NON-CRYSTALLINE MATERIALS

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3.012 Fund of Mat Sci: Structure Lecture 21 NON-CRYSTALLINE MATERIALS Images of a silicon nanocrystal removed for copyright reasons. Light amplification for crystalline silicon in a glassy SiO 2 matrix

Homework for Fri Dec 2 Study: Chapter 2 of Allen-Thomas until 2.3.1

Last time: 1. Tensors, and their transformations 2. Orthogonal matrices 3. Neumann s principle 4. Symmetry constraints on physical properties 5. Curie s principle

Physical properties and their relation to symmetry Density (mass, from a certain volume) Pyroelectricity (polarization from temperature) Conductivity (current, from electric field) Piezoelectricity (polarization, from stress) Stiffness (strain, from stress)

Curie s Principle a crystal under an external influence will exhibit only those symmetry elements that are common to both the crystal and the perturbing influence

Loss of periodic order Liquids ( fluid ) Glasses ( solid ) Oxide glasses (continuous random networks) Polymeric glasses (self-avoiding random walks Oddballs Quasicrystals Superionics

Table of the applications of noncrystalline materials removed for copyright reasons.

Principle of operation of a CD-RW As Deposited (amorphous) After Initialisation/erase (crystalline) Written mark (amorphous) Erase/Write Readout of data: Difference in %R between amorphous & crystalline states E.g. %R amorphous = 5%; %R cryst = 25% Delta R=20% Figure by MIT OCW.

Principle of operation of a CD-RW Writing - Amorphous The active layer is heated above its melting point and quenched into the amorphous phase with a short laser pulse to produce marks. Erasure Crystalline Intermediate laser power is used, so that the active layer does not melt, but rather remains within the crystallization temperature region long enough that the amorphous marks re-crystallize. 800 C Liquid Melting temperature 800 C Liquid Melting temperature o C) 600 Quench o C) 600 Temperature ( 400 200 A B Amorphous Crystal 99% 1% Temperature ( 400 200 A B Crystallize 99% 1% Amorphous t min 0 10-2 10 0 10 2 10 4 10 6 10 8 10 10 Time (ns) t min 0 10-2 10 0 10 2 10 4 10 6 10 8 10 10 Time (ns) Figure by MIT OCW.

Erasure: nucleation and growth of crystalline material Figure by MIT OCW.

Te-Sb-Ge Alloy 3 Element Phase Diagram Nucleation dominated: 4.7 GB DVD-RAM (Sb 2 Te 3 to GeTe) Growth dominated: CD- RW, DVD-RW, Blu-ray (Sb 69 Te 31 eutectic) Sb 2 Te 3 30 Sb Atomic % 40 50 60 70 80 90 Sb 100 Growth dominated SbTeGe 20 10 Ge 0 0 10 20 30 40 50 60 70 80 90 100 GeTe Ge Atomic % Figure by MIT OCW.

Structural Descriptors Long-range order Short-range order

What do ice and silicon have in common? Source: Wikipedia

What do ice and silicon have in common? Photo courtesy of Ansgar Walk.

What do ice and silicon have in common? Figure by MIT OCW. Figure by MIT OCW.

What do ice and silicon have in common? Compression 11 GPa 13 GPa 16 GPa 36 GPa 42 GPa 79 GPa Si(I) diamond z= Si(II) β-tin z=6 Si(XI) Imma z=6 Si(V) hexagonal Si(VI) orthorhombic Si(VII) hcp Si(X) fcc z=8 z=10 z=12 z=12 Slow Pressure Release 9 GPa 2 GPa >480 K Si(II) β-tin Si(XII) R8 Si(III) BC-8 Si(IV) hex. diamond z=6 z= z= z= Fast Pressure Release Si(VIII) and Si(IX) tetragonal Figure by MIT OCW.

What do ice and silicon have in common? -7.84 Si 100 400 (Ry/atom) E structure -7.86-7.88 4 fcc 3 bcc hcp sc β-tin o C) Temperature ( 0-100 Liquid III Hexagonal Ice II V VI VII VIII X 300 200 Temperature (K) -7.90 2 Diamond Hexagonal Diamond 1-200 XI IX 100-7.92 0.6 0.7 0.8 0.9 1.0 1.1 Volume Figure by MIT OCW. Figure by MIT OCW. 0.1 1.0 10 100 Pressure (GPa) 0

Phase transitions in silicon Energy B A B A Volume

Order Parameters for Silicon 1 µ = θi N i 1 1 2 2 2 N i ¹ σ = θ µ Before compression During compression P = 40 GPa M. J. Demkowicz and A. S. Argon, Phys. Rev. Lett. 93, 25505 (2004)

Pair correlation functions Graphs of the pair-distribution functions for gas, liquid/gas, and monatomic crystal removed for copyright reasons. See page 41, Figure 2.5 in in Allen, S. M., and E. L. Thomas. The Structure of Materials. New York, NY: J. Wiley & Sons, 1999.

Pair correlation function: water Courtesy of Dr. J. Kolafa. Used with Permission. See animation at http://www.icpf.cas.cz/jiri/movies/water.htm.

Pair correlation function: water

Count thy neighbours Z r Thickness dr Y X Figure by MIT OCW.

Models of disorder: hard spheres Bernal random close packed sphere model Photos of the Bernal random close-packing model removed for copyright reasons. See them at the Science & Society Picture Library: Image 1, Image 2.

Models of disorder: hard spheres Voronoi polyhedra (in a crystal: Wigner- Seitz cell) Normal Distance Volume Facial Area Solid Angle Quantitative Definitions of Voronoi Polyhedra Figure by MIT OCW.

Mean Square Displacements

Mean Square Displacements

Mean Square Displacements