tools to model inorganic crystal structures
TRANSCRIPT
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CRYSTAL STRUCTURES
Ti
Ti
Ti
Ti
Ca
Ti
Ti
Ti
Ti
Atoms
Coordinationpolyhedra Cages of zeolites
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TETRAHEDRAL / OCTAHEDRAL MODULES
T O TO
+ =
TOT beams
biopyriboles
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BIOPYRIBOLES
amphibole
chesterite
jimthompsonite
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Cubic and Hexagonalperovskites
Cubic ABCPolytype 3C
Hexagonal ACPolytype 2H
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PEROVSKITE MODULES AND TECHNOLOGY
Ti
Ti
Ti
Ti
Ca
Ti
Ti
Ti
Ti
Modules of perovskite-type structure alternated with other modules occur in
materials of interest for science and technology → hybrid or intergrowth
perovskites
Three-dimensional (sharing of corners along three directions)
Two-dimensional (sharing of corners along two directions)
Mono-dimensional (sharing of corners along one direction)
Zero-dimensional (isolated octahedra)
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PEROVSKITE MODULES AND TECHNOLOGY
Projection in the planes (100), (1-10) and (001), in the order, of the octahedral sheets stacked along [001], [111], and [110]. Different periodicities in the stacked planes are selective of the interlayer.
[001] [111] [110]
(100) (1-10) (001)
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PEROVSKITE MODULES AND TECHNOLOGY
TlBa2Can-1CunO2n+3 tallium cuprate series of superconductors
n = 31223
n = 4 1234
n = 51245
n = 1121
n = 21212
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PEROVSKITE MODULES AND TECHNOLOGYTl2Ba2Can-1CunO2n+4 tallium cuprate series of
superconductors
n = 1221 n = 2
2212
n = 32223 n = 4
2234
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PEROVSKITE MODULES AND TECHNOLOGY
SUPERCONDUCTING OXYCARBONATES
Polysomatic series (Sr2CuO2CO3)m(XpSr2CuO5)n (m > n) based on (001) perovskite layers connected by CO3 groups
A
B
CuO2
Sr2CO3
CuO2
SrO
XO
SrO
A
B
CuO2
Sr2CO3
CuO2
SrO
XO
SrO
m = 1 n = 1m = 1 n = 0 m = 2 n = 1
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PEROVSKITE MODULES AND TECHNOLOGYORGANIC-INORGANIC HYBRID PEROVSKITES
(RNH3)2An-1BnX3n+1 series based on (001) layersEngineering in the (C4H9NH3)2(CH3NH3)n-1SnnI3n+1 polysomatic series1. n =1 → large band gap semiconductor2. The resistivity decreases by increasing n3. Metallic behaviour for n ≥ 34. The n = ∞ material (CH3NH3)SnI is a p-type metalNon-linear optical properties and electroluminescence
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PEROVSKITE MODULES AND TECHNOLOGYORGANIC-INORGANIC HYBRID PEROVSKITES
A'2AmBmX3m+2 (n = 1, 2, 3) series based on (110) layers
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PEROVSKITE MODULES AND TECHNOLOGYORGANIC-INORGANIC HYBRID PEROVSKITES
A'2Aq-1BqX3q+3 (n = 1, 2, 3) series based on (111) layers
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Perovskite modules (anion)intercalated with organic molecules (cation).
Combining properties of the organic part (e.g., luminescence andplastic) with those of the inorganic part (e.g., electrical and
mechanical). Tailoring can play on:
Nature of the A (dodecahedral) and B (octahedral) cations.Nature of the X anion (usually a halide).Orientation and thickness of the perovskite layer.
Series of organic-inorganic layered perovskites can be built by:1. Keeping fix the perovskite layer and changing organic interlayer;2. Keeping fix the interlayer and changing the thickness of perovskite;3. Varying the thickness of both layers.
PEROVSKITE MODULES AND TECHNOLOGYORGANIC-INORGANIC HYBRID PEROVSKITES
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PEROVSKITE MODULES AND TECHNOLOGY
An+1BnX3n+1 polysomatic series (Ruddlesden-Popper series) n (001) perovskite layers alternate with one sodium-chloride-like layer
On (La,Ba)2CuO4 (n = 1) Bednorz and Müller (1986) discovered high-Tc superconductivity with Tc ~ 30 K.
Sr1.8La1.2Mn2O7 (n = 2) shows colossal magnetoresistance.
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LEFT - Palmierite-type structure = 9Rperovskite with partial filling oftetrahedral and octahedral sites.
RIGHT – Alternation of palmierite-typeand 2H-perovskite modules
PALMIERITE TYPE
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MAGNETOPLUMBITE-TYPE
(111) spinel layers
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T+O+T
TETRAHEDRAL / OCTAHEDRAL MODULESLAYER SILICATES
chloritetalc
mica
+ empty interlayer+ cations
+ O layer
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TOT MODULES AND TECHNOLOGY
PILLARED CLAYS
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MODULES IN REAL STRUCTURES
talc
ph
phengite
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MICA (module M) BAFERTISITE (module B)
ASTROPHYLLITE (B1M1)NAFERTISITE (B1M2)
HETEROPHYLLOSILICATESA row of Ti polyhedra periodically substitutes a row of Sitetrahedra in a TOT layer. Three types of HOH layers are
known. BmMn polysomatic series.
+ Ti octahedra (pyramids) =
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MEMBERS OF THE BmMn SERIES
B1M0 bafertisite
Ba2{(Fe,Mn)4[Ti2O2(O,OH)2Si4O14](O,OH)2}
B1M1 astrophyllite
(K,Na)3(Fe,Mn)7[Ti2O3Si8O24](O,OH)4
I2+nY4+3n[Ti2(O)2+pSi4+4nO14+10n](O)2+2n
B1M2 nafertisite
(Na,K,�)4(Fe2+,Fe3+,�)10[Ti2O3Si12O34](O,OH)6
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HOH MODULES AND TECHNOLOGYPILLARED HETEROPHYLLOSILICATES?
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PALYSEPIOLES
sepiolite palygorskite kalifersite
Indigofera suffruticosa
+
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