journal

J. Am. Ceram. Soc., 83 [4] 780 86 (2000)

Electronic Structure and Bonding of

-SiAlON
64110

Wai-Yim Ching,* Ming-Zhu Huang, and Shang-Di Mo

Department of Physics, University of Missouri-Kansas City, Kansas City, Missouri The - and -SiAlONs are ceramic solid solutions with charge-neutral substitutions in - and -Si3N4. They have high potential for applications as structural materials. We have calculated the electronic structure and bonding of -Si6 zAlzOzN8 z for z 0, 1, 2, 3, 4 using a first-principles method. Total energy calculations show that the bulk modulus of -Si6 zAlzOzN8 z decreases as z increases, in general agreement with experimental trends. Simultaneous substitution of the (Si,N) pair by (Al,O) results in impurity-like states in the upper portion of the bandgap of -Si3N4. As z increases, more and more states are introduced into the gap, forming a new conduction band (CB) edge for SiAlON. At z 4, the calculated bandgap is 1.3 eV. Density of states (DOS) calculations show the top of the valence band remains steep for all z, and the bottom of the CB is formed predominately by SiO antibonding states. Orbitally resolved partial DOS calculations in the CB region are used to predict the trends of the electron-energy-loss near-edge spectra (ELNES) of Si-L2,3, Al-L2,3, Si-K, Al-K, O-K, and N-K edges in -SiAlON. The impurity-like states near the CB edge result in pre-edge structures in all ELNES spectra. Effective charge and bond order calculations show that the overall bond strength in -SiAlON decreases only slightly as z increases. Although the stronger SiN bonds are replaced by weaker AlO bonds, the remaining SiN and AlO bonds actually strengthen as z increases because of the effective charge redistribution after substitution. This is a very interesting finding that may partly explain the superior mechanical properties of the SiAlON system that render them suitable for structural applications. I. Introduction

ITROGEN ceramics, especially Si3N4 and SiAlONs, are important structural ceramic materials used in a variety of engineering and microelectronic applications.1 4 This is because of their many outstanding properties, such as high strength, wear resistance, and chemical inertness. For structural applications, the mechanical properties and microstructure of the bulk material are central to its success. Although Si3N4 has been studied for a long time,5,6 SiAlON ceramics have been developed mostly within the past 15 years.7,8 SiAlON materials are easier to densify and more ductile at high temperatures than Si3N4.8,9 Over the years, many researchers have found that the intergranular glassy phase, mostly of oxides between -Si3N4 grains or at triple junctions, substantially controls the mechanical properties and the fracture behavior of sintered materials at elevated temperature.10 14 It has also been found that the thickness (usually of the order of 1 nm), the properties of the intergranular phases, and the aspect ratio of the Si3N4 grains can be altered by different sintering aids, mostly rare-earth elements.12,1517 The presence of aluminum and oxygen in the intergranular films affects the

R. H. Frenchcontributing editor

Manuscript No. 189633. Received January 12, 1999; approved August 12, 1999. Supported by U.S. Department of Energy under Grant No. DE-FG0284ER45170. *Member, American Ceramic Society.

growth of elongated grains and the strength of the crystalline/glass interface.18 20 It has been suggested that the increased hightemperature ductility of SiAlON may be related to enhanced selfdiffusivity in the presence of the ionic AlO pairs.9 The precise control and nature of atomistic bonding at the crystalline/glass boundary is one of the biggest problems facing the materials community. Microscopic understanding of the ceramic material when it is macroscopically deformed is the key to its improvement. Needless to say, this problem has attracted many researchers using different techniques to elucidate the structure, composition, and behavior of the intergranular phases in Si3N4.2126 Despite these endeavors, no clear understanding has emerged. Experimental development is usually conducted by a trial-and-error approach. Because of the structural complexity at interphase boundaries, theoretical investigations of such systems are almost nonexistent or are done in an oversimplified manner. Tanaka and co-workers9,27 are perhaps the only group who have attempted electronic structure calculations using the molecular orbital method to explain the mechanical properties and solution effects in the SiAlON system. Recently, Dudsek and Benco28 have studied simple models of Si3N4(110) surfaces and interfaces and interpreted their results in terms of the electron density of states (DOS). They show that a SiAlON-like boundary phase should have a stable electronic configuration with all states in the valence band (VB) occupied. There are two major SiAlON systems, - and -SiAlON, derived from - and -Si3N4 by substitution of (Si,N) pairs by (Al,O) pairs, respectively. Similar pair substitutions in Si2N2O result in the so-called O -SiAlON series, which also has gained recent attention.8,29 Epitaxial growth of SiAlON on -Si3N4 particles has been observed. Sun et al.15 found that an increase of (Al,O) content appears to strengthen the interfacial toughness of the SiAlON epitaxial layer at the interface. It is also possible to have mixed phases that can improve mechanical properties.25 Recently, it was reported that dilute SiAlON ceramics consisting of a mixture of -SiAlON and O -SiAlON can reduce or eliminate residual glassy films and increase hardness.17 Transformation properties between - and -SiAlONs also have been a subject of active pursuit.30,31 There are SiAlON polytype phases that are ordered based on the wurtzite structure of AlN.32 It is conceivable that many glassy phases in the intergranular thin films can have compositions and local bonding similar to SiAlON solid solutions. Here, we report a systematic investigation of the electronic structure and bonding in -Si6 zAlzOzN8 z, providing insight into the nature of intergranular phases. Our goal is to understand the structure and properties of intergranular thin films, their interfaces with Si3N4 crystallites, and their dependence on dopants in the glassy phase. The atomic-scale structure of such systems is too complicated for an exact calculation. In the -Si6 zAlzOzN8 z series, the geometric structure of the system is known unambiguously. Specifically, we perform ab initio band structure calculations for the -Si6 zAlzOzN8 z solid solutions for z ranging from 0 to 4. Here, z represents the number of (Al,O) pairs substituting for (Si,N) pairs in -Si3N4. The complex interplay between the more covalent SiN and AlN bonding and the more ionic AlO and SiO bonding, as a function of z, sheds light on the overall bonding and debonding mechanisms in the SiAlON system. The primary results of our study are the density of states (DOS), atomic and orbitally resolved partial DOS (PDOS), the bulk modulus, and its variation with z. Effective charges and the overlap 780

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population (also called bond order) calculation, together with the charge density map, enable us to reveal the details of bonding in -SiAlON. We pay particular attention to the orbitally resolved PDOS in the empty conduction band (CB), which can be used to interpret Si-L2,3, Al-L2,3, O-K, and N-K edges from electronenergy-loss near-edge spectroscopy (ELNES).33 Electron-energyloss spectroscopy (EELS) has been widely used for quantitative chemical analysis of materials with high spatial resolution. In particular, ELNES, which probes the inner shell excitation of a core electron to the unoccupied CB states, can provide useful information on the local chemical and structural environment of the excited atom.33 Such studies are most effective when the measured data are interpreted together with parallel theoretical calculations, as was recently demonstrated for the YAlO compounds34 and in the grain boundaries of SrTiO3.35 Careful and systematic calculations of the ELNES spectra in the SiAlON system can facilitate interpretation of the data on phase boundaries between -Si3N4 and the intergranular glassy films.21,22 II. Method of Calculation

In Eq. (1), the summation over En(k) is for the occupied bands and over the entire BZ using special k point sampling. Vxc and Ve-e are the exchange-correlation and electron-electron parts of the potential, and xc the exchange-correlation energy functional represented by the Wigner interpolation formula.36 The last term represents the interaction between the nuclei of the ions. III. Results of Calculation

The electronic structure of -Si6 zAlzOzN8 z is calculated using the ab initio orthogonalized linear combination of atomic orbitals (OLCAO) method36 with local approximation to the density functional theory (LDA).37 The method of calculation has been applied to many complex crystals and has been welldocumented.36 The calculations are similar to the ones for -Si3N4, -Si3N4, and Si2N2O bulk crystals.38 Recently, Zhao and Bachlechner39 applied the same method to study the electronic structure of the Si(111)/Si3N4(001) interface. In the present calculation, the lattice constants for -Si6 zAlzOzN8 z solid solutions are given by a 7.603 0.02967z and c 2.907 0.02554z based on X-ray powder diffraction data.8 For each z, appropriate substitutions of (Si,N) pairs by (Al,O) pairs are identified first among the 14 atoms in the unit cell of -Si3N4 with the lattice constants scaled according to z. Lattice relaxation as a result of substitution is ignored. Its effect on the electronic structure of the solid solution is expected to be small. The crystal structure for z 0 is that of Borgen and Seip40 used in our earlier studies.38 Although a controversy continues as to whether the structure of -Si3N4 should have a space group of P63/m or P63 without mirror symmetry, as suggested by Grun,41 we believe the difference between the two has little effect on the electronic structure of the SiAlON solid solutions. For z 0, several sites for substitution are possible. We have investigated this effect on a few representative cases for each z and again found the electronic structure is not very sensitive to the specific sites of substitution. Ideally, it is desirable to use a supercell of -Si3N4 with a large number of atoms and include all possible substitutions to represent the structure of -Si6 zAlzOzN8 z. However, in the absence of any reliable electronic structure results, the present calculation based on the unit cell of -Si3N4 is a realistic first attempt at such studies. The DOS and PDOS are calculated using the wave functions obtained at the 30 k points in the Brillouin zone (BZ) of the unit cell and the Mulliken analysis scheme42 as described before.43,44 The effective charges on each atom and the bond order between pairs of atoms are obtained by separate minimal basis calculations. One of the special advantages of the OLCAO method is the ease with which the effective charge and the bond order can be obtained, because the basis functions are expanded in terms of atomic orbitals. This facilitates the interpretation of the electronic structure and bonding in complex solid solutions. For each value of z, the total energy (TE) of the solid solution is calculated according to the usual expression from the LDA theory.
occ

(1) Bulk Properties The TE calculation for the solid solution is repeated for different crystal volumes. The calculated TE data are fitted to the Murnaghan equations of states (EOS)45 and also to the Birch Murnaghan EOS46 to obtain the bulk modulus B and the pressure coefficient B for each crystal. The results from the two different equations of states are quite similar, and those obtained by the Murnagahan EOS are summarized in Table I. The results for -Si3N4 (z 0) are slightly different from the previous studies44 because of slightly improved basis functions used in the present case. Figure 1 shows that the calculated bulk modulus B decreases smoothly as z increases. Also displayed are the experimental data9 for the z dependence of the Youngs modulus Y. Both B and Y are related to the elastic properties of the materials, and Fig. 1 shows that the trends in the z dependence are similar. (2) DOS and PDOS Figure 2 shows the total DOS of -Si6 zAlzOzN8 z for different values of z. The zero of energy is set at the top of the VB. For -Si3N4, the VB DOS consists of two segments, mainly originating from N-2s (from 14.3 to 18.9 eV) and N-2p (from 0 to 11.0 eV) states. The sharp peak centered at 1.5 eV is the signature of the nitrogen nonbonding orbital. The DOS in the CB consists of multiple peaks. The calculated bandgap is 4.2 eV compared with the reported experimental values ranging from 4.0 to 5.5 eV.47 The discrepancy in the experimental values of the gap is probably due to variation among samples prepared at different temperatures and under different conditions, because single crystal -Si3N4 is not available. Both the CB and the VB edges in the DOS are very sharp, as is typical for large-gap insulators. When a pair of (Al,O) atoms is substituted for a pair of (Si,N) atoms, the DOS becomes much more complex (Fig. 2(b)) because of the introduction of AlN, AlO, and SiO bonds. In the VB, multiple peaks of O-2s origin appear in the 22 to 23 eV region. Additional states appear below the N-2p band edge of 11 eV and above the N-2s band edge of 14.3 eV. These states are related to the O-2p bonding orbitals with silicon and aluminum. The top of the VB has a single sharp peak attributed to the AlN interaction. Most conspicuous is the presence of peaks at 1.5, 2.6, and 3.4 eV in the gap of -Si3N4. These can be interpreted as impurity-like states resulting from the substitution. As z increases from 1 to 4 (see Figs. 2 (b)(e)), these additional features grow with a concomitant reduction in the N-2s and N-2p states. For z 4, the VB can be divided into regions of O-2s (18.3 to 22 eV), N-2s (12.2 to 16.5 eV), and a mixture of N-2p and O-2p from 0 to 11.2 eV. As more impurity-like bands fill into the upper portion of the gap, a new CB edge is formed, and a reduced bandgap of 1.3 eV is obtained.

Table I. Calculated Equilibrium Volume, Bulk Modulus B (GPa), and Pressure Coefficient B in -Si6 zAlzOzN8 z
z V/V0 B B

ET
n,k

En k z z
,

xc

V xc

Ve 2

dr

(1)

0 1 2 3 4

0.99 0.99 0.99 0.995 0.995

343 311 286 250 237

4.32 4.36 4.18 4.27 4.38

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Fig. 1. (F) Calculated bulk modulus of -Si6 zAlzOzN8 z. (E) Experimental data for Youngs modulus from Ref. 9.

The PDOS of these 14 atoms are shown in Fig. 3. The left (right) panel is for atoms in the top (lower) layer. The lower layer contains the (Al,O) pair (also see Fig. 4(a)). In the first-order approximation, these 14 PDOS can be grouped into six types: (1) silicon with four nitrogen atoms as NN (Si(3), Si(4), Si(5)); (2) silicon with three nitrogen atoms and one oxygen atom as NN (Si(1), Si(2)); (3) nitrogen with three silicon atoms as NN (N(8), N(10), N(11), N(13)); (4) nitrogen with two silicon atoms and one aluminum atom as NN (N(7), N(9), N(14)); (5) the substituted Al(6) that bonds to three nitrogen atoms and one oxygen atom; and (6) the substituted O(12) that bonds to two silicon atoms and one aluminum atom. The PDOS of the atoms within the same group are almost the same. The minor differences reflect the second NN effects. In the case of the nitrogen sites, it also depends on whether the sites are 6h or 2c, because of their different bond lengths. Figure 3 shows that the impurity-like gap states near the CB edge originate from antibonding states between Si(2) and O(12). The extra-sharp peak at the top of the VB is due to the interaction of Al(6) with N(7) and N(14). The shift of the centroid of the DOS in the upper VB region as z increases (Fig. 2) can be understood by comparing the PDOS of nitrogen and oxygen (Fig. 3) in the same energy region. The sharp peak at 13.5 eV in Fig. 2(b) is the result of bonding between Al(6) and N(7). (3) Charge Distribution The valence charge density distribution of -Si5AlON7z (z 1) on a (001) plane containing the substituted aluminum and oxygen atoms is shown in Fig. 4. This is the same configuration whose PDOS is shown in Fig. 3. At first glance, one cannot distinguish

Fig. 2. Calculated total DOS in -Si6 zAlzOzN8 z for (a) z 1, (c) z 2, (d) z 3, and (e) z 4.

0, (b) z

To identify specific bonding in -SiAlON, we consider the PDOS of -Si5AlON7 (z 1) in more detail. It was reported by Suzuki et al.23 that the most desirable mechanical and thermal properties of -SiAlON, which is prepared by slip casting, are obtained for small values of z ranging from 0.5 to 1.0.25 We index the 14 atoms in the unit cell for z 1 as follows: Si(1) to Si(5), Al(6), N(7) to N(11), O(12), N(13), and N(14). Positions 1 to 6 are Si (6h) sites, 7 to 12 are N (6h) sites, and the last two are N (2c) sites, with reference to the -Si3N4 crystal.40 The structure can be viewed as two staggered (Si3N4)n layers perpendicular to the c-axis. The z 1 configuration considered here is the one in which Al(6) replaces Si(6) and O(12) replaces N(12) at the 6h sites, so that (Al,O) pairs are nearest neighbors (NN) in the same layer.

Fig. 3. Calculated atom-resolved PDOS in -Si5Al1O1N7. The 14 atoms in the unit cell are as indicated (see text for detail). Left panel is for the upper-layer, right panel for the lower-layer atoms. Atom No. 6 and No. 12 in the right panel are substituted aluminum and oxygen atoms, respectively. N(13) and N(14) are nitrogen at (2c) sites. Other atoms are at (6c) sites.

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Fig. 4. (a) Calculated valence charge density of -Si5Al1O1N7 in the extended zone for the lower plane c-axis. Dashed parallelogram indicates the unit cell boundary. Silicon and aluminum atoms are as indicated. Atoms numbered 10, 11, 14 are nitrogen atoms and atom 12 is an oxygen atom. Contour lines are from 0.01 to 0.25 by 0.005 in unit of electrons/(a.u.)3. (b) Difference contour between crystalline and atomic valence charges in the same plane as (a). Dashed lines are for negative values of charge density.

between silicon and aluminum or between oxygen and nitrogen. This indicates that the substitution of the (Al,O) pair for the (Si,N) pair has little effect as far as charge density is concerned. This may be the reason why, experimentally, it is difficult to identify the substituted sites in the dissolved solid solution. This also justifies our assumption that there should be little or no lattice relaxation as a result of substitution. The silicon and aluminum atoms lose electrons, while nitrogen and oxygen gain them, with the difference between the substituted pairs fairly balanced even though O (Al) is more electronegative (electropositive) than N (Si). Our ab initio calculation in Fig. 4(a) shows strong bonding between Si (Al) and the next neighbor N (O). Figure 4(b) shows the difference between the charges in the solid solution and the superposition of free atoms in the same plane as in Fig. 4(a). Again, the presence of the AlO pair is barely noticeable, indicating very efficient charge redistribution in the -SiAlON system. (4) Effective Charge and Bond Order The calculated effective charges, Q* per atom (averaged over all sites), in -Si6 zAlzOzN8 z are calculated from the minimal basis wave functions using the Mulliken scheme and are listed in * Table II. For -Si3N4, the Q* and QN are 2.45 and 6.17, Si respectively (or equivalently, 2.44 and 1.83, respectively, in ionic notation). This is very close to the earlier values of 2.50 and 1.87 using a real-space integration scheme.38 Both indicate a substantial covalent-bonding character in Si3N4. For -SiAlON solid solutions with a much more complex bonding structure among the four elements, the minimal basis Mulliken scheme is a

very effective way to study the trends of charge transfer as z varies. * Table II shows that Q* and QAl fluctuate between z 0 and 4, Si * * while QN and QO increase steadily as z increases. The overall picture from the effective charge calculation is that of an increase in the ionic character as z increases. This is expected, because Al2O3 is much more ionic than Si3N4. The results of bond order calculations are shown in Fig. 5 and reveal several interesting facts: (1) The SiN and AlN bonds are much stronger than the SiO and AlO bonds; (2) As z increases, the average SiN and AlO bond orders actually increase, and the average AlN and SiO bond orders remain roughly constant; (3) The bond order of AlO at z 4 is almost double that of z 1, indicating that an isolated AlO bond in Si3N4 is a very weak bond; and (4) The total bond strength in -Si6 zAlzOzN8 z is obtained by averaging all pairs of bond orders in the solid solution. Bond strength decreases only slightly as z increases and is mainly due to the replacement of the stronger SiN bonds with weaker AlO bonds. This result is consistent with the variation of the bulk modulus of the solid solution discussed in Section III(1). SiAlON s slow decrease in overall bond strength with substantial substitution

Table II. Calculated Average Effective Charge per Atom in -Si6 zAlzOzN8 z
Average effective charge 0 1 z 2 3 4

Q* Si Q* Al * QN Q* O

2.445 6.166

2.459 1.600 6.169 6.921

2.454 1.617 6.174 6.952

2.502 1.560 6.182 6.968

2.434 1.582 6.233 6.969

Fig. 5. (F) Overall bond strength in -Si6 zAlzOzN8 z as function of z. ( ) SiN, (X) AlN, ( ) SiO, and (E) AlO.

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of (Si,N) pairs by (Al,O) pairs is the main reason it can be as tough a ceramic as -Si3N4 for structural applications. The microscopic explanation of this is the effective charge redistribution in the SiAlON system. Although the stronger SiN bonds are replaced by weaker AlO bonds, the remaining SiN bonds and increased AlO bonds actually become stronger as z increases.

(5) ELNES Spectra The orbitally resolved PDOS of each atom in the unoccupied CB region can be used to interpret the ELNES spectra.33 The Si-L2,3 and Al-L2,3 edges involve transitions from the 2p core levels of silicon and aluminum and should be roughly represented by the (s d) components of the PDOS of the respective atoms in the CB. Likewise, Si-K, Al-K, O-K, and N-K edges are related to transitions from the 1s core states, so the p component of the PDOS in the CB should mimic the K edges of these atoms. The PDOS interpretation of the ELNES spectra neglects the effect of core hole interaction, which may be important for the L2,3 edges.48 Inclusion of core hole effect is not attempted in the present study. Although no systematic measurements of the ELNES on well-characterized SiAlON samples have been reported, it is our belief that such measurements will be available soon, and our calculation will be useful for their interpretation. Recently, there have been some reports of ELNES spectra on intergranular thin films of Si3N4 that consist of a silicate glassy phase.23 The calculated orbitally resolved PDOS (s d and p components) for silicon, aluminum, oxygen, and nitrogen in -Si6 zAlzOzN8 z averaged over each type of atom are shown in Fig. 6 8. A Gaussian broadening of 1 eV has been applied to each PDOS curve, and the zero of energy is set at the top of the VB. The theoretical ELNES spectra represented by PDOS are very rich in structure because of the presence of multiple bonding and the complex local environments of each atom. It is premature to attach any significance to the specific structure in the PDOS, and it is more important to observe the general trends of the spectra as z varies. We focus our discussion on -Si3N4 (z 0), -Si5AlON7 (z 1) cases, whose atomic-scale structures are described in Section III(2), and also on the limiting case of z 4, where the numbers of nitrogen and oxygen atoms in the unit cell are equal. The most significant feature in all these spectra is the presence of a pre-edge structure that grows as z increases. The pre-edge structure is related to the impurity-like states in the gap of -Si3N4 and the formation of the new lower CB edge discussed earlier, which could be detected experimentally. For the Si-L2,3 edges, the (s d) PDOS (Fig. 6, left panel) consists of many multiple structures, even for z 0, where there are only two atomic speciessilicon and nitrogen. This is related to the complexity of the crystal structure of -Si3N4 itself. These structures can be grouped into three regions, R1, R2, and R3, separated by two deep minima at 8.3 and 20.9 eV. The major peaks in these three regions are A at 5.9 eV; B1, B2, and B3 at 10, 12, and 16 eV, respectively; C at 25.8 eV; and additional minor peaks. The relative positions and strengths of the peaks change as z increases. At z 4, the main peaks A1, A2, B1, B2, B3, and C are at 5.3, 7.6, 10.2, 12.0, 16.0, and 22.1 eV, respectively, in addition to the pre-edge structure in the 2.0 eV range. For the Al-L2,3 edge (Fig. 6, right panel) in the z 1 case, there is only one aluminum atom. The spectra show a deep minimum at 19.5 eV and a major peak at 12.0 eV. There are many other structures that evolve as z increases, reflecting a steady increase of the AlO bonds relative to the SiN bonds. A remarkable feature is that the main edge at 5.5 eV is relatively independent of z, even with the presence of the pre-edge structure discussed earlier. The PDOS (p component) for the Si-K and Al-K edges are shown in Fig. 7. Experimentally, the Si-K and Al-K edges have a much lower energy resolution because of the higher transition energies for the 1s core electron. There are many structures in both spectra, and the amplitudes decrease as energy increases. At z 4, Si-K has two well-defined peaks at 5.2 and 8.0 eV. The presence

Fig. 6. (s d) components of orbitally resolved PDOS of silicon (left panel) and aluminum (right panel) of -Si6 zAlzOzN8 z in the CB region. These spectra should mimic Si-L2,3 and Al-L2,3 edges. Curves are broadened by a Gaussian of 1 eV.

of the pre-edge structure is again obvious. The centroid of the overall spectra is at a lower energy in Si-K than in Al-K. The PDOS for the N-K and the O-K edges are shown in Fig. 8. For N-K, we can separate the spectra into two regions above and below the minimum at 20 eV. We may consider the structures below 20 eV as a single broad peak that centers at 10 eV in -Si3N4. As z increases, the peak position shifts slightly upward, and the width of the peak increases. For the O-K edge, we can again divide the spectra into two regionsabove and below 15 eV. For z 1, where there is only a single oxygen in the unit cell, the main peak in the lower region centers at 6.5 eV. This peak structure again evolves as z increases, and, at z 4, the peak looks more like a plateau with rather sharp edges on either side. There are multiple structures in the region above 15 eV in both cases that are difficult to interpret in a simple way. IV. Conclusions

Based on detailed ab initio calculations of the electronic structure and bonding in -Si6 zAlzOzN8 z for z ranges of 0 to 4, the main conclusions are as follows: (1) The bulk modulus and bonding strength in the SiAlON solid solution decrease only slightly with z. (2) At z 1, impurity-like states are introduced near the CB edge, and, at a higher z, the crystal is a semiconductor with a gap of the order of 1.3 eV. (3) The charge density plot shows very little disturbance as a result of pair substitution. Effective charge calculation shows only

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Fig. 7. Same as Fig. 6 for the p-component of PDOS, which should represent Si-K and Al-K edges.

Fig. 8. p-component of orbitally resolved PDOS of nitrogen (left panel) and oxygen (right panel) of -Si6 zAlzOzN8 z mimics O-K and N-K edges, respectively. All spectra are broadened by a Gaussian of 1 eV.

a slight decrease in the covalent character of the solid solution as z increases. (4) Substitution of the (Si,N) pair with (Al,O) actually strengthens the remaining bonds because of the efficient redistribution of charge. This is one of the reasons SiAlON can be an effective structural ceramic with superior mechanical properties. (5) Orbitally resolved DOS and PDOS calculations reveal the intricate interplay of the SiN, SiO, AlN, and AlO bonds in the solid solution. The orbitally resolved PDOS in the CB are used to predict the z dependence of the ELNES spectra, which has yet to be measured experimentally. These results also affect the electronic structure of the intergranular thin films, consisting mainly of doped silicates, between Si3N4 particles. Detailed ab initio results can be used to construct effective pair potentials for large-scale simulations where ab initio calculations become prohibitive. Recently, such effective pair potentials for - and -Si3N4 have been obtained with very satisfactory results.44 For intergranular phases, good pair potentials are more difficult to obtain because of the multiple atomic species present and the need to account for the environmental dependence of the potentials. Electronic structure calculations should be extended to -SiAlON and the O -SiAlON series to see if changes in local bonding can affect the ELNES spectra and be detected experimentally. Calculations should also be conducted on more-complicated solid solutions, such as in the Y-SiAlON series. This will enable us to ascertain the solution effect of the rare-earth elements. The room-temperature toughness of -SiAlON can be significantly improved by a small addition of Y2O3.20 The fact that

an increase in the Y:Al and O:N ratio promotes interface debonding demonstrates the importance of interfacial chemistry and composition in determining the mechanical properties. It is also desirable to model the structures at the interface between Si3N4 crystal and the glassy phases and then conduct direct electronic structure calculations of these models. Together with increased experimental effort, greater understanding can be obtained of the structure and bonding of the intergranular phases and the determining role they play in a materials mechanical properties, which are crucial for its application as a structural ceramic. References
1 D. W. Richerson and P. M. Stephan, Evolution of Applications of Si3N4-Based Materials, Mater. Sci. Forum, 47, 282307 (1989). 2 Silicon Nitride Ceramics, Materials Research Society Symposium Proceedings, Vol. 287. Edited by I-W. Chen, P. F. Becher, M. Mitomo, G. Petzow, and T.-S. Yen. Materials Research Society, Pittsburgh, PA, 1993. 3 M. J. Hoffmann, P. F. Becher, and G. Petzow (Eds.), Silicon Nitrides 93, TransTech Publications, Aedermannsdorf, Switzerland, 1994. 4 R. Raj, Fundamental Research in Structural Ceramics for Service near 2000 C, J. Am. Ceram. Soc., 76, 214774 (1993). 5 S. Wild, P. Grieveson, and K. H. Jack, Special Ceramics, Vol. 5; p. 385. Edited by P. Popper. British Ceramic Research Association, Stoke-on-Trent, U.K., 1972. 6 J. Weiss, Silicon Nitride Ceramics: Composition, Fabrication Parameters, and Properties, Annu. Rev. Mater. Sci., 11, 38199 (1981). 7 (a)K. H. Jack and W. I. Wilson, Ceramics Based on the Si-Al-O-N and Related Systems, Nature (London), Phys. Sci., 238, 28 29 (1972). (b)K.H. Jack, The SiAlONs, Mater. Res. Bull., 13, 132733 (1978). 8 T. Ekstrom and M. Nygren, SiAlON Ceramics, J. Am. Ceram. Soc., 75 [2] 259 76 (1992). 9 I. Tanaka, S. Nasu, H. Adachi, Y. Miyamoto, and K. Niihara, Electronic Structure behind the Mechanical Properties of -SiAlONS, Acta Metall. Mater., 40 [8] 19952001 (1992).

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10 D. R. Clarke, On the Equilibrium Thickness of Intergranular Glass Phases in Ceramic Materials, J. Am. Ceram. Soc., 70, 1522 (1987). 11 D. R. Clarke, High-Temperature Microstructure of a Hot-Pressed Silicon Nitride, J. Am. Ceram. Soc., 72, 1604 609 (1989). 12 M. J. Hoffmann, Analysis of Microstructural Development and Mechanical Properties of Si3N4 Ceramics; pp. 59 72 in Tailoring the Mechanical Properties of Si3N4 Ceramics. Edited by M. J. Hoffmann and G. Petzow. Kluwer, Dordrecht, The Netherlands, 1994. 13 7. X. Pan, H. Gu, R. v. Weeren, S. C. Danforth, R. W. Cannon, and M. Ruhle, Grain-Boundary Microstructure and Chemistry of a Hot Isostatically Pressed High Purity Silicon Nitride, J. Am. Ceram. Soc., 79 [9] 231320 (1996). 14 H.-J. Kleebe, M. K. Cinibulk, I. Tanaka, J. Bruley, J. S. Vetrano, and M. Ruhle, High Resolution Electron Microscopy Studies on Silicon Nitride Ceramics; pp 259 274 in Tailoring of High Temperature Properties of Si3N4 Ceramics. Edited by M. J. Hoffmann and G. Petrow. Kluwer, Dordrecht, The Netherlands,1994. 15 H.-J. Kleebe, M. K. Cinibulk, R. M. Cannon, and M. Ruhle, Statistical Analysis of the Intergranular Film Thickness in Silicon Nitride Ceramics, J. Am. Ceram. Soc., 76 [8] 1969 77 (1993). 16 E. Y. Sun, P. F. Becher, S. B. Waters, C. H. Hsueh, K. P. Plucknett, and M. J. Hoffmann, Control of Interface Fracture in Silicon Nitride Ceramics: Influence of Different Rare Earth Elements; in Ceramic Microstructures 96. Edited by A. P. Tomsia and A. Glaser. Plenum, New York, 1998. 17 G. Pezzotti, K. Ota, and H.-J. Kleebe, Grain-Boundary Relaxation in HighPurity Silicon Nitride, J. Am. Ceram. Soc., 79 [9] 2237 46 (1996). 18 T. Ekstrom, P. O. Kall, M. Nygren, and P.O. Olsson, Dense Single-Phase SiAlON Ceramics by Glass-Encapsulated Hot Isostatic Pressing, J. Mater. Sci., 24, 1853 61 (1989). 19 G. Pezzotti, H.-J. Kleebe, K. Ota, and K. Yabuta, Supression of Viscous Grain-Boundary Sliding in a Dilute SiAlON Ceramic, J. Am. Ceram. Soc., 72, 1604 609 (1989). 20 P. F. Becher, E. Y. Sun, C. H. Hsueh, K. B. Alexander, S. L. Hwang, S. B. Waters, and C. G. Westmoreland, Debonding of Interfaces between -Silicon Nitride Whiskers and Si-Al-Y Oxynitride Glasses, Acta Mater., 44 [10] 388193 (1996). 21 H. Gu, R. M. Cannon, and M. Ruhle., Composition and Chemical Width of Ultrathin Amorphous Films at Grain Boundaries in Silicon Nitride, J. Mater. Res., 13 [2] 376 87 (1998). 22 R. H. French, H. Mullejans, D. J. Jones, G. Duscher, R. M. Cannon, M. Ruhle, Dispersion Forces and Hamaker Constants for Intergranular Films in Silicon Nitride from Spatially Resolved Valence Electron Energy Loss Spectrum Imaging, Acta Mater., 46, 2271 87 (1998). 23 S. Suzuki, N. Takakuni, S. Hayama, and M. Ozawa, Mechanical and Thermal Properties of -Sialon Prepared by Slip Casting Method, J. Am. Ceram. Soc., 79 [6] 1685 88 (1996). 24 L. L. K. Falk, Z.-J. Shen, and T, Ekstrom, Microstructural Stability of Duplex -Sialon Ceramics, J. Eur. Ceram. Soc., 17, 1099 112 (1997). 25 X. Jiang, Y.-K. Baek, S.-M. Lee, and S.-J. L. Kang, Formation of an -SiAlON Layer on -SiAlON and its Effect on Mechanical Properties, J. Am. Ceram. Soc., 81 [7] 190712 (1998). 26 A. J. Pyzik and D. R. Beaman, Microstructure and Properties of Self-Reinforced Silicon Nitride, J. Am. Ceram. Soc., 76 [1] 328 (1993). 27 (a)T. Nakayasu, T. Yamada, I. Tanaka, H. Adachi, and S. Goto, Electronic -SiAlONs, with Correlation to Solubility and Solution Effect, Structure of Ln3 J. Am. Ceram. Soc., 79 [10] 252732 (1996). (b)Calculation of Grain-Boundary Bonding in Rare Earth-Doped -Si3N4, ibid., 81 [3] 56570 (1998). 28 P. Dudsek and L. Benco, Cation-Aided Joining of Surfaces of -Silicon Nitride: Structural and Electronic Aspects, J. Am. Ceram. Soc., 80 [5] 1248 54 (1998).

29 M. E. Bowden, G. C. Barris, and I. W. M. Brown, A New, Low-Temperature Polymorph of O -SiAlON, J. Am. Ceram. Soc., 81 [8] 2188 90 (1998). 30 H. Mandal, D. P. Thompson, and T. Ekstrom, Reversible 7 Sialon Transformation in Heat-Treated Sialon Ceramics, J. Eur. Ceram. Soc., 12, 42129 (1993). 31 M. Camuscu, D. P. Thompson, and H. Mandal, Effect of Starting Composition, Type of Rare Earth Sintering Additive, and Amount of Liquid Phase on 7 Sialon Transformation, J. Eur. Ceram. Soc., 17, 599 613 (1997). 32 D. P. Thompson, P. Korgul, and A. Hendry, The Structural Characterization of Sialon Polytypoids; pp. 6174 in Progress in Nitrogen Ceramics. Edited by F. L. Riley. Martinus Nijhoff, The Hague, The Netherlands (1983). 33 R. F. Egerton, Electron Energy Loss Spectroscopy in the Electron Microscope. Plenum, New York, 1993. 34 M. Gulgun, Y.-N. Xu, W. Y. Ching, and M. Ruhle, Electron States of YAG Probed by Energy-Loss Near-Edge Spectrometry and ab initio Calculations, Philos. Mag., B, 79 [6] 921 (1999). 35 S.-D. Mo, W. Y. Ching, M. F. Chisholm, and G. Duscher, Structure and Bonding of a Grain Boundary Model in SrTiO3, Phys. Rev. B: Condens. Matter, 60 [4] 2416 24 (1999). 36 W. Y. Ching, Theoretical Studies of the Electronic Properties of Ceramic Materials, J. Am. Ceram. Soc., 73, 3135 60 (1990). 37 (a)P. Hohenberg and W. Kohn, Inhomogeneous Electron Gas, Phys. Rev. [Sect.] B, 136, B864 B871 (1964). (b)W. Kohn and L. J. Sham, Self-Consistent Equations Including Exchange and Correlation Effects, Phys. Rev. [Sect.[ A, 140, A1131A1138 (1965). (c)L. J. Sham and W. Kohn, One-Particle Properties of an Inhomogeneous Interacting Electron Gas, Phys. Rev. 145, 561 67 (1966). 38 Y.-N. Xu and W. Y. Ching, Electronic Structure of - and - Phases of Silicon Nitride, Silicon Oxynitride, and with Comparison to Silicon Dioxide, Phys. Rev. B: Condens. Matter, 51, 17379 89 (1991). 39 G. L. Zhao and M. E. Bachlechner, Electronic Structure and Charge Transfer in -and -Si3N4 and the Si(111)/Si3N4(001) Interface, Phys. Rev. B, 58, 188795 (1998). 40 O. Borgen and H. M. Seip, The Crystal Structure of -Si3N4, Acta Chem. Scand., 15, 1789 89 (1961). 41 R. Grun, The Crystal Structure of -Si3N4: Structural and Stability Consider ations between - and -Si3N4, Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem., 35, 800 804 (1979). 42 (a)R. S. Mulliken, Electron Population Analysis on LCAO-MO Molecular Wave Functions, I, J. Am. Chem. Soc., 23, 1833 40(1955). (b)Electron Population Analysis on LCAO-MO Molecular Wave Functions, II, ibid., 23, 1841 46 (1955). 43 W. Y. Ching, Y.-N. Xu, and M. Ruhle, Ab initio Calculation of Y-Substitutional Impurity in -Al2O3, J. Am. Ceram. Soc., 80 [12] 3199 204 (1997). 44 W. Y. Ching, Y.-N. Xu, J. D. Gale, and M. Ruhle, Ab initio Total Energy Calculation of - and -Phases of Silicon Nitride and the Derivation of Effective Inter-Atomic Pair Potentials with Application to Lattice Dynamics, J. Am. Ceram. Soc., 81 [12] 3189 96 (1998). 45 F. D. Murnagahn, The Compressibility of Media under Extreme Pressures, Proc. Natl. Acad. Sci., U. S. A, 30, 244 47 (1944). 46 F. Birch, Finite Strain Isotherm and Velocities for Single Crystal and Polycrystalline NaCl at High Pressure and 300 K, J. Geophy. Res., D: Atmos., 83, 1257 68 (1978). 47 J. T. Milek, Handbook of Electronic Materials, Vol. 3. IFI/Plenum, New York, 1971. 48 J. Zaanen, Theory of Correlated Holes (and Electrons): from Satellites to Luttinger Liquids; pp. 89 137 in Unoccupied Electronic StatesFundamentals for XANES, EELS, IPS and BIS, Topics in Applied Physics, Vol. 69. Edited by J. C. Fuggle and J. E. Inglesfield. SpringerVerlag, New York, 1992.