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Oxide Thermoelectric Materials: A Structure–Property Relationship

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Abstract

Recent demand for thermoelectric materials for power harvesting from automobile and industrial waste heat requires oxide materials because of their potential advantages over intermetallic alloys in terms of chemical and thermal stability at high temperatures. Achievement of thermoelectric figure of merit equivalent to unity (ZT ≈ 1) for transition-metal oxides necessitates a second look at the fundamental theory on the basis of the structure–property relationship giving rise to electron correlation accompanied by spin fluctuation. Promising transition-metal oxides based on wide-bandgap semiconductors, perovskite and layered oxides have been studied as potential candidate n- and p-type materials. This paper reviews the correlation between the crystal structure and thermoelectric properties of transition-metal oxides. The crystal-site-dependent electronic configuration and spin degeneracy to control the thermopower and electron–phonon interaction leading to polaron hopping to control electrical conductivity is discussed. Crystal structure tailoring leading to phonon scattering at interfaces and nanograin domains to achieve low thermal conductivity is also highlighted.

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Abbreviations

Z :

Figure of merit

T :

Absolute temperature

ZT :

Dimensionless figure of merit

S :

Seebeck coefficient

σ :

Electrical conductivity

κ :

Thermal conductivity

η :

Conversion efficiency

T h :

Hot-side temperature

T c :

Cold-side temperature

T m :

Mean temperature

k B :

Boltzmann constant

n :

Number of charge carriers

e :

Electronic charge

μ c :

Chemical potential

H :

Heat transport per particle

s :

Configurational entropy

E :

Internal energy

V :

Internal volume

g :

Electronic degeneracy

N v :

Number of available sites

ρ :

Ratio of charge carriers to sites

U 0 :

On-site Coulomb interaction

ν ph :

Optical-phonon frequency

N TM :

Number of transition-metal ions per unit volume

R :

Average hopping distance

M v :

Ratio of transition-metal ion concentration

α :

Electron wavefunction decay constant

W :

Activation for conduction

θ D :

Debye temperature

h :

Planck’s constant

W h :

Polaron hopping energy

W d :

Disorder energy

N(E F):

Density of states at the Fermi level

κ el :

Electronic contribution to thermal conductivity

κ lattice :

Lattice component of thermal conductivity

L :

Lorenz factor

C V :

Specific heat per unit volume

ν s :

Velocity of sound

τ :

Phonon relaxation time

l ph :

Phonon mean free path

R O :

Radius of oxygen

R A :

Radius of A cation

R B :

Radius of B cation

t :

Tolerance factor

m * :

Effective mass

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Nag, A., Shubha, V. Oxide Thermoelectric Materials: A Structure–Property Relationship. J. Electron. Mater. 43, 962–977 (2014). https://doi.org/10.1007/s11664-014-3024-6

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