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Important Structure Types Important Structure Types 5/23/2013 L.Viciu| ACII| Imprtant structure types 1 A. Structures derived from cubic close packed 1. NaCl- rock salt 2. CaF2 – fluorite/Na2O- antifluorite 3. diamond 4. ZnS- blende B. Structures derived from hexagonal close packed 1. NiAs – nickel arsenide 2. ZnS – wurtzite 3. CdI2 – cadmium iodide 4. CdCl2 – cadmium chloride C. Non close packed structures 1. CsCl – cesium chloride 2. MoS2 - molybdenite D. Metal oxide structures 1. TiO2- rutile 2. ReO3 – rhenium trioxide 3. CaTiO3 – perovskite 4. MgAlO4 - Spinel 5/23/2013 L.Viciu| ACII| Imprtant structure types 2 Voids in f.c.c. structure • O Oh sites in f.c.c. arrangement of • T Td sites in the f.c.c . arrangement anions (fcc unit cell) of anions •4 Oh sites in total •8 Td sites in total 1 •Location: on the body diagonals – two • location: 12 1(centre) 4 on each body diagonal at ¼ of the 4 (edge) distance from each end. 5/23/2013 L.Viciu| ACII| Imprtant structure types 3 A-1. Rock salt: NaCl (halite), Sp. Group, Fm-3m Ionic structure r 1.81 Cl r 0.95 Na r Na 0.52 r Cl Red balls are Cl- + Purple balls are Na Edge shared Oh Na Oh coordinated Cl- form the c.c.p. array Na+ fills all the Oh holes while the Td holes are empty Na+: 8x1/8+6x ½= 4 Cl-: 12x ¼ +1=4 4 NaCl per unit cell 5/23/2013 L.Viciu| ACII| Imprtant structure types 4 Compounds with NaCl-rock salt structure • Halides: LiX, NaX, KX, RbX, AgX –except AgI • Oxides: MgO, CaO, SrO, BaO, TiO, MnO, FeO, CoO • Chalcogenides: MgS, CaS, MnS, MgSe, CaSe, CaTe, At room temperature, they are electrical insulators and transparent in the visible spectral region. At elevated temperatures, they could become ionic conductors, with the major contribution to charge transport from positive ion vacancy motion. 5/23/2013 L.Viciu| ACII| Imprtant structure types 5 A-2. CaF2-fluorite/Na2O antiflorite (Fm-3m) Ionic compound I. Ca2+ ions form the c.c.p. array - F fills all Td voids (Oh voids are empty) 2+ 1 Ca : 8 x /8 + 6 x ½ = 4 - F : 8 x 1=8 Edge shared FCa4 Td II. F- ions form a simple cubic array 2+ Ca – in the ½ of the cubic sites - 1 F : 8 x /8 +12 x ¼ + 6x ½ +1= 8 Ca2+: 4 x 1 = 4 4 CaF2 in the unit cell C.N.: Ca-8(cubic): F-4(Td) Corner shared CaF8 cubes In the Anti-Fluorite (Na2O) structure, Cation and Anion positions are reversed! 5/23/2013 L.Viciu| ACII| Imprtant structure types 6 Compounds with CaF2 (fluorite) and Na2O (antifluorite) structure: • Fluorite: Halides: SrF2, SrCl2, BaF2, BaCl2, CdF2, HgF2 Oxides: PbO2, CeO2, PrO2,ThO2 • Antifluorite: Oxides: Li2O, Na2O, K2O, Rb2O Chalcogenides: Li2S, Li2Se, Na2S, Na2Se, Na2Te, K2S, K2Se, K2Te Compounds with fluorite structure are ionic conductors: the charge is carried by anions The fluorite structure favors anion motion because the anions have less charge and are closer together than the cations 5/23/2013 L.Viciu| ACII| Imprtant structure types 7 Fluorite type compounds: Fast Ionic Conductors 2- ZrO2 stabilized with CaO or Y2O3: conduction through O High mobility of anion vacancies gives rise to fast ionic (anionic) conduction in fluorite type structure. Batteries = energy conversion + energy storage Solid oxide fuel cells = energy conversion http://www.gepower.com/research/seca/sofc_research.htm 8 A-3. Diamond Structure Covalent structure: the directionality of the covalent bonds dictates the crystal structure. C- hybridized sp3 ½ of the C form the c.c.p. array ½ of C fills ½ of the Td voids (Oh voids ½ 0,1 are empty) ¾ ¼ 1 0,1 ½ C: 8 x /8+6 x ½ = 4 ¼ ¾ C: 4 x 1 = 4 C.N.: 4 The most stable covalent structure 5/23/2013 L.Viciu| ACII| Imprtant structure types 9 Properties of diamond •High pressure allotrope of C (graphite diamond @80kbars) •Insulator (Eg = 5.4 eV) and transparent; color in diamonds originates from impurities i.e. colored diamond: • good thermal conductivity i.e. used in semiconductors industry to prevent them from overheating (thermal sink) • high refractive index and high optical dispersion(shine) 5/23/2013 L.Viciu| ACII| Imprtant structure types 10 Compounds with diamond like structure Group 4 of elements: Si, Ge and -Sn Lattice Melting Conductor? Eg(eV) constant (Å) Point (ºC) Carbon - 3.56 3550 Insulator 5.4 diamond radius Silicon 5.43 1410 Semiconductor 1.1 Germanium 5.66 940 Semiconductor 0.7 -Tin 6.49 230 Zero gap 0 semiconductor All have the cubic structures (space group: Fd-3m) Eg is inverse proportional with the bond lengths Longer bonds are weaker and the electrons are easily liberated small band gaps -Tin is the largest in the group weakest bonds (larger unit cell) 5/23/2013 L.Viciu| ACII| Imprtant structure types 11 Changing the motif in diamond structure diamond Zinc Blende 5/23/2013 L.Viciu| ACII| Imprtant structure types 12 A-4. ZnS- Zinc Blende (Sphalerite) Similar with diamond structure A Corner shared ZnS Td Red spheres – S2- 4 Layers of ZnS4 Td stacked Green spheres – Zn2+ ..ABCABC.. •S2- form the c.c.p. array •Zn2+ fills ½ of the Td voids (Oh voids are empty) • 1 S: 8 x /8+6 x ½ = 4 The crystal may be thought of as two interpenetrating •Zn: 4 x 1 = 4 fcc lattices, one for sulfur the other for zinc, with their •C.N.: 4 origins displaced by one quarter of a body diagonal. 5/23/2013 L.Viciu| ACII| Imprtant structure types 13 Compounds with Zinc Blende- type structure • CuF, CuCl, -CuBr, -CuI, -AgI This small cation structure is found for small metallic elements, which tend to form • -MnS red, -MnSe, BeS, , ZnS, strong sp3 covalent bonds. • -SiC, BN, BP • III-V compounds: GaP, GaAs, GaSb, InP, InAs, InSb Note: Crystals containing tetrahedral groups are often piezoelectric (a Td symmetry doesn’t have an inversion center). i.e. Zinc blende is piezoelectric Unstressed ZnS4 Td Stressed ZnS4 Td 5/23/2013 L.Viciu| ACII| Imprtant structure types 14 Most semiconductors of commercial importance are isomorphous with diamond and zinc blende Structure – electronic properties relations important for evaluating: Band gap Mobility 5/23/2013 L.Viciu| ACII| Imprtant structure types 15 Band Gap (Eg) -conductivity Eg / kT -mobility ~ e Eg-Band gap T- temperature K-Boltzman constant Eg increases with increasing the electronegativity difference between constituent ions. Generally, band gap and transparency are interconnected Band gap generally increases with ionicity Band gap increases with ionicity Covalent semiconductors have narrow Eg 16 5/23/2013 L.Viciu| ACII| Imprtant structure types Mobility () for rock salt and zinc blende type materials Eg / kT ~ e In materials free of defects, the mobility is determined by the effective mass interaction difference difference with lattice vibration 1. Mobility as the molecular weight (heavy mass gives low scattering) Electronegativity Compounds with ionic bonding have low electron mobility 2. Mobility as the electronegativity difference btw ions (polarization effect of mobile electrons or holes on the surrounding atoms) 17 5/23/2013 L.Viciu| ACII| Imprtant structure types Typical Semiconductors Silicon GaAs Diamond Cubic Structure ZnS (Zinc Blende) Structure 4 atoms at (0,0,0)+ FCC translations 4 Ga atoms at (0,0,0)+ FCC translations 4 atoms at (¼,¼,¼)+FCC translations 4 As atoms at (¼,¼,¼)+FCC translations Bonding: covalent Bonding: covalent, partially ionic 5/23/2013 L.Viciu| ACII| Imprtant structure types 18 Properties GaAs Si Crystal structure zinc blende diamond Lattice constant 5.6532 5.43095 Band gap (eV) at 300 K 1.424 (direct) 1.12 (indirect) Mobility (cm2/V.s) 8500 1500 Intrinsic carrier conc. (cm-3) 1.79x106 1.45x1010 Difficulty in growing stoichiometric GaAs crystals due to the loss of arsenic evaporation (>600ᵒ); also the crystals are very brittle crystal perfection and purity in silicon has reached levels never achieved with any other synthetic materials. 5/23/2013 L.Viciu| ACII| Imprtant structure types 19 • Why semiconductors have diamond or ZnS –blende structure? 5/23/2013 L.Viciu| ACII| Imprtant structure types 20 • Why semiconductors have diamond or ZnS –blende structure? Due to the covalent character of its bonding interaction (the lattice is always composed of those elements with the smallest difference in electronegativity). 5/23/2013 L.Viciu| ACII| Imprtant structure types 21 Structural Changing Graphite pressureDiamond Zinc blende type : InAs,CdS,CdSe pressure NaCl type 3 Graphite : C.N.= 3; dC-C = 1.415Å; =2.26g/cm 3 Diamond: C.N. = 4 dC-C = 1.54Å; = 3.51g/cm U. Müller-Inorganic Structural Chemistry • Pressure –coordination rule: “with increasing pressure an increase of the coordination number takes place” • Pressure-distance paradox: “when the coordination number increases according to the previous rule, the interatomic distances also increases” 5/23/2013 L.Viciu| ACII| Imprtant structure types 22 Voids in f.c.c. structure • O Oh sites in f.c.c. arrangement of • T Td sites in the f.c.c . arrangement anions (fcc unit cell) of anions •4 Oh sites in total •8 Td sites in total 1 •Location: on the body diagonals – two • location: 12 1(centre) 4 on each body diagonal at ¼ of the 4 (edge) distance from each end. 5/23/2013 L.Viciu| ACII| Imprtant structure types 23 Filling voids in c.c.p. structures CaF ZnS 2 all Td ½ Td Li3Bi NaCl ½ Td c.c.p. all Td and all Oh all Oh L.Viciu| ACII| Imprtant structure types 24 5/23/2013 Ulrich all Td sites filled Müller: “Inorganic structural chemistry” ½ of the Td sites filled ¼ of the Td sites filled Fig.
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