M.Sc.

Research Proposal Electronic Structures, Elastic Constants and the Stability of a Novel Spinel Structure by Ab initio Calculations
Okeke, Onyekwelu Uzodinma. okekeo@science.pg.wits.ac.za or okekeou@gmail.com Supervisor : Professor J E Lowther October 3, 2006

Summary of Proposal
Spinel structures are class of oxides with a chemical formula AB2 O4 where the cation to anion ratio distribution is 3:4. This work involves the computational modelling of the spinel materials resulting from the group-III oxides and nitrides by ab initio plane wave pseudopotential calculations. The theoretical properties of the electronic structures (the ground state energies, the band structures, density of states and charge densities), elastic constants and their stabilities will be investigated.

Spinel Structure
The spinel structure of novel materials are rapidly emerging as having potential ultra-hard properties. Basically, a spinel-structured material has the ratio 3:4 in their cation to anion distribution. Spinel could be in binary (e.g Si3 N4 ), or in ternary (e.g MgAl2 O4 ) or in quaternary phases (e.g Si6z Alz Oz N8z ) [1]. The main study on this research work would be based on the ternary spinel structures. In general, spinel structures refers to a class of oxides with a chemical formula AB2 O4 where A and B are either divalent (+2) and trivalent (+3) or tetravalent (+4) and divalent cations. The structural models of spinel is illustrated in Fig. (1) and (2). In both gures the anion sites are at the corners of octahedral/tetrahedral.

Figure 1: Atomistic models of the cubic spinel structure, where the octahedral cation sites are highlighted with octahedral and the tetrahedral cation sites are represented with balls [2].

Figure 2: Atomistic models of the cubic spinel structure, where the tetrahedral cation sites are highlighted with tetrahedral and the octahedral cation sites are represented with balls [2].

The oxygen ions or arrays of anions in the spinel structures are in close-packing (ccp or fcc) structure, where two types of interstices known as the octahedral and tetrahedral are found. A and B cations occupy the tetrahedral and the octahedral interstitial sites [2, 3]. Eight 1

formula units make up a unit cell of spinel (A8 B16 O32 ) which contains 56 atoms . Spinel structure can be divided into two types: normal (or direct) and inverse spinel. The unit cell of the normal spinel has 32 oxygen ions, 32 octahedral interstices with B cations at the 1 1 1 1 ( 1 , 2 , 1 ) positions and 64 tetrahedral interstices with A cations at the ( 8 , 8 , 8 ) positions. In 2 2 inverse spinel, the cations may shift between the A and B sites. Half of the B cations go to the tetrahedral sites and the A cations go to octahedral interstices. The general formula for an inverse spinel structure is given as B(AB)O4 [4]. The range of cation distribution for both the normal and inverse spinel can be determined by their relative ionicity or ionic radii [5]. Additionally, mixed spinel structure of the form (A12 B2 )(A2 B22 ), could also be possible, where is the inversion parameter ranging from 0 for the normal to 0.5 for the inverse spinel [6]. Spinel belongs to the space group of f d3m (No. 227) [7]. The focus of this research work will be to investigate a novel spinel structure with chemical formula A3 NO3 , where A represents Boron (B), Aluminium (Al), Galium (Ga), and Indium (In) which are the group 3 elements of the periodic table. Spinel of these form could be regarded as a double spinel with A occupying both the tetrahedral and octahedral sites. The chemical equation for the spinel is given as:

A3 NO3 A2 O3 + AN where the right hand side of equation (1) represents the group-III oxides and nitrides.

(1)

Forms of Group-III Oxide

The oxides of group-III elements (atoms) are B2 O3 , Al2 O3 , Ga2 O3 , In2 O3 . The exist in two or more crystallographical phases especially in their stable and metastable states. The phases of the group-III atoms are given as follows:

Boron oxide (B2O3)

Boron oxide or boron (III) oxide B2 O3 is one of the important industrial minerals commonly used. It has a very rich chemistry as compared to carbon. Boron and its compounds (e.g B2 O3 ) have excellent properties like superhardness, insulation, linear and nonlinear optical behavior which have made them attractive for electronic and optoelectronic devices. Boron oxide can be produced by direct reaction of boron and oxygen under pressure. It has the advantage of very low heat expansion, high refractive index and high ion conductivity. Because of these characteristics it exhibit, boron oxide is used widely in glass forming materials after silica. And as such when doped on ceramic materials, it enhance conductivity and structural stability [8, 9]. B2 O3 is also one of the additives used to modify textural and acid based properties of metal oxides such as Al2 O3 , Ti2 O3 and MgO [10]. The structure of B2 O3 has been a subject of debate for many years now. However, as a results of many spectroscopic investigations (such as neutron and X-ray diraction, Ramman spectroscopy, Molecular dynamic simulations as well as NMR and NQR spectroscopy), it has been widely viewed and accepted that boron oxide is a network of oxygen-sharing BO3 triangles. Three BO3 triangles combine to form a mixed random network of boroxol rings B3 O6 [11, 12, 13, 14]. A model of vitreous B2 O3 with boron atoms residing in the boroxol rings is shown in Fig. 3 [11]. B2 O3 consists of two polymorph or form in which the boron atoms have dierent coordination numbers. They are B2 O3 -I and B2 O3 -II. 3

Figure 3: A model of vitreous B2 O3 structure with boron atoms residing in the boroxol rings [11].

B2 O3 -I is known as the low-pressure structure of B2 O3 , obtained at a pressure of 2 GPa with a hexagonal unit cell. It crystallizes in space group P 31 with a = 4.336, c = 8.340 as A reported by Gurr et al [15]. B2 O3 -II is the high-pressure phase structure of B2 O3 obtained at a pressure of 6.5 GPa and temperature of 1100 o C. The structure of B2 O3 -II is orthorhombic with a = 4.6130.001, b = 7.803 0.002, c = 4.129 0.001, and space group Ccm2, built up by two sets of tetrahedral A with shared corners as described by Prewitt and Shannon [16]. It could be observed that under pressure, crystal B2 O3 undergoes a structural transformation that increases the boron coordination from BO3 triangular unit into the BO4 tetrahedral unit [17]. The structures of B2 O3 -I and B2 O3 -II are shown in Fig. (4) and (5).

Aluminum Oxide (Al2O3)

Aluminum oxide or alumina has a unique range of industrial applications as structural ceramic and optical materials. It is extensively used as a high temperature, corrosion resistant refractory material due to its hardness, chemical durability, abrasive resistance, mechanical strength, high surface area and good electrical insulation. Alumina exist in two major crystallographic phases known as the stable or ground state structure and the metastable or transition structures. The Stable phase is commonly known as corundum (-Al2 O3 ) has the 4

Figure 4: Two unit cell of B2 O3 -I [15].

Figure 5: B2 O3 -II structure [16].

hexagonal close packed (hcp) rhombohefral crystal structure with stacking sequence ABAB and lattice parameter ao = 0.476 nm and co = 1.299 nm [18, 19]. The transition alumina exist in many transient metastable forms such as , , , , , and alumina where , , , , possess a face centered cubic (fcc) array of oxygen anions with the aluminum cations ocupying a portion of the available octahedral and tetrahedral interstices and , and are the metastable form of the hexagonal close packed (hcp) array of oxygen anions [20]. Among the transition alumina, , , and are all believe to be spinel-based with cation to anion ratio of 2:3. However, in recent studies, tetragonal representations of the aluminua structure with I41 /amd space group symmetry and a maximum subgroup of F d have 3m been proposed [18].

Gallium Oxide (Ga2O3)

Gallium oxide is a thermally and chemically stable materials which is insulating at room temperature but semiconducting at higher temperatures. Ga2 O3 has several polymorphs, but the two major forms are , which can be classied under high and low temperature polymorph of gallium oxide. High temperature Ga2 O3 is the most stable form of the metal oxide. It has a monoclinic structure with a space group C2/m and contains both octahedral and tetrahedral cation sites in equal quantities. The wide band gap energy is about Eg = 4.8 eV. Ga2 O3 is the low temperature phase of gallium oxide with a rhombohedral structure.

The phase transition temperature from Ga2 O3 to Ga2 O3 is about 600 o C. Ga2 O3 thus has the strong advantage of low synthesis temperature as compared to that of Ga2 O3 [21, 22].

Indium Oxide (In2O3)

Indium oxide is a wide band gap semiconductor with energy gap Eg 3.70 eV. It has been widely used as a material for transparent electrodes in electronic devices such as liquid crystal displays, solar cells, as a barrier layer in tunnel junctions, as a sensing materials in gas sensors, and in nanowire technology. In2 O3 exit in two crystal phases namely: the body-centered cubic (bcc) and the rhombohedral (rh) structures. The bcc-In2 O3 has a cubic cell lattice constant of a = 10.118 and space A group symmetry of the unit cell is Ia3 whereas the rh-In2 O3 lattice constants are a = 5.478 A and c = 14.51 and with space group symmetry of R-3C [23]. The physical and optical A properties of bcc-In2 O3 as reported by [23] are not well known and whereas for rh-In2 O3 , no information are available.

Forms of Group-III Nitrides

The group-III nitrides namely: BN, AlN, GaN, and InN, are currently being investigated due to their promising potentialities. They have potential for high-temperature, high-power, and high-frequency electronics which are characterized by large band gaps, strong (mixed ionic and covalent) bonding, and dielectric constants. Furthermore, the properties of their zinc-blende and/or wurtzite phase, such as hardness, high melting point, high thermal conductivity, large bulk moduli also makes them useful for protective coatings. Apart from BN, the group-III nitrides crystalize in two forms or phases, namely: the stable wurtzite structure and the metastable sphalerite or zincblende which is normally regarded as cubic structure. BN has hexagonal and cubic phases that are quiet similar to the graphite and diamond phases of carbon [24, 25, 26]. Among all the phases, cubic BN (which has a zinc-blende structure) is the most interesting both technologically and scientically. c-BN is the second hardest material known after diamond and has excellent thermal and conductivity. It has the ability to form both nand p- type semiconductors when doped appropriately [27]. Aluminum nitride, (AlN) is unique for its ultrahigh direct-gap of more than 6 eV as well as the ability of the band gap engineering through the use of alloying and heterostructures with GaN [28]. The nitrides of Ga and In are equally of great importance. GaN is a wide band gap wurtzite structure, used for optoelectronic and high-frequency devices in the wavelength ranging from bluegreen to ultraviolet. On the other hand, InN and its alloys have also emerged as promising materials for optoelectronic devices such as light-emiting diodes and solar cells [29, 30]. The physical properties of nitrides are summarized in Table 1, stating their band gap, lattice constants and bond lengths, ionicity and their respective ratio of states numbers.

Table 1: Physical properties of group-III nitrides [26]. Material Band gap (eV) GaN wurtzite 3.5 Lattice constants (a, c) Ionicity and bond lenghts (b, d) () A (Phillips) a = 3.1892 c = 5.1850 c/a = 1.626 b/c = 0.377 b = 1.955; d = 1.9486 a = 4.511 c = 2.1923 a = 3.1106 c = 4.9795 c/a = 1.601 b/c = 0.3821 b = 1.90; d = 1.807 a = 4.38 b = 2.1287 a = 3.54 c = 5.70 c/a = 1.601 a = 4.98 b = 2.4203 a = 2.54 c = 4.17 c/a = 1.64 b/c = 0.375 b = 1.156; d = 1.556 a = 3.616 b = 1.7573 0.43 Ratio of states nos. Valence N/Ga = 3.5 Ga/N = 0.28 Conduc. 0.67 1.49

GaN cubic AlN wurtzite

3.3 6.1

0.44

N/Ga = 3.4 Ga/N = 0.29 N/Al = 4.4 Al/N = 0.23

0.98 1.29 0.64 1.56

AlN cubic InN wurtzite

4.5 6.2 1.9

0.57

N/Al = 4.6 Al/N = 0.22 N/In = 4.4 In/N = 0.23 N/B = 4.0 B/N = 0.25 N/B = 2.2 B/N = 0.45

0.80 1.25 0.96 1.04 0.97 1.03 0.85 1.18

InN cubic BN hex

1.9 2.0 5.4 5.8

0.36

BN cubic

6.1 6.4

N/B = 1.96 B/N = 0.51

0.80 1.25

Techniques and Methodology

The electronic structure of materials represents the interatomic ionic, covalent, and metallic bonds formed by electrons which form the solid. The electronic structure provides information on the density of states (DOS) of the valence, conduction bands, charge density, and ionic charges as well as the prediction and description of the ground state properties of materials such as metals, semiconductors, and insulators. The electronic structural calculations of the spinel materials, their bulk moduli and elastic constants will be investigated by an ab initio (or rst principle) technique that is base on density functional theory (DFT).

Density Functional Theory.

Density functional theory is the quantum mechanical approach for solving the many-electron systems of the time-independent, non-relativistic Schrdinger equation o Hi (x1 , x2 , ..., xN , R1 , R2 , ..., RM ) = Ei i (x1 , x2 , ..., xN , R1 , R2 , ..., RM )

(2)

where H is the Hamiltonian for a system consisting of M nuclei and N electrons and the wave-function is a function of all the electronic and nuclear denoted by xi and RI . 1 H= 2
N

2 i
i=1

1 2 1 2 A=1 MA A

i=1

ZA + riA A=1

i=1 j>i

1 ZA ZB + riA A=1 B>A RAB

(3)

The sum over A and B run over the M nuclei while the sum over i and j run over the N electrons. Hartree atomic units, = m = e = 1, will be used throughout. The rst two parts describe the kinetic energy of the electrons and nuclei respectively. The remaining three terms represent the attractive electrostatic (Coulomb) interaction between 9

the nuclei and the electrons and the repulsive potential due to the electron and nucleusnucleus interactions respectively [31]. The fundamental quantity in DFT is the electron density. This theory has made it possible to replace the complicated N -electron wave-function, and the associated Schrdinger equao tion as expressed in eqn. (2) by electronic density and its associated schemes. All aspects of the electronic structure of the system of interacting electrons in an external potential, are determined by the electronic charge density [32]. The Hohenberg-Kohn Theorems and the Kohn-Sham approach has been the building block that gave birth to the DFT theory. Hohenberg-Kohn [33] proved that the ground-state energy can be written as a unique functional of the electron density. Kohn-Sham [34] derived Schrdinger-like single-particle equations by introducing an energy functional for the total o energy of the electronic system which can be written as, 1 2 (r1 )(r2 ) + r12

E[] = T [] +

VN e (r)dr + Exc []

(4)

Eqn. (4) contains the individual contributions of the kinetic energy, T [], the classical Coulomb interaction, the attractive electrostatic interaction between the nuclei and the electrons and a term called the exchange-correlation energy that captures all many-body interaction. All quantities except for Exc [] are known and could be easily calculated from the wave-function of the non-interacting system. The exchange-correlation energy, Exc [], is the functional which contains everything that is unknown, and it is normally resolved through approximations. Therefore, when all the various contributions in Eqn. (4) are known, then the orbitals, including the ground state density and the ground state energy can be determined. There are basically dierent types of approximations involved in a DFT calculation for the unknown Exc [] functional. The approximation that is of interest in this research will involve constructing an expression for the unknown Exc [] functional, which contains all the manybody aspects of the problem [see. Eq.(4)] [19]. The approximations to be investigated are Local Density Approximation (LDA) and the Generalized Gradient Approximation (GGA). The results of the ground state properties of these approximations would be compared in this work.

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Local Density Approximation (LDA)

This is known as a local functional. It is the basis of all approximate exchange-correlation functions. At the center of this model is the idea of an uniform electron gas. A uniform electron gas is such in the limit N , V (where N is the number of electron and V is the volme), with density, = N , remaining nite and attains a constant value everywhere. V LDA assumes that the charge density of a non-uniform (inhomogeneous) systems is the same as the density of a uniform electron gas, where the charge density is the same in the entire space. The Exc [] functional, for the LDA is of the form
LDA Exc [] =

(r)xc (r)dr

(5)

where xc (r) is the exchange-correlation energy density of the uniform electron gas of density (r) [31].

Generalized Gradient Approximation (GGA)

This is known as the gradient-dependent functionals. The GGA depends not only on the density at a particular point r but also supplement the density with information about the gradient of the charge density, (r) in order to account for the non-homogeneity of the true electron density. GGA Exc [] functional can be expressed as
GGA Exc [ , ] =

f ( , , , )d(r)

(6)

As could be observed from Eqn. (6), the explicit dependence of this integrand f on the GGA desities and their gradients exit. In practice, Exc is usually split into its exchange and correlation contributions: GGA GGA GGA + Ec (7) Exc = Ex and approximations for the two terms are sought individually [31].

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Computational Implementation
The ab initio calculations will be implemented by the Vienna Ab-initio Simulation Package (VASP). Vasp is a package for performing ab-initio quantum-mechanical molecular dynamics (MD) using pseudopotentials and a plane wave basis set. It is a density functional code developed by Georg Kresse and Jrgen Furthmller [35]. u u

Plane Wave Pseudopotential Method

Ab initio electronic structure computations are carried out numerically using a basis set of orbitals. Basis set refers to the one-particle functions used to build molecular orbitals. A plane wave basis set method will be employed in this research work. This method is employed to expand the Kohn-Sham orbitals as it relies on the use of boundary conditions whereby the basic simulation cell is repeated periodically in all directions. The periodic boundary conditions allows the use of Bloch theorem whereby the electronic wave-function can be written as a product of a cell periodic part and a wavelike part given as: i (r) =
G

ci , Gei(K+G)r

(8)

where G are the reciprocal lattice vectors. The sum is truncated at a cut-o energy, Ecut = max|K + G|2 /2. The concept of pseudopotential is introduced in the use of the plane wave basis set to signicantly reduce the large number of plane waves which arise when the valence wave-functions oscillates rapidly within the core region due to the the orthogonalization of the core or inner electronic wave-functions. In using the pseudopotential, the inner electrons are ignored since they are inert and are not signicantly involved in bonding. Therefore, the use of an eective potential, a pseudopotential, that approximate the potential felt by the valence electrons ensures the a smaller number of plane wave basis states [35].

Motivation
The motivation is the search for a new novel spinel ultra-hard material that would be important for industrial applications both locally and abroad.

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