**3.1 STM of the Si (111)-(7 × 7) and impact of NH3 adsorption**

The atomic structure of the pristine surface (7 × 7) and the surface with chemisorbed ammonia on Si (111) (obtained at 750°C, 4 min, PNH3 = 10<sup>−</sup><sup>7</sup> Torr) were investigated in real space by the scanning tunneling microscopy (STM) method. STM images of these surfaces are presented in **Figure 4a** and **b** (at operating parameters V = +1 V and I = 0.025 nA). The images were obtained in empty electronic states of silicon. Comparing images a and b in **Figure 4**, we can conclude that ammonia is adsorbed mainly to the central adatoms and rest atoms of the structure (7 × 7). In **Figure 4b**, it is also clearly seen that the chemisorption of ammonia induces a disorder on the surface. We consider chemisorption of ammonia as the initial process of nitridation at the silicon surface, followed by the formation of an amorphous nitride phase, since the interaction of ammonia with the dangling bonds of surface silicon atoms (111) does not change the sp3 hybridization of the orbitals of these atoms. We recall that in the amorphous phase of Si3N4, silicon atoms also have sp3 hybridization of orbitals.

### **3.2 STS of the Si (111)-(7 × 7) and impact of NH3 adsorption**

We performed measurements of the scanning tunneling spectroscopy (STS) of a clean surface (7 × 7) and on a surface with chemisorbed ammonia (**Figure 4c**). The spectra of pristine silicon surface for various characteristic points, such as corner adatoms, central adatoms, rest atoms, and hole atoms, on the Si (111)-(7 × 7) surface are shown. Each curve for a particular characteristic point is obtained by summing 30–40 volt-ampere curves at equivalent characteristic points on the STM image. One can see a good coincidence of the STS spectra for all these characteristic points on a clean silicon surface. Peaks in the density of states for bias voltages of −0.3, −0.8, −1.5, and −2.3 V, as well as peaks for empty states +0.3 V and +0.8 V, are observed. Similar peaks were observed by many groups [21, 24, 32–37], and they are usually denoted as S1 = −0.3 eV, S2 = −0.8 eV, and S3 = −1.4 eV; we also observed a state at −2.3 eV, which was detected by the XPS method [38]. Some authors associate certain peaks in the density of state spectrum with specific atoms on the surface (7 × 7), for example, peaks at −0.3 and + 0.3 V are associated with adatoms [21, 32], and the peak at −0.8 V is associated with rest atoms [32, 37], that is, they are considered in the framework of the approximation of the local density of electronic states of a given atom. However, our experimental data, namely the presence of identical peaks for the entire family of spectra, for both adatoms and rest atoms and other characteristic points, show that these peaks on the surface of pure silicon should be considered as a manifestation of the surface two-dimensional bands of

**37**

**Figure 4.**

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

states of the structure (7 × 7). Measurements of the STS on the surface with chemisorbed ammonia show different spectra for the same family of the characteristic points. The more pronounced difference in the spectra is observed for corner and central Si adatoms, which was also manifested in STM images, as indicated above. In this case, a stronger local chemical interaction of ammonia with the central adatoms than with the corner adatoms occurs. The surface band structure of the clean surface (7 × 7) is destroyed. Essentially, when random Si-N chemical bonds

*STM images: (a) the clean surface of Si (111) with reconstruction (7 × 7); (b) the surface of silicon (111) treated with ammonia. The lines indicate the nearest equivalent points. (c) STS spectra of a clean surface of Si (7 × 7) (family of curves 1–4) and spectra after adsorption of ammonia (family of curves 5–8). Curves 1, 5.* 

*correspond to corner adatoms; 2, 6. to central adatoms; 3, 7. rest atoms; 4, 8. "corner holes".*

Interaction of ammonia with the (111) silicon surface at elevated temperatures (800–1150°С) results to (8 × 8) structure, as discussed above, in contrast to disordered structure appeared during adsorption of ammonia at lower temperatures. A typical STM image of the structure (8 × 8) at the working offset Vs = −3 V is shown in **Figure 5a**, that is, the image in the filled states of the sample. The periodic structure (8/3 × 8/3) with a distance between the nearest neighboring protrusions *a* = 10.2 Å clearly manifests itself in the figure, in agreement with numerous experimental data, see, for example [22, 23, 39]. In addition, in **Figure 5a**, a honeycomb structure is clearly observed, with a hexagon whose side *b* is approximately 6 Å in

are formed, various localized electronic states appear.

**3.3 STM/STS of the structure (8 × 8)**

*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 4.**

*2D Materials*

**the Si (111)**

have sp3

β-Si3N4 or the amorphous phase of Si3N4.

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

**3. Comparative STM/STS study of the (7 × 7) and (8 × 8) structures on** 

The atomic structure of the pristine surface (7 × 7) and the surface with che-

investigated in real space by the scanning tunneling microscopy (STM) method. STM images of these surfaces are presented in **Figure 4a** and **b** (at operating parameters V = +1 V and I = 0.025 nA). The images were obtained in empty electronic states of silicon. Comparing images a and b in **Figure 4**, we can conclude that ammonia is adsorbed mainly to the central adatoms and rest atoms of the structure (7 × 7). In **Figure 4b**, it is also clearly seen that the chemisorption of ammonia induces a disorder on the surface. We consider chemisorption of ammonia as the initial process of nitridation at the silicon surface, followed by the formation of an amorphous nitride phase, since the interaction of ammonia with the dangling bonds

of these atoms. We recall that in the amorphous phase of Si3N4, silicon atoms also

We performed measurements of the scanning tunneling spectroscopy (STS) of a clean surface (7 × 7) and on a surface with chemisorbed ammonia (**Figure 4c**). The spectra of pristine silicon surface for various characteristic points, such as corner adatoms, central adatoms, rest atoms, and hole atoms, on the Si (111)-(7 × 7) surface are shown. Each curve for a particular characteristic point is obtained by summing 30–40 volt-ampere curves at equivalent characteristic points on the STM image. One can see a good coincidence of the STS spectra for all these characteristic points on a clean silicon surface. Peaks in the density of states for bias voltages of −0.3, −0.8, −1.5, and −2.3 V, as well as peaks for empty states +0.3 V and +0.8 V, are observed. Similar peaks were observed by many groups [21, 24, 32–37], and they are usually denoted as S1 = −0.3 eV, S2 = −0.8 eV, and S3 = −1.4 eV; we also observed a state at −2.3 eV, which was detected by the XPS method [38]. Some authors associate certain peaks in the density of state spectrum with specific atoms on the surface (7 × 7), for example, peaks at −0.3 and + 0.3 V are associated with adatoms [21, 32], and the peak at −0.8 V is associated with rest atoms [32, 37], that is, they are considered in the framework of the approximation of the local density of electronic states of a given atom. However, our experimental data, namely the presence of identical peaks for the entire family of spectra, for both adatoms and rest atoms and other characteristic points, show that these peaks on the surface of pure silicon should be considered as a manifestation of the surface two-dimensional bands of

Torr) were

hybridization of the orbitals

**3.1 STM of the Si (111)-(7 × 7) and impact of NH3 adsorption**

of surface silicon atoms (111) does not change the sp3

**3.2 STS of the Si (111)-(7 × 7) and impact of NH3 adsorption**

hybridization of orbitals.

misorbed ammonia on Si (111) (obtained at 750°C, 4 min, PNH3 = 10<sup>−</sup><sup>7</sup>

**36**

*STM images: (a) the clean surface of Si (111) with reconstruction (7 × 7); (b) the surface of silicon (111) treated with ammonia. The lines indicate the nearest equivalent points. (c) STS spectra of a clean surface of Si (7 × 7) (family of curves 1–4) and spectra after adsorption of ammonia (family of curves 5–8). Curves 1, 5. correspond to corner adatoms; 2, 6. to central adatoms; 3, 7. rest atoms; 4, 8. "corner holes".*

states of the structure (7 × 7). Measurements of the STS on the surface with chemisorbed ammonia show different spectra for the same family of the characteristic points. The more pronounced difference in the spectra is observed for corner and central Si adatoms, which was also manifested in STM images, as indicated above. In this case, a stronger local chemical interaction of ammonia with the central adatoms than with the corner adatoms occurs. The surface band structure of the clean surface (7 × 7) is destroyed. Essentially, when random Si-N chemical bonds are formed, various localized electronic states appear.

#### **3.3 STM/STS of the structure (8 × 8)**

Interaction of ammonia with the (111) silicon surface at elevated temperatures (800–1150°С) results to (8 × 8) structure, as discussed above, in contrast to disordered structure appeared during adsorption of ammonia at lower temperatures. A typical STM image of the structure (8 × 8) at the working offset Vs = −3 V is shown in **Figure 5a**, that is, the image in the filled states of the sample. The periodic structure (8/3 × 8/3) with a distance between the nearest neighboring protrusions *a* = 10.2 Å clearly manifests itself in the figure, in agreement with numerous experimental data, see, for example [22, 23, 39]. In addition, in **Figure 5a**, a honeycomb structure is clearly observed, with a hexagon whose side *b* is approximately 6 Å in

#### **Figure 5.**

*(a) STM image of the structure (8 × 8). The white figures are marking elementary cells (8/3 × 8/3) and hexagons; (b) STS spectra measured for three characteristic points: 1. protrusion, 2. the vertices of hexagon that not occupied by protrusion, 3. center of hexagon (corresponding three characteristic points are marked in*  **Figure 5a***).*

length and rotated at 30° relative to the unit cell of (8/3 × 8/3). **Figure 5b** clearly shows that the protrusions of the phase (8/3 × 8/3) are brighter than the "vertices" and "sides" of the hexagons. Consequently, the protrusions (8/3 × 8/3) lie on top of the honeycomb structure. In our opinion, protrusions correspond to an ordered adsorption phase, which occupy only three of the six vertices of the hexagons. The relationship between the side length of a hexagon and the distance between protrusions is defined by the expression *a* = 2 × *b* × cos(30°). It is clear that the periodicities of adsorption phase and hexagons are the same. There are vacancies in the adsorption phase. This confirms the high mobility of atoms in the adsorption phase, which was noted in the work [24]. At present, it is difficult to unequivocally indicate the nature of the protrusions, perhaps they consist of one, two, or several silicon atoms [40, 41]. For the current study, the hexagonal structure is most interesting, since it determines an atomic arrangement in the structure (8 × 8).

The authors of the work [24] also have observed a honeycomb structure and have explained it by the manifestation of the crystal structure of β-Si3N4. The size of the hexagon side in the STM images represented by the authors (see **Figure 5a** and **b** in the article [24]), as well as in our case, was about 6 Å. Let us recall that in the crystal structure of β-Si3N4, there is a characteristic fragment—a "small" hexagon with a side of 2.75 Å, as shown experimentally, for example, in work [42] with the help of highresolution TEM. The hexagonal periodic structure with lattice constant of 7.62 Å of the β-Si3N4 is constructed of these "small" hexagons, but there are no hexagons with

**39**

**Figure 6.**

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

the 6 Å side in the structure. Consequently, the honeycomb structure detected in this work and in the work [24] does not correspond to the structure of the β-Si3N4 crystal. It seems that in most studies devoted to STM of the (8 × 8) structure, only the adsorption phase (8/3 × 8/3) was clearly observed because usually the ordering of the structure is not very high due to the mobility of adatoms (see [21, 24]); hence, the 6 Å honeycomb structure did not be taken into account until now at the model-

**Figure 5b** shows the STS spectra measured for three different characteristic points: 1. the protrusions, 2. the vertices of the hexagons that not occupied by the protrusions, and 3. the centers of the hexagons. Each curve is obtained by averaging of 30–40 equivalent points. There is a good coincidence of the curves for various characteristic points, as might be expected for a periodic structure. In our opinion, the position of the peak in the density of states at −1.1 eV corresponds to the maximum of the valence band for the surface periodic structure (8 × 8). The band gap of the structure (8 × 8) is about 2.2 eV, and it is determined by the energy gap between the bonding π and antibonding π\* orbitals (as discussed below). The band gap of 2.2 eV is much less than the band gap of crystalline β-Si3N4 or amorphous Si3N4 (4.9–5.3 eV). For comparison, **Figure 6** shows the spectra of a pristine silicon surface with (7 × 7) reconstruction (curve 1), the structure (8 × 8) (curve 2), and a thin amorphous Si3N4 layer (curve 3). The STS spectrum of the amorphous phase of Si3N4 has a characteristic peak at energy of about −4 eV, which is observed by many groups [21, 24, 43–45]. The authors of [21, 43] refer it to adsorbed nitrogen atoms on the surface, but since this peak exists in thick crystalline β-Si3N4 and amorphous Si3N4 layers, as demonstrated in works [24, 44, 45], this peak corresponds to the valence-band maximum of bulk Si3N4; by the other words, it is the highest occupied

The peak at −1.1 eV of the structure (8 × 8) (curve 2) corresponds to the π orbitals, since it has the highest energy among the occupied electron states HOMO and this peak is much higher than peak of σ bonding band (−4 eV) [46]; moreover, this peak is absent in the spectrum of amorphous Si3N4. The peak at −1.1 eV was also observed by the method of photoelectron spectroscopy (PES) in [47]. However, the authors attributed it to the dangling silicon or nitrogen bonds of β-Si3N4 phase within the framework of the generally accepted concept of the (8 × 8) structure description as a β-Si3N4 crystal. However, in **Figure 5** of the work [47],

*Scanning tunneling spectra: 1. of the clean silicon surface of Si (111) with reconstruction (7 × 7); 2. of the* 

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

molecular orbital (HOMO) of σ bonding band.

*structure (8 × 8); and 3. of the amorphous phase Si3N4.*

ing of (8 × 8) structure.

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

the 6 Å side in the structure. Consequently, the honeycomb structure detected in this work and in the work [24] does not correspond to the structure of the β-Si3N4 crystal. It seems that in most studies devoted to STM of the (8 × 8) structure, only the adsorption phase (8/3 × 8/3) was clearly observed because usually the ordering of the structure is not very high due to the mobility of adatoms (see [21, 24]); hence, the 6 Å honeycomb structure did not be taken into account until now at the modeling of (8 × 8) structure.

**Figure 5b** shows the STS spectra measured for three different characteristic points: 1. the protrusions, 2. the vertices of the hexagons that not occupied by the protrusions, and 3. the centers of the hexagons. Each curve is obtained by averaging of 30–40 equivalent points. There is a good coincidence of the curves for various characteristic points, as might be expected for a periodic structure. In our opinion, the position of the peak in the density of states at −1.1 eV corresponds to the maximum of the valence band for the surface periodic structure (8 × 8). The band gap of the structure (8 × 8) is about 2.2 eV, and it is determined by the energy gap between the bonding π and antibonding π\* orbitals (as discussed below). The band gap of 2.2 eV is much less than the band gap of crystalline β-Si3N4 or amorphous Si3N4 (4.9–5.3 eV). For comparison, **Figure 6** shows the spectra of a pristine silicon surface with (7 × 7) reconstruction (curve 1), the structure (8 × 8) (curve 2), and a thin amorphous Si3N4 layer (curve 3). The STS spectrum of the amorphous phase of Si3N4 has a characteristic peak at energy of about −4 eV, which is observed by many groups [21, 24, 43–45]. The authors of [21, 43] refer it to adsorbed nitrogen atoms on the surface, but since this peak exists in thick crystalline β-Si3N4 and amorphous Si3N4 layers, as demonstrated in works [24, 44, 45], this peak corresponds to the valence-band maximum of bulk Si3N4; by the other words, it is the highest occupied molecular orbital (HOMO) of σ bonding band.

The peak at −1.1 eV of the structure (8 × 8) (curve 2) corresponds to the π orbitals, since it has the highest energy among the occupied electron states HOMO and this peak is much higher than peak of σ bonding band (−4 eV) [46]; moreover, this peak is absent in the spectrum of amorphous Si3N4. The peak at −1.1 eV was also observed by the method of photoelectron spectroscopy (PES) in [47]. However, the authors attributed it to the dangling silicon or nitrogen bonds of β-Si3N4 phase within the framework of the generally accepted concept of the (8 × 8) structure description as a β-Si3N4 crystal. However, in **Figure 5** of the work [47],

#### **Figure 6.**

*Scanning tunneling spectra: 1. of the clean silicon surface of Si (111) with reconstruction (7 × 7); 2. of the structure (8 × 8); and 3. of the amorphous phase Si3N4.*

*2D Materials*

**38**

**Figure 5.**

**Figure 5a***).*

length and rotated at 30° relative to the unit cell of (8/3 × 8/3). **Figure 5b** clearly shows that the protrusions of the phase (8/3 × 8/3) are brighter than the "vertices" and "sides" of the hexagons. Consequently, the protrusions (8/3 × 8/3) lie on top of the honeycomb structure. In our opinion, protrusions correspond to an ordered adsorption phase, which occupy only three of the six vertices of the hexagons. The relationship between the side length of a hexagon and the distance between protrusions is defined by the expression *a* = 2 × *b* × cos(30°). It is clear that the periodicities of adsorption phase and hexagons are the same. There are vacancies in the adsorption phase. This confirms the high mobility of atoms in the adsorption phase, which was noted in the work [24]. At present, it is difficult to unequivocally indicate the nature of the protrusions, perhaps they consist of one, two, or several silicon atoms [40, 41]. For the current study, the hexagonal structure is most interesting,

*(a) STM image of the structure (8 × 8). The white figures are marking elementary cells (8/3 × 8/3) and hexagons; (b) STS spectra measured for three characteristic points: 1. protrusion, 2. the vertices of hexagon that not occupied by protrusion, 3. center of hexagon (corresponding three characteristic points are marked in* 

The authors of the work [24] also have observed a honeycomb structure and have explained it by the manifestation of the crystal structure of β-Si3N4. The size of the hexagon side in the STM images represented by the authors (see **Figure 5a** and **b** in the article [24]), as well as in our case, was about 6 Å. Let us recall that in the crystal structure of β-Si3N4, there is a characteristic fragment—a "small" hexagon with a side of 2.75 Å, as shown experimentally, for example, in work [42] with the help of highresolution TEM. The hexagonal periodic structure with lattice constant of 7.62 Å of the β-Si3N4 is constructed of these "small" hexagons, but there are no hexagons with

since it determines an atomic arrangement in the structure (8 × 8).

an appreciable difference in the electronic structures (state densities) β-Si3N4 and (8 × 8) is seen. Moreover, in the works [48, 49], devoted to the calculation of electronic states (0001) β-Si3N4, HOMO states associated with dangling bonds did not found. As it will be shown further, it is better to associate this peak in the density of states (8 × 8) with π-band.
