Report

Outline 1. 2. 3. 4. 5. 6. 7. 8. 9. Epitaxy in Semiconductor Crystal Growth Elastic Description of Strain in Cubic Semiconductor Crystals Atomistic Description of Strain Molecular Statics and Force Fields Keating's Valence Force Field Stillinger-Weber Potential Tersoff Potential Simulation of Nanostructures Piezoelectricity in Zincblende and Wurtzite crystals TMCS III, Leeds 18th Jan 2012 Slide 1 Semiconductors Group IV: Si, Ge, C Group III-V: GaAs, InAs, AlAs, GaP, InP, AlP, GaN, InN, AlN, GaSb, InSb, AlSb Group II-VI: CdSe, ZnSe, ZnS, CdS, MgSe, ZnTe InN TMCS III, Leeds 18th Jan 2012 Slide 2 Epitaxy Epitaxy: (Greek; epi "above" and taxis "in ordered manner") describes an ordered crystalline growth on a monocrystalline substrate. Homo-epitaxy (same layer and substrate material) Hetero-epitaxy (different layer and substrate material). In the Hetero-epitaxy case growth can be: Lattice Matched: same, or very close, lattice constant of layer and substrate e.g. GaSb/InAs or AlAs/GaAs Lattice Mismatched: different lattice constant of layer and substrate material e.g. InP/GaAs or InN/GaN. TMCS III, Leeds 18th Jan 2012 Slide 3 Lattice Matched and Mismatched Epitaxy Lattice Matched TMCS III, Leeds 18th Jan 2012 Lattice Mismatched Slide 4 Lattice Mismatched Epitaxy In lattice mismatched heteroepitaxy the layer material can be made to “adapt” (can become smaller or larger) its in plane lattice constant to match that of the substrate (pseudomorphic growth). Consequently volume conservation (though volume is not perfectly conserved) dictates that the lattice constant in the growth direction needs to become larger/smaller. In this way the lattice periodicity is maintained in the growth plane, but lost in the growth direction. Lattice Mismatched TMCS III, Leeds 18th Jan 2012 Slide 5 Quantum Mechanics in action Nanostructures: 2D Growth, 2D Growth + etching, 3D Growth 1D Quantum Well 2D Multi Quantum Wires In0.52Al0.48As AlAs AlAs In0.84Ga0.16As In0.52Al0.48As Taurino et al Mat Sci and Eng B, 67 (1999) 39 Growth direction Scanning Tunneling Microscopy TMCS III, Leeds 18th Jan 2012 Green: Free Carrier, Red: Confinement Slide 6 Outline 1. 2. 3. 4. 5. 6. 7. 8. 9. Epitaxy in Semiconductor Crystal Growth Elastic Description of Strain in Cubic Semiconductor Crystals Atomistic Description of Strain Molecular Statics and Force Fields Keating's Valence Force Field Stillinger-Weber Potential Tersoff Potential Simulation of Nanostructures Piezoelectricity in Zincblende and Wurtzite crystals TMCS III, Leeds 18th Jan 2012 Slide 7 Elastic Strain Semiconductors are produced by depositing liquid or gasses that when coalesce and solidify follow the crystal structure of the “seed”, usually a substrate of high crystalline quality. During this deposition, often done in very small amounts (low growth rate), as small as depositing one atomic layer at the time, if the layer material has a bulk lattice constant larger than the substrate, then the crystal will appear slightly deformed from its equilibrium state. We refer to this material as “strained”. z zˆ y yˆ xˆ Unstrained TMCS III, Leeds 18th Jan 2012 Strained x We chose the axes vectors x,y,z arbitrarily, but need to be linearly independent. Note that while the axes vectors are chosen to be unitary (in units of the lattice constant) in the unstrained case, the strained axes are not necessarily unitary. Slide 8 zˆ Elastic Strain This picture is general and valid for all types of crystals, not just simple cubic. z y yˆ xˆ Unstrained Strained x Unstrained and strained axis can be easily related: x 1 xx xˆ xy yˆ xz zˆ y yx xˆ 1 yy yˆ yz zˆ z zx xˆ zy yˆ 1 zz zˆ TMCS III, Leeds 18th Jan 2012 The numerical coefficient εij define the deformation of all the atoms in the Crystal. The diagonal terms εii control the length of the axis, while the off diagonal terms εij control the angles between the axis. Slide 9 Elastic Strain This set of equations are in the form of a mathematical entity called Tensor. x 1 xx xˆ xy yˆ xz zˆ The equations define the strained position of any atom within the crystal that upon strain moves from R to R’. z zˆ R Unstrained yˆ R y yx xˆ 1 yy yˆ yz zˆ z zx xˆ zy yˆ 1 zz zˆ Unstrained and strained positions are written in terms of the old and new axis: y R xˆ yˆ zˆ R xˆ yˆ zˆ xˆ TMCS III, Leeds 18th Jan 2012 Strained x Important: notice how the coefficients α,β,γ are the same in the unstrained and strained system Slide 10 Elastic Strain We now substitute the new axis with the expressions for the distortion: R xˆ yˆ zˆ x 1 xx xˆ xy yˆ xz zˆ y yx xˆ 1 yy yˆ yz zˆ z zx xˆ zy yˆ 1 zz zˆ After a little manipulation and taking into account the expression for R: R R xx yx zx xˆ xy yy xz yˆ xz yz zz zˆ Provided the original position and the distortion tensor are known, this expression gives a practical way of calculating the position of any atom inside a strained unit cell. TMCS III, Leeds 18th Jan 2012 Slide 11 Strain Components Often there is confusion between the terms strain and distortion. In this lectures we follow the notation used in Jasprit Singh’s book, for which the strain components eij are different from the distortion components but related to them by: e xx xx e yy yy e xy x y yx xy e zz zz e yz y z zy yz e xz x z zx xz The final expressions for the off-diagonal terms eij are an approximation in the limit of small strain. Dilation: expresses how much the volume of the unit cell changes, and in the limit of small strain is given by: e xx e yy e zz Biaxial Strain: expresses how much the unit cell is strained in the z direction compared to the x and y: ebx e zz 1 2 e xx e yy Uniaxial Strain: strain in one direction only, e.g. if eij= constant and eii=0 then the strain is uniaxial in the [111] TMCS III, Leeds 18th Jan 2012 Slide 12 Stress Components Stress components: the force components (per unit area) that causes the distortion of the unit cell. There are 9 components: Xx, Xy, Xz, Yx, Yy, Yz, Zx, Zy, Zz Capital letters: direction of the force Subscript: direction normal to the plane on which the stress is applied (x is normal to yz, y is normal to xz, z is normal to xy, ) zˆ xˆ Xx xy TMCS III, Leeds 18th Jan 2012 yˆ The number of independent components reduces when we consider that in cubic systems (like diamond or zincblende) there is no torque on the system (stress does not produce angular acceleration). Therefore Xy= Yx, Yz= Zy, Zx= Xz And we are only left with 6: Xx, Yy, Zz ; Yz, Zx, Xy Slide 13 Elastic constants The stress components are connected to the strain components via the small strain elastic constants: X x c11 e xx c12 e yy c13 e zz c14 e yz c15 e zx c16 e xy Y y c 21 e xx c 22 e yy c 23 e zz c 24 e yz c 25 e zx c 26 e xy Z z c 31 e xx c 32 e yy c 33 e zz c 34 e yz c 35 e zx c 36 e xy Y z c 41 e xx c 42 e yy c 43 e zz c 44 e yz c 45 e zx c 46 e xy Z x c 51 e xx c 52 e yy c 53 e zz c 54 e yz c 55 e zx c 56 e xy X y c 61 e xx c 62 e yy c 63 e zz c 64 e yz c 65 e zx c 66 e xy In practice we never have to deal with all 36 elastic constants. First of all it is always the case that cij=cji which reduced the total to 21. Second in real crystals, particularly cubic, the lattice symmetry reduces the number even more. Therefore in ZB we only have 3 independent constants: c11,c12,c44 In WZ there are 5: c11,c12,c13, c33, c44 TMCS III, Leeds 18th Jan 2012 Slide 14 Some more definitions Elastic strain energy density for ZB: U 1 2 c11 e xx e yy e zz c12 e xx e yy e xx e zz e zz e yy c 44 e xy e yz e xz 2 2 2 Bulk Modulus for ZB: 2 B 2 c11 2 c12 3 Shear Constant for ZB: C c11 c12 2 TMCS III, Leeds 18th Jan 2012 Slide 15 2 Properties of Semiconductors ZB Si Ge C Ga-As In-As Al-As Ga-P In-P Al-P Ga-N In-N Al-N Ga-Sb In-Sb Al-Sb a (Ǻ) 5.431 5.658 3.567 5.653 6.058 5.662 5.451 5.869 5.463 4.500 4.980 4.380 6.096 6.479 6.135 TMCS III, Leeds 18th Jan 2012 B (Mbar) 0.980 0.713 0.442 0.757 0.617 0.747 0.921 0.736 0.886 2.060 1.476 2.030 0.567 0.476 0.855 C’ (Mbar) 0.502 0.410 0.478 0.364 0.229 0.288 0.440 0.269 0.329 0.825 0.424 0.698 0.270 0.183 0.414 c11 c12 c44 (Mbar) (Mbar) (Mbar) 1.660 0.640 0.796 1.260 0.440 0.677 10.79 1.24 5.78 1.242 0.514 0.634 0.922 0.465 0.444 1.131 0.555 0.547 1.507 0.628 0.763 1.095 0.556 0.526 1.325 0.667 0.627 3.159 1.510 1.976 2.040 1.190 1.141 2.961 1.565 2.004 0.927 0.378 0.462 0.720 0.354 0.341 1.407 0.579 0.399 Slide 16 Strain in Lattice Mismatched Epitaxy Poisson ratio: is a measure of the tendency of materials to stretch in one direction when compressed in another. This ratio depends on the substrate orientation and the type of crystal. For cubic crystals including ZB: c11 [001] 2 c12 c11 2 c12 c 44 c11 c12 4 c 44 [111] Strain: in pseudomorphic growth one can consider, independent of the substrate orientation, strain to have only two components, one parallel to the growth plane and one perpendicular. e a Substrate a Layer 1 e e Important: in [001] growth: e = exx= eyy and e= ezz TMCS III, Leeds 18th Jan 2012 Slide 17 Strain in [111] pseudomorphically grown layers Important: in [111] growth the combination of e and e results in a strain tensor with exx = eyy = ezz and exy = exz = eyz The distortions in this case are: xx yy zz 2 1 2 c11 4 c12 4 c 44 e // 3 3 c11 2 c12 4 c 44 xy yz xz 1 1 2 c11 4 c12 4 c 44 e // 3 3 c11 2 c12 4 c 44 z [111] y (1,1,1) x TMCS III, Leeds 18th Jan 2012 Important: the distortions are expressed in the basis system where x, y and z are aligned with the [100], [010] and [001] directions. Instead e and e are defined so that they relate to strain in the (111) plane and the [111] direction, respectively. Slide 18 Outline 1. 2. 3. 4. 5. 6. 7. 8. 9. Epitaxy in Semiconductor Crystal Growth Elastic Description of Strain in Cubic Semiconductor Crystals Atomistic Description of Strain Molecular Statics and Force Fields Keating's Valence Force Field Stillinger-Weber Potential Tersoff Potential Simulation of Nanostructures Piezoelectricity in Zincblende and Wurtzite crystals TMCS III, Leeds 18th Jan 2012 Slide 19 Tetrahedral Bonding In the Zincblende crystal, just like in the diamond one, atoms bond together to form tetrahedrons. Hence the individual atomic orbitals merge to form sp3 hybrid orbitals TMCS III, Leeds 18th Jan 2012 Slide 20 Wurtzite While Zinblende is the preferred crystal structure of III-As, III-P and III-Sb, III-N tend to crystallize preferentially in hexagonal form. The hexagonal crystal with a two atom basis consisting of cations and anions is called Wurtzite. View from the top Perspective View Zincblende Wurtzite Two adjacent tetrahedrons overlap in the z direction in WZ but not in ZB. Hence second nearest neighbours in WZ are actually closer than in ZB at equilibrium. The modified inter-atomic forces result in a slight reduction of the interatomic distance between the first nearest neighbours. TMCS III, Leeds 18th Jan 2012 Slide 21 The 7th elastic parameter Is a description based on 6 strain components enough to describe all deformations in a ZB or WZ crystals? The distance that the atom is displaced by is characterized by the Kleinman parameter z a 4 With a the lattice constant and γ the shear strain. This results in a crystal where the atomic bonds are not all of the same length. Strain in the [111] TMCS III, Leeds 18th Jan 2012 + + + + Only 3 identical sp3 orbitals Slide 22 Strain from atomic positions Given the 5 coordinates of the atoms in a tetrahedron how do we reverse engineer the strain? 1 xx yx zx 1 xx yx zx xy xz x1 1 yy yz zy 1 zz x1' ' y1 y1 z z' 1 1 1 xx yx zx xy xz x 0 1 yy yz zy 1 zz xy x 0' ' y0 y0 z z' 0 0 xz x 2 1 yy yz zy 1 zz x 2' ' y2 y2 z z' 2 2 This become a simple system of linear equations easily solvable. The solution gives the 6 components of the strain tensor. However the deformation on the position of the yellow atom, dependant on the Keinman parameter, is still undetermined and requires a separate calculation. TMCS III, Leeds 18th Jan 2012 Slide 23 The issue of local/global composition Furthermore strain is a relative property (variation of e.g. bond length compared to an initial state). Microscopists refer to strain as difference in the bond lengths compared to the host. Theorists think of strain as deformation of a material from its bulk state. Everyone else does not usually know what they are talking about!! If dealing with an alloy and if wanting to take the theorist approach, one needs to know what the lattice constant of the alloy is. But what does composition mean? It makes sense for a large uniform block, not for non uniform. We take the approach of counting atoms up to second nearest neighbour form the centre of the tetrahedron TMCS III, Leeds 18th Jan 2012 Slide 24 Outline 1. 2. 3. 4. 5. 6. 7. 8. 9. Epitaxy in Semiconductor Crystal Growth Elastic Description of Strain in Cubic Semiconductor Crystals Atomistic Description of Strain Molecular Statics and Force Fields Keating's Valence Force Field Stillinger-Weber Potential Tersoff Potential Simulation of Nanostructures Piezoelectricity in Zincblende and Wurtzite crystals TMCS III, Leeds 18th Jan 2012 Slide 25 Modelling Strain in Real Structures Because of its impact on the electronic properties strain in semiconductor nanostructures always needs to be evaluated with the highest possible accuracy. Measurements (usually involving electron microscopy analysis) are not usually sufficiently accurate, so modelling is the only viable alternative. Simple elasticity formulas are acceptable when dealing with standard cases where strains are uniform or approximating strains as uniform is acceptable, e.g. a simple quantum well. They become useless however in complex quantum well structures, wires and dots where strains are non uniform. In time several methods have been developed ranging from continuum, finite element, analytic and atomistic. Atomistic methods are now widely used for quantum dots while continuum methods are the preferred methods for quantum wells. TMCS III, Leeds 18th Jan 2012 Slide 26 Molecular Dynamics • Molecular Dynamics is a computer simulation in which a starting set of atoms or molecules is made to interact for a period of time following the laws of Physics (e.g Newton’s Laws). • In Semiconductor science one can build an atomistic model of a strained crystal but if the strain is not known a priori then atoms are not going to be in their equilibrium positions. • Then their motion paths are dictated by the “force field” generated by the potential of the solid. TMCS III, Leeds 18th Jan 2012 Slide 27 Molecular Dynamics Initial Position of the atoms r0i Potential V (r0i) Forces F=-grad V (r0i) Velocities and acceleration Evaluate the positions after Δt Repeat till Forces are low Often the simulation does not require very large atomic motion. For instance for calculating strain one might only want to allow small atomic displacements from the crystal structure, without atom switching. When Energy minimisation is the fundamental criterion and forces are used to direct the geometry optimisation rather than predicting the final positions, we are using a “Molecular Statics” simulation. TMCS III, Leeds 18th Jan 2012 Slide 28 Outline 1. 2. 3. 4. 5. 6. 7. 8. 9. Epitaxy in Semiconductor Crystal Growth Elastic Description of Strain in Cubic Semiconductor Crystals Atomistic Description of Strain Molecular Statics and Force Fields Keating's Valence Force Field Stillinger-Weber Potential Tersoff Potential Simulation of Nanostructures Piezoelectricity in Zincblende and Wurtzite crystals TMCS III, Leeds 18th Jan 2012 Slide 29 Valence Force Field The “force field” that is generated by the potential of the atoms in the solid can be represented as a 3 body potential. In the Keating's Valence Force Field: The Potential is the sum of the potential energy between the pairs of atoms i and j (two VV F F V 2 ( R i R j ) V 3 (ˆijk ) ij ij body), plus a term that depends on the angle between i,j and a nn 3 ij 2 1 third atom k (three body). 2 0 2 V2 ( R R ) ( d ) i j ij 0 2 Rj 2 8 (d ) i V3 j nn 1 2 i ij 3 i , jk ( R j R i ) ( R k R i ) ( d ) cos 0 j ,k i 8 ( d ) 0 ij 2 0 ij 2 2 jki j i Ri k k k dij0 is the unstrained bond length of atoms i and j and 0 is the unstrained bond angle (e.g. for zinc-blend cos0=-1/3), and ijk is the angle between atoms i, j and k. The local chemistry is contained in the parameters and , which are fitted to the elastic constants P.N. Keating, Phys. Rev. 145, 637 (1966) TMCS III, Leeds 18th Jan 2012 Rk Slide 30 Valence Force Field The VFF is widely used for all types of nanostructures. VFF is basically a parabolic approximation to the potential of solids V(R) Ω is the volume occupied by one atom R0 2 Uniform: same distortion in x,y and z B R 1 d E dv 2 E Ecoh 1 3 R v R 1 Binding Energy The main limitation is that there are only 2 parameters ( and ) but 3 elastic constants even for Zincblende!!! Non Uniform: z stretch, x,y compress (by the same amount) and viceversa 2 C ' 1 d E d c11 a 3 c12 c 44 TMCS III, Leeds 18th Jan 2012 1 a 4 1 R y R y / (1 ) 1 Rz Rz a E Ecoh R x R x (1 ) 1 1 2 Slide 31 Progress in Valence Force Field Anharmonicity correction: • Ability to reproduce anharmonic effects is linked to the quality of prediction of the phonon spectrum. • Some progress has been presented (e.g. Lazarenkova et al, Superlattices and Microstructures 34, 553 (2003)). • Not clear why phonon frequencies, elastic constants and mode Grüneisen parameters are not correlated (Porter et al J. Appl. Phys. 81, 96 (1997)). • For Ionicity in Zincblende to solve this problem check recent P. Han and G. Bester, Phys. Rev. B 83 174304 (2011) Distance between 2 ions, one of which is in the central cell U c 1 2 Z Z e l 2 l 0 , 0 rs Ionicity and Wurtzite: • Empirical potentials were historically developed for Si and Ge (pure covalent bonds) • III-V are mainly covalent, partially ionic. II-VI are both covalent and ionic • Only for infinite crystals or systems were the charge is uniformly distributed this it’s not a big deal. • Important in III-N WZ (Grosse and Neugebauer, PRB 63, 085207 (2001)), and can be incorporated following Ewald summation scheme (codes available). • Also check Camacho et al (Physica E, Vol. 42, p. 1361 (2010)) “application of Keating’s valence force field to non–ideal wurtzite materials” TMCS III, Leeds 18th Jan 2012 Slide 32 Outline 1. 2. 3. 4. 5. 6. 7. 8. 9. Epitaxy in Semiconductor Crystal Growth Elastic Description of Strain in Cubic Semiconductor Crystals Atomistic Description of Strain Molecular Statics and Force Fields Keating's Valence Force Field Stillinger-Weber Potential Tersoff Potential Simulation of Nanostructures Piezoelectricity in Zincblende and Wurtzite crystals TMCS III, Leeds 18th Jan 2012 Slide 33 Stillinger-Weber The “force field” that is generated by the potential of the atoms in the solid can be represented as a 3 body potential. In the Stillinger-Weber potential: The Potential is the sum of the 2 nn nn potential energy between the 1 V SW V 2 ( rij ) V 3 ( rij ) cos ijk pairs of atoms i and j (two 3 ij ijk body), plus a term that depends 1 nn on the angle between i,j and a 1 rij a p q V 2 A B rij rij e third atom k (three body). 2 i j Rj j This in an adaptation of the well known Lennard-Jones potential used for liquefied noble gasses. jki Ri i 2 1 1 nn Rk rij a rik a 1 1 V3 e cos ijk k k 2 i j ,k i 3 k This potential works very well for Si in diamond structure where the bond angle cos0=-1/3. The local chemistry is contained in the parameters A, B , p, q , a, λ and γ which are fitted to various material properties. F. Stillinger and T. A. Weber, Phys. Rev. B 31, 5262 (1985) TMCS III, Leeds 18th Jan 2012 Slide 34 Stillinger-Weber The SW is not as widely used as VFF, but it has his niche (thermodynamics of Si mainly). In a way it should perform much better than VFF as it is not a parabolic approximation to the potential of solids. Parameterisations take into account the crystal phase diagram and check that diamond is the lowest energy structure Works reasonably well for diamond-Si but not for other crystal structures. TMCS III, Leeds 18th Jan 2012 Slide 35 Outline 1. 2. 3. 4. 5. 6. 7. 8. 9. Epitaxy in Semiconductor Crystal Growth Elastic Description of Strain in Cubic Semiconductor Crystals Atomistic Description of Strain Molecular Statics and Force Fields Keating Valence Force Field Stillinger-Weber Potential Tersoff Potential Simulation of Nanostructures Piezoelectricity in Zincblende and Wurtzite crystals TMCS III, Leeds 18th Jan 2012 Slide 36 Tersoff Potential The “force field” that is generated by the potential of the atoms in the solid can be represented as a 3 body potential. In the Tersoff potential: The Potential is the sum of the potential energy between the ij ( rij re ) ij ( rij re ) pairs of atoms i and j (two body), V ij Aij e bij B ij e multiplied times a term (bij) that depends on the angle between i,j and a third atom k (three body). bij 1 ij ij Rj 1 2 ni ni The expression for bij (known as bond order) is written as to emulate the atomic coordination number Z. Hence ζ is sometimes called the pseudo-coordination. ij jki j i k k i, j g(θ) and ω describe the angular and radial forces dependence. g ( ijk ) 1 ci di 2 2 ci d i ( h i cos jki ) 2 TMCS III, Leeds 18th Jan 2012 2 ijk e Rk k k f c ( rik ) g ( ijk ) ijk Ri 3 ( rij rik ) 3 Slide 37 Tersoff Potential g ( ijk ) 1 jki ci di 2 2 ci d i ( h i cos jki ) 2 ijk e 2 ω g j 3 ( rij rik ) 3 i k k k θeq θ 3 ( rij rik ) 3 angular forces: resistance to bend radial forces: resistance to stretch • When fitting to Bulk Modulus g(θ) is always g(θeq) and ωijk==1 • When fitting to Shear Constant g(θ)≠ (θeq) but ωijk==1 • When fitting c44 then both g(θ) ≠ (θeq) and ωijk ≠ 1 • Hence the Kleinman parameter links angular and radial forces!!! TMCS III, Leeds 18th Jan 2012 Slide 38 Tersoff Potential This potential describes covalent bonding and works very well for different crystal structures for group IV and despite the partial ionicity of the bond, group III-V. The local chemistry is contained in the parameters A, B , re, α, β , γ, c, d, h, n and λ, which are fitted to various material properties. J. Tersoff, Phys Rev Lett 56, 632 (1986) & Phys Rev B 39, 5566 (1989) Sayed et al, Nuclear Instruments and Methods in Physics Research 102, 232 (1995) TMCS III, Leeds 18th Jan 2012 Slide 39 Tersoff Potential The TP is not as widely used as VFF, but its use is rapidly increasing as parameterizations are improved. Again it should perform much better than VFF as it is not a parabolic approximation to the potential of solids. As there are many parameters, parameterisations can take into account many things, including the crystal phase diagram, all the cohesive and elastic properties and many more. 2 c 44 1 d E coh d 2 E E coh R x R x R y R y R y R z R z Works rather well for zincblende and diamond group IV and III-V but it is not yet optimized for thermodynamic and vibrational properties. D. Powell, M.A. Migliorato and A.G. Cullis, Phys. Rev. B 75, 115202 (2007) TMCS III, Leeds 18th Jan 2012 Slide 40 Progress in Tersoff The Kleinman parameter • The many parameters need putting to good use. • Kleinman deformation is critical because expresses the balance between radial and angular forces (Powell et al PRB 75, 115202 (2007)) hydrostatic distortion 0.00 sublattice displacement 0.9 0.02 0.04 0.06 0.08 0.10 circles: InAs squares: GaAs DFT 0.8 0.7 0.6 Tersoff 0.5 0.4 0.3 DFT Range of physical shear strains 0.2 0.00 0.02 0.04 0.06 shear distortion 0.08 0.10 Tersoff Ionicity and Phonons • Ionicity, like VFF, is missing. • Crystal growth only possible if ionic contribution is included (Nakamura et al J. Cryst. Growth 209, 232 (2000) • Phonons are still independent of elastic constants (Powell et al, Physica E 32, 270th(2006) TMCS III, Leeds 18 Jan 2012 Slide 41 Beyond Tersoff: bond order potentials Π versus σ –bonding • Tersoff neglects Π–bonding. Is it of consequence? • Tersoff can to some extent reproduce surface reconstruction energies (Hammerschmidt, PhD thesis) Beyond σ -bonding 1 bij 1 ij ij ni g ( ijk ) 1 ci di 2 ni ij f c ( rik ) g ( ijk ) ijk k i, j 2 2 ci d i ( h i cos jki ) 2 2 ijk e 3 ( rij rik ) 3 • It is generally possible to rewrite the bij with expressions directly obtained from tight binding. (D.G. Pettifor, “Many atom Interactions in Solids”, Springer Proceedings in Physics 48, 1990, pag 64)) • In this way the “bond order” can be explicitly obtained analytically to any order (Murdick et al, PRB 73, 045206 (2006)). • The second moment approximation is essentially equivalent to Tersoff (Conrad and Scheerschmidt, PRB 58, 4538 (1998)) TMCS III, Leeds 18th Jan 2012 Slide 42 Outline 1. 2. 3. 4. 5. 6. 7. 8. 9. Epitaxy in Semiconductor Crystal Growth Elastic Description of Strain in Cubic Semiconductor Crystals Atomistic Description of Strain Molecular Statics and Force Fields Keating's Valence Force Field Stillinger-Weber Potential Tersoff Potential Simulation of Nanostructures Piezoelectricity in Zincblende and Wurtzite crystals TMCS III, Leeds 18th Jan 2012 Slide 43 General Tips for MD Building Models: • If possible try and use existing software • Try and guess final positions: it saves a lot of computational time Empirical Potentials: • Codes that use VFF, SW and Tersoff are usually freely available! • IMD (Stuttgart), CPMD (IBM-Zurich) are parallel (for running on clusters) and open source • Nemo3 (Purdue) uses VFF • Always check what version of the potentials are being used!! Molecular Statics: • Make sure that the parameters that control the length of time the simulation is running for are set to reasonable values • Build your simulation up in size to see what you can get away with in terms of system sizes and check that results do not depend on the size chosen Strain: • Good strain algorithms exist and are freely available • If you write your own you need a nearest neighbour list. Usually MD produces one Gridding: • Strain is first obtained onto the atomic grid. Then to use it often it needs converting to an ordered grid. One can use various methods like Gaussian smoothing or weighted average. TMCS III, Leeds 18th Jan 2012 Slide 44 MD of QDs using Tersoff Potential After MD Before MD 300 300 -0.06500 -0.06690 250 -0.05500 250 -0.05690 -0.04500 -0.03500 -0.04690 200 200 -0.04500 -0.02500 -0.03690 -0.006900 150 -0.02690 [001] Å [001] Å 0.01500 -0.01500 150 0.005000 -0.05500 -0.05500 -0.01690 100 100 -0.02500 -0.005000 -0.005000 -0.01500 -0.03500 0.005000 0.01500 -0.006900 0.02500 0.005000 50 εxx 0.03500 50 2.000E-4 0.04500 50 100 150 200 250 300 50 350 100 150 [010] Å 200 250 300 350 [001] Å 300 300 0.001500 -0.09850 -0.06690 -0.08850 250 250 -0.07850 -0.05690 [001] Å -0.04690 -0.04690 -0.05690 -0.01690 -0.006900 150 -0.03850 -0.04850 -0.03690 -0.02690 -0.02690 -0.03690 100 -0.06850 -0.05850 200 [001] Å Floating 200 0.01150 -0.01690 -0.04850 -0.03850 150 εyy -0.02850 -0.008500 -0.01850 -0.02850 -0.01850 100 -0.008500 0.001500 -0.006900 0.01150 50 50 2.000E-4 0.02150 0.02900 0.001500 50 100 150 200 250 300 350 50 100 150 [010] Å 200 250 300 350 [010] Å 300 300 -0.09800 -0.008000 -0.02175 -0.08800 -0.01175 -0.07800 -0.001750 250 250 0.008250 PBC -0.03800 0.02825 200 -0.02800 0.002000 0.01200 0.02200 0.06825 0.07825 [001] Å [001] Å 0.04825 150 150 0.08825 0.05825 100 0.1082 100 -0.01800 -0.008000 0.002000 0.01200 0.02200 0.03200 0.03200 0.04200 0.09825 -0.03800 -0.02800 200 0.03825 0.05825 -0.05800 -0.04800 0.01825 0.05825 -0.06800 -0.01800 0.04200 -0.008000 -0.01800 0.07200 0.08200 0.1282 0.1382 Fixed 50 100 150 200 [010] Å TMCS III, Leeds 18th Jan 2012 50 0.002000 0.002000 0.1482 0.1500 250 300 350 0.05200 0.06200 0.1182 50 0.04200 0.09200 0.1020 0.1120 0.1220 0.002000 50 100 0.1320 150 200 250 300 350 [010] Å Slide 45 0.1420 0.1500 εz z Outline 1. 2. 3. 4. 5. 6. 7. 8. 9. Epitaxy in Semiconductor Crystal Growth Elastic Description of Strain in Cubic Semiconductor Crystals Atomistic Description of Strain Molecular Statics and Force Fields Keating's Valence Force Field Stillinger-Weber Potential Tersoff Potential Simulation of Nanostructures Piezoelectricity in Zincblende and Wurtzite crystals TMCS III, Leeds 18th Jan 2012 Slide 46 Kleinman Parameter 2 c 44 1 d E coh d 2 E E coh R x R x R y R y R y R z R z The distance that the atom is displaced by is characterized by the Kleinman parameter z a 4 With a the lattice constant and γ the shear strain. This results in a crystal where the atomic bonds are not all of the same length. TMCS III, Leeds 18th Jan 2012 Slide 47 Piezoelectricity In the case of a uniaxial distortion the displacement is in the [111] direction, and can still be characterized by the Kleinman parameter R x R x R y R z 2 2 2 Ry 2 Rx R y Rx 4 identical sp3 orbitals 2 2 Rz xy z Rz 4 R y Rz + a Strain in the [111] - + + + + + + + Only 3 identical sp3 orbitals The displacement of cations relative to anions in III-V semiconductors results in the creation of electric dipoles in the polar direction which in ZB is the direction that lacks inversion symmetry. TMCS III, Leeds 18th Jan 2012 Slide 48 Piezoelectricity in Zincblende The effect can be quantified by writing a general expression for the polarization as a function of the so called “piezoelectric coefficients” and the distortion components. Px e xkl kl Convention is: xx=1, yy=2, zz=3, yz=4, zx=5, xy=6 e ykl kl In ZB, for symmetry, the only non zero coefficients are e14= e25= e36 e zkl kl k ,l x , y , z Py k ,l x , y , z Pz k ,l x , y , z P e14 yz zy zx xz xy yx In actual fact this picture is incomplete as only includes coefficients linked to linear terms in the strain. In the past 6 years the importance of including also coeffiecients linked to quadratic terms in the strain (e.g. xx2 or xy xz ) has been highlighted (so called non linear or second order Piezo effect). • M.A. Migliorato et al, Phys. Rev. B 74, 245332 (2006) • L. C. Lew Yan Voon and M. Willatzen, J. Appl. Phys. 109, 031101 (2011) REVIEW • A. Beya-Wakata et al, Phys. Rev. B 84, 195207 (2011) TMCS III, Leeds 18th Jan 2012 Slide 49 Piezoelectricity in Wurtzite Zincblende Wurtzite Spontaneous polarization Strain induced polarization Quadratic terms in the strain (e.g. xx2 or xy xz ) are also important. There is still some controversy between the early accepted values of mainly for the spontaneous polarization coefficients • L. C. Lew Yan Voon and M. Willatzen, J. Appl. Phys. 109, 031101 (2011) REVIEW • J. Pal et al, Phys. Rev. B 84, 085211 (2011) TMCS III, Leeds 18th Jan 2012 Thank you!!! Acknowledgments: Joydeep Pal , Umberto Monteverde, Geoffrey Tse, Vesel Haxha, Raman Garg (University of Manchester) Dave Powell (University of Sheffield) GP Srivastava (University of Exeter) TMCS III, Leeds 18th Jan 2012 Slide 51