface as a rule is amorphous [14–18]. However, at the initial stage of this process, the (8 × 8) structure is formed. The structure (8 × 8) was first discovered by van Bommel and Meyer in 1967 [19]. This structure has been actively studied later. "Modifications" of this structure such as (11/8 × 11/8) and (3/8 × 3/8) have been discovered and described. Models explaining the appearance of (8 × 8) structure by forming a layer of crystalline silicon

In our experiments, the nitridation of the silicon surface is started by the onset of ammonia flux onto the clean Si (111) substrate heated to temperatures above 750°C [25]. Two different stages of the silicon nitridation were distinguished by reflection high energy electron diffraction (RHEED): the first stage is a fast formation of the (8 × 8) structure and the following stage is a slow formation of amorphous Si3N4 phase. The ordered (8 × 8) structure appears within a few seconds under ammonia flux for the all used temperatures. RHEED pattern of (8 × 8) obtained after exposure of the surface during 6 s under ammonia flux FNH3 = 10 sccm at a temperature T = 1050°C is shown in **Figure 1a**. The following bright diffraction spots corresponding to the (8 × 8) structure are clearly observed (**Figure 1a**): (0 -3/8), (0 -5/8), (0 -6/8), (0 -11/8), as well as weaker reflections of (0 -1/8), (0 -2/8), and (0 -7/8) along with the fundamental reflexes (0 0), (0 1), and (0 1) of the Si (111) surface. However, the diffraction spots such as (0 ± 4/8) or (±4/8 ± 4/8) related to the fundamental periodicity of the crystalline phase of β-Si3N4 were not observed. This experimental fact indicates that the structure (8 × 8) does not correspond to the β-Si3N4 phase, in contrast to the dominating interpretation of nature of the structure

Further nitridation at the same conditions (the second stage) results in silicon nitride amorphous phase (a-Si3N4) formation that was accompanied by the total disappearance of all diffraction spots in the RHEED pattern within several minutes. The behavior of intensities of the fractional (0 3/8) diffraction spot as a function of time (i.e., kinetic curves) at different substrate temperatures is shown in **Figure 1b**. **Figure 1b** clearly demonstrates the fast rise of the fractional (0 3/8) spot intensity (the first fast stage) and its further decay of the diffraction spot (the second slow stage). The thickness of a-Si3N4 in our experiments was about 5–30 Å, depending on the duration of nitridation. These data do not confirm the possibility of epitaxial growth of crystalline β-Si3N4 layers, as was supposed in works [22, 23]. We revealed that the diffraction spot intensity decay as function of time is well described by the exponential law *I(t) = I0(*T*) × exp(−k2(*T*)*⋅*t)* at all investigated temperatures T,

**32**

(8 × 8) [20–24].

*(a) RHEED pattern of the structure (8 × 8) appeared on the Si (111) substrate after its exposure to 10 sccm ammonia flux for 6 s at temperature of 1050°C; (b) the behavior of fractional (0 3/8) spot intensities at different substrate temperatures, from [25]. The inset* **Figure 1b** *shows approximation of the kinetic curve taken at T = 1050°C (gray, solid) by the exponential function (red, dash).*

where *k2* is the rate constant and *t* denotes time, and so this process corresponds to a first-order reaction. As an example, the inset in **Figure 1b** shows approximation of the experimental curve by the exponential law at T = 1050°C. The activation energy of the amorphous silicon nitride phase formation of 2.4 eV and pre-exponential factor of 107 –108 1/s is found.

**Figure 2a** shows the normalized kinetic curves for the formation of the (8 × 8) structure, measured by the intensity evolution of the (0 3/8) spot. The figure clearly shows that there is a slight decrease in the rate of formation of the structure (8 × 8) with increasing temperature, which indicates the absence of an activation barrier in this process in contrast to a-Si3N4 formation. This fact also does not agree with the formation of a crystalline β-Si3N4 layer, which requires the overcoming of a large activation barrier [26].

As shown in work [25], at the formation of the structure (8 × 8), the main role is played by mobile silicon adatoms (Si<sup>a</sup> ), which are in equilibrium with the surface of the silicon crystal at a given temperature, and the heat of the mobile adatoms formation is 1.7 eV. The existence of mobile adatoms is well known, for example, in the

#### **Figure 2.**

*(a) Evolution of the intensity of the (0 3/8) spot during the formation of the (8 × 8) structure at different temperatures: 1. 900°*С*, 2. 1000°*С*, 3. 1050°*С*, 4. 1150°*С*; (b) kinetic curves of thermal decomposition of the structure (8 × 8): 1. 980°*С*, 2. 1005°*С*, 3. 1030°*С*, 4. 1040°*С*, 5. 1055°*С*. All curves are normalized to their own maximum intensity. The inset* **Figure 2a** *demonstrates energy diagrams: the solid curve corresponds to formation and decomposition of the structure (8 × 8) and the dashed-dotted curve corresponds to formation of amorphous Si3N4.*

temperature range of about 1000°C, and mobile silicon adatoms provide movement of steps on the surface, the formation and/or disappearance of two-dimensional islands, and participate in oxidation processes and other surface reactions [27–29]. Since the rate of formation of the structure (8 × 8) is high during the nitridation process, then the equilibrium concentration of mobile adatoms Si<sup>a</sup> does not have time to be established and the coverage of the surface by the two-dimensional phase (8 × 8) is determined by the initial concentration of mobile silicon adatoms at the Si surface at a given temperature. In diffraction, this is manifested in the temperature dependence of the maximum intensity *I0(*T*)*. It should be emphasized one more time that the formation of the structure (8 × 8) originates from interaction of ammonia with the mobile silicon adatoms rather than the dangling bonds of silicon atoms incorporated in lattice site (i.e., immobile) on the Si (111) surface.

#### **2.2 Thermal decomposition of a two-dimensional layer (8 × 8)**

We investigated the stability of the phase (8 × 8) by studying the kinetics of thermal decomposition of the structure (8 × 8) under ultrahigh vacuum conditions for the temperature range 980–1055°С using the RHEED spots intensity evolution. When the sample was held for several minutes at a fixed temperature, the fractional

**35**

**Figure 3.**

106

(107

*Van der Waals and Graphene-Like Layers of Silicon Nitride and Aluminum Nitride*

sition rate of the structure (8 × 8), and T is the surface temperature.

of the (8 × 8) structure formation estimated here.

*Arrhenius dependence of the rate constant of the (8 × 8) decomposition.*

processes differ by a factor of 106

diffraction spots of the structure (8 × 8) were faded away and the (1 × 1) pattern of the clean silicon surface was restored. **Figure 2b** shows the normalized kinetic curves of the thermal decomposition of the structure (8 × 8) at different temperatures. Analysis of these curves showed that the rate of thermal decomposition increases with increasing temperature, that is, the (8 × 8) structure decomposition is a normal activation process. Curves are well described by a decreasing exponential law *I(t) = I0 exp(−k(*T*)/t)*, where *t* is the time, *k* is the constant of the decompo-

The thermal decomposition constant *k* as function of temperature is presented in the Arrhenius coordinates in **Figure 3**. The activation energy (Ea) of the structure (8 × 8) thermal decomposition, Ea = 4.03 eV, and the pre-exponential factor, k0 = 2.4 × 1013 1/s, are found. The value of Ea is close to the known binding energy of Si-N bond in Si3N4—4.5 eV [30]. Since the activation energy of the decomposition cannot be less than the heat of formation (that is, Ea ≥ ΔH), then the heat of formation of the structure (8 × 8) ΔH is no more than 4 eV. The inset of **Figure 2a** schematically illustrates the relationship between the heat of formation and the activation energy of the thermal decomposition of the structure (8 × 8), as well as it shows the energy diagram of the Si3N4 amorphous phase formation. The heat of formation of bulk β-Si3N4 is about 8 eV [26, 31], which is much larger than the heat

The decomposition rate of the β-Si3N4 crystalline phase surface, which was studied in the work [31], is much slower in comparison with the decomposition of the structure (8 × 8), for example, at a temperature of 1740°C, the surface decomposition process took more than an hour. In our case, at a much lower temperature, T = 1055°C, the complete decay of the structure (8 × 8) takes about a minute, which confirms the lower thermal stability of the structure (8 × 8) in comparison with the β-Si3N4 crystal. The activation energy of the decomposition of the structure (8 × 8) measured here coincides with the activation energy of the surface thermal decomposition of β-Si3N4 (93 kcal/mol), but the pre-exponential factor (2.4 × 1013 1/s) is

times higher than the pre-exponential factor of β-Si3N4 surface decomposition

 1/s) [31]. The coincidence of activation energies shows that in both cases, the limiting stage of the processes is the breaking of the Si-N bonds but the rates of the

has a normal value of ~1013 1/s, which implies a simple decomposition mechanism.

. We note that the measured pre-exponential factor

*DOI: http://dx.doi.org/10.5772/intechopen.81775*

*Van der Waals and Graphene-Like Layers of Silicon Nitride and Aluminum Nitride DOI: http://dx.doi.org/10.5772/intechopen.81775*

diffraction spots of the structure (8 × 8) were faded away and the (1 × 1) pattern of the clean silicon surface was restored. **Figure 2b** shows the normalized kinetic curves of the thermal decomposition of the structure (8 × 8) at different temperatures. Analysis of these curves showed that the rate of thermal decomposition increases with increasing temperature, that is, the (8 × 8) structure decomposition is a normal activation process. Curves are well described by a decreasing exponential law *I(t) = I0 exp(−k(*T*)/t)*, where *t* is the time, *k* is the constant of the decomposition rate of the structure (8 × 8), and T is the surface temperature.

The thermal decomposition constant *k* as function of temperature is presented in the Arrhenius coordinates in **Figure 3**. The activation energy (Ea) of the structure (8 × 8) thermal decomposition, Ea = 4.03 eV, and the pre-exponential factor, k0 = 2.4 × 1013 1/s, are found. The value of Ea is close to the known binding energy of Si-N bond in Si3N4—4.5 eV [30]. Since the activation energy of the decomposition cannot be less than the heat of formation (that is, Ea ≥ ΔH), then the heat of formation of the structure (8 × 8) ΔH is no more than 4 eV. The inset of **Figure 2a** schematically illustrates the relationship between the heat of formation and the activation energy of the thermal decomposition of the structure (8 × 8), as well as it shows the energy diagram of the Si3N4 amorphous phase formation. The heat of formation of bulk β-Si3N4 is about 8 eV [26, 31], which is much larger than the heat of the (8 × 8) structure formation estimated here.

The decomposition rate of the β-Si3N4 crystalline phase surface, which was studied in the work [31], is much slower in comparison with the decomposition of the structure (8 × 8), for example, at a temperature of 1740°C, the surface decomposition process took more than an hour. In our case, at a much lower temperature, T = 1055°C, the complete decay of the structure (8 × 8) takes about a minute, which confirms the lower thermal stability of the structure (8 × 8) in comparison with the β-Si3N4 crystal. The activation energy of the decomposition of the structure (8 × 8) measured here coincides with the activation energy of the surface thermal decomposition of β-Si3N4 (93 kcal/mol), but the pre-exponential factor (2.4 × 1013 1/s) is 106 times higher than the pre-exponential factor of β-Si3N4 surface decomposition (107 1/s) [31]. The coincidence of activation energies shows that in both cases, the limiting stage of the processes is the breaking of the Si-N bonds but the rates of the processes differ by a factor of 106 . We note that the measured pre-exponential factor has a normal value of ~1013 1/s, which implies a simple decomposition mechanism.

**Figure 3.** *Arrhenius dependence of the rate constant of the (8 × 8) decomposition.*

*2D Materials*

**34**

**Figure 2.**

*amorphous Si3N4.*

temperature range of about 1000°C, and mobile silicon adatoms provide movement of steps on the surface, the formation and/or disappearance of two-dimensional islands, and participate in oxidation processes and other surface reactions [27–29]. Since the rate of formation of the structure (8 × 8) is high during the nitridation

*(a) Evolution of the intensity of the (0 3/8) spot during the formation of the (8 × 8) structure at different temperatures: 1. 900°*С*, 2. 1000°*С*, 3. 1050°*С*, 4. 1150°*С*; (b) kinetic curves of thermal decomposition of the structure (8 × 8): 1. 980°*С*, 2. 1005°*С*, 3. 1030°*С*, 4. 1040°*С*, 5. 1055°*С*. All curves are normalized to their own maximum intensity. The inset* **Figure 2a** *demonstrates energy diagrams: the solid curve corresponds to formation and decomposition of the structure (8 × 8) and the dashed-dotted curve corresponds to formation of* 

time to be established and the coverage of the surface by the two-dimensional phase (8 × 8) is determined by the initial concentration of mobile silicon adatoms at the Si surface at a given temperature. In diffraction, this is manifested in the temperature dependence of the maximum intensity *I0(*T*)*. It should be emphasized one more time that the formation of the structure (8 × 8) originates from interaction of ammonia with the mobile silicon adatoms rather than the dangling bonds of silicon

We investigated the stability of the phase (8 × 8) by studying the kinetics of thermal decomposition of the structure (8 × 8) under ultrahigh vacuum conditions for the temperature range 980–1055°С using the RHEED spots intensity evolution. When the sample was held for several minutes at a fixed temperature, the fractional

does not have

process, then the equilibrium concentration of mobile adatoms Si<sup>a</sup>

atoms incorporated in lattice site (i.e., immobile) on the Si (111) surface.

**2.2 Thermal decomposition of a two-dimensional layer (8 × 8)**

When the Si-N bonds break, the formation of activated N\* nitrogen atoms weakly bound to the surface and following formation of N2 (N\* + N\* = N2) molecules occurs. Thus, the structure (8 × 8) at a temperature above 980°C is destroyed, both during exposure to vacuum and during the continuation of nitridation process under ammonia flux, when it is converted to amorphous Si3N4. Indeed, at lower temperatures, the structure (8 × 8) is stable. Therefore, the experimental data on the transformation into an amorphous phase and thermal decomposition evidence the metastability of the phase (8 × 8), in contrast to the stable crystalline phase of β-Si3N4 or the amorphous phase of Si3N4.
