Literature review

Richard and Fine (1948) first generalized the thermodynamic treatment of thermoelectric
involving the irreversible processes at steady state operation. Applying the generalized laws of
thermodynamics, Lord Kelvin (Thomson) proved the validity of the relationships
dTdT = and =T where is the Peltier Coefficient and is the Seebeck Coefficient. In
1931, the Onsager symmetry relationships were developed. These complemented the theory of
thermoelectricity and using these relationships, the thermodynamic foundations for analyzing the
irreversible steady state processes have been laid. A detailed account and justification of the
thermodynamic framework in establishing the connections between all the thermoelectric effects
could be found in the monographs of de Groot, (1962) and Haase, (1990). The use of
semiconductors in thermoelectric refrigeration was proposed (Goldsmid and Douglas, 1954) as
the materials have high mean atomic weights and high thermoelectric powers. The relationship
between cooling capacity and the Coefficient of Performance (COP) were examined for a single
stage unit (Parrott, 1960) with respect to a given temperature difference between the hot and cold
junctions, and the design equations and performance graphs were presented. Recently, a new
approach to design thermoelectric cooling systems optimally has been proposed by Yamanashi in
1996. He succinctly introduced the dimensionless entropy flow equations to analyze the
thermoelectric cooling performance. Interface effects in thermoelectric micro-refrigerators were
studied by Sungtaek and Ghoshal (2000). They employed a phenomenological model to examine
the behavior of thermoelectric refrigerators as a function of thermal and electrical contact
resistance, the Seebeck coefficient and heat sink conductance. Ghoshal et al. (2002) described a
structured point-contact thermoelectric device, which defines the thermal gradient and electric
fields at the cold junction, and exploited the reduction of thermal conduction, tunneling
properties of point contacts and poor electron-phonon coupling at the junctions. They have
proposed a thermoelectric figure of merit, called the ZT parameter, which has a range of 1.4-1.7
at room temperature. In 1961, Landecker and Findlay studied extensively the transient behavior
of Peltier junctions by devising a method for measuring the thermo-junction temperature after
the passage of transient current pulse. They have theoretically demonstrated that the cold
junction temporal profile is a function of both pulse current and duration. Snyder et al., (2002)
reported the possibility of having a super cooler that employs a Peltier device and exploiting the
short time-scale behaviour of the current pulse at a magnitude several folds higher than that of
the non-pulsing period. The Peltier cold junction breaks contact momentarily with the surface to
be cooled prior to the arrival of the Joulean heat, where the latter is a heat transfer phenomenon
with a slower timescale. Such a transient operation of the thermoelectric has enable these cooling
devices to reach an unprecedented low temperature level, typically about 220 - 240K which
widens the application potential of pulsed thermoelectric, for example, a cryo cooler for surgery
applications or the cooling of infrared detectors. In 1999, Miner et al. modified a traditional
thermoelectric cooler by using the intermittent contact of a mechanical element, which was
synchronized with an applied pulsed current for a finite time. The proposed technique effectively
increases the thermoelectric figure of merit by a factor of 1.8 but there is no experimental result
to justify the proposed concept. Temperature entropy (T-s) formulation of thermoelectric cycles
has been developed (Chua et al., 2002(b)) within the framework of irreversible thermodynamics
and they have presented the steady state results. Similar work on the T-s diagram of the
thermoelectric module was also performed by Arenas et al. (2000) but they found a close link
between the Seebeck coefficient and the entropy per unit electric current. Also in 2000 and using
a finite time method, Nuwayhid et al. presented a procedure of minimizing the entropy
generation so as to maximize the cooling power of thermoelectric device. Solid state superlattice
structures could also be used to enhance the thermoelectric device performance by reducing the
thermal conductivity between the hot and cold junctions and provide selective emission of hot
carriers through the thermionic emission (Mahan, 1994). With much work performed in the study
of superlattice thermoelectric properties, (Antonyuk et. al., 2001), the idea of increasing ZT
parameter could be derived by enhancing the density of electron flow with reduced dimensions.
Recent study shows that superlattice thermal conductivity in the cross-plane direction is lower
than that of in-plane direction and such hetrostructures could be used for thermionic emission to
increase the cooling. The superlattice thermoelectric module consists of n-type and p-type super-
lattices (Shakuri and Bowers, 1997 and Elsner etal., 1996).