Solid State Chemistry and its Applications. Anthony R. WestЧитать онлайн книгу.

Perovskite‐rock salt intergrowth structures: K₂NiF₄, Ruddlesden–Popper, Aurivillius and Dion Jacobsen phases and layered cuprate superconductors

The K₂NiF₄ structure is the simplest structure of a large family of related materials that has attracted much attention in recent years because several of them are superconductors. The structure may be regarded as alternating layers of perovskite and rock salt structures, as shown in Fig. 1.50. The formula K₂NiF₄ could be written in expanded form as KNiF₃.KF to indicate the perovskite and rock salt components. The structure is body centred tetragonal with perovskite‐like layers of octahedra centred at c = 0 and c equals one half . K⁺ ions lie at the interface between rock salt and perovskite blocks and have a coordination number of 9. The coordination number of K in rock salt would be 12 but the rock salt blocks are less than one unit cell thick and the K coordination in rock salt is interrupted by the atomic displacements that generate perovskite blocks. The K₂NiF₄ structure occurs with a range of fluorides and chlorides containing small divalent cations, Table 1.26, and with a range of oxides with different charge combinations such as A₂ ⁺B⁶⁺O₄, A₂ ²⁺B⁴⁺O₄, A₂ ³⁺B²⁺O₄, A²⁺A′³⁺B³⁺O₄ and A₂ ³⁺B_1/2 +B′ _1/2 ³⁺ O ₄ containing large A and small B cations; probably other cation combinations are also possible.

Table 1.25 Examples of A, B, X combinations in garnets

Garnet	A	B	X	O
Grossular	Ca₃	Al₂	Si₃	O₁₂
Uvarovite	Ca₃	Cr₂	Si₃	O₁₂
Andradite	Ca₃	Fe₂	Si₃	O₁₂
Pyrope	Mg₃	Al₂	Si₃	O₁₂
Almandine	Fe₃	Al₂	Si₃	O₁₂
Spessartine	Mn₃	Al₂	Si₃	O₁₂
	Ca₃	CaZr	Ge₃	O₁₂
	Ca₃	Te₂	Zn₃	O₁₂
	Na₂Ca	Ti₂	Ge₃	O₁₂
	NaCa₂	Zn₂	V₃	O₁₂

A‐site cation ordering occurs in A⁺A′³⁺B⁴⁺O₄: A = Na, A′ = La → Lu, B = Ti; Na and the lanthanides occupy different layers in the c direction. Anion‐deficient and anion‐excess K₂NiF₄ structures exist. For example, in Sr₂XO₃: X = Cu, Pd, one‐quarter of the oxygens are removed, giving square planar coordination for X and seven‐coordinate Sr, whereas in La₂NiO_4+x, interstitial oxygens are present.

The Ruddlesden–Popper series of compounds have the K₂NiF₄ structure as their simplest family member; other family members exist with more layers in the perovskite blocks. Thus, with strontium titanates, a family of phases exists with general formula Sr_{n + 1}Ti_nO_{3n + 1} and consist of nSrTiO₃ perovskite blocks interleaved with SrO rock salt layers. Two members of this family are Sr₃Ti₂O₇ (n = 2) and Sr₄Ti₃O₁₀ (n = 3). The n = ∞ member corresponds to SrTiO₃ perovskite. These phases retain a tetragonal unit cell with similar a dimensions but have much longer c axes. A similar family of phases forms for La_{n + 1}Ni_nO_{3n + 1} : n = 1, 2, 3, ∞. In most cases, only one or two members of the Ruddlesden–Popper series are known, with examples such as

StartLayout 1st Row upper S r 3 normal upper B 2 normal upper O 7 colon normal upper B equals upper I r comma upper T i comma upper Z r comma upper C r comma upper F e 2nd Row upper C a 3 normal upper B 2 normal upper O 7 colon normal upper B equals upper M n comma upper T i 3rd Row upper S r 4 normal upper B 3 normal upper O 10 colon normal upper B equals upper I r comma upper T i comma upper Z n 4th Row upper C a 4 normal upper B 3 normal upper O 10 colon normal upper B equals upper M n comma upper T i 5th Row normal upper K 3 upper Z n 2 normal upper F 7 comma normal upper K 3 upper F e 2 normal upper F 7 comma upper R b 3 upper C d 2 normal upper F 7 comma normal upper K 3 upper M n 2 upper C l 7 comma upper R b 3 upper M n 2 upper C l 7 comma upper C s 3 upper C a 2 upper C l 7 6th Row upper R b 4 upper C d 3 upper C l 10 period EndLayout

A large and diverse family of Cu‐based perovskite‐rock salt intergrowth phases contains many examples of the high T _c cuprate superconductors. The key element for the superconductivity is Cu and it shows enormous structural diversity in the cuprates with coordination numbers ranging from 2 (linear) to 4 (square planar), 5 (pyramidal) and 6 (octahedral), as discussed in Section 8.3.6. In addition to YBa₂Cu₃O₇ and related materials which are basically oxygen‐deficient perovskites, Bi‐ and Tl‐based cuprates are perovskite–rock salt intergrowth phases with considerable compositional and structural complexity. The BiSCCO superconductors consist of three phases that are labelled according to their Bi:Sr:Ca:Cu ratios: 2201, 2212 and 2223. The 2212 phase (80 K superconductor), Bi₂Sr₂CaCu₂O₈ has rock salt‐like layers, Bi₂O₂, that separate double perovskite layers containing Cu in octahedral sites, whereas the 2223 phase (110 K superconductor) has triple perovskite layers. In these structures, SrO layers form a coherent interface between rock salt and perovskite components.

Schematic illustration of (a) the K2NiF4 structure. Schematic illustration of (b) the Bi2O2 layers that form part of the intergrowth structure of Aurivillius phases.

Figure 1.50 (a) The K2NiF4 structure. (b) The Bi2O2 layers that form part of the intergrowth structure

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