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@PHDTHESIS{Rahmani:848213,
author = {Rahmani, Meimanat},
title = {{O}ptimization of powder and ceramic processing, electrical
characterization and defect chemistry in the system
{Y}b$_{x}${C}a$_{1-x}${M}n{O}$_{3}$},
volume = {54},
school = {RWTH Aachen},
type = {Dissertation},
address = {Jülich},
publisher = {Forschungszentrum Jülich GmbH Zentralbibliothek, Verlag},
reportid = {FZJ-2018-03475},
isbn = {978-3-95806-323-5},
series = {Schriften des Forschungszentrums Jülich. Reihe Information
/ Information},
pages = {XIV, 164 S.},
year = {2018},
note = {RWTH Aachen, Diss., 2018},
abstract = {Mixed valence alkaline earth manganites
RE$_{x}$A$_{1-x}$MnO$_{3}$ with very rich and complex
crystal physics and chemistry have attracted a great deal of
attention recently. Two innovative potential applications
for rare earth manganites are non-volatile memories based on
resistive switching and waste heat recovery techniques by
thermoelectric generators. The resistive switching mechanism
and thermoelectric properties strongly depend on the
concentration and nature of the charge carriers. Defect
chemistry mechanism involved in these process have not been
understood clearly yet. The lack of information in the
literature is certainly also due to complexity of this
material system, since manganese cations possess several
valence states in the quaternary oxide. The other reason
possibly is due to the formation of cracks or deformation of
ceramic compounds in to the powder during electrical
measurements in the reduction regions. Therefore, in the
present thesis comprehensive studies were performed for the
first time in order to find the way for reducing or
preventing crack formation that occurs during sintering. For
this purpose the effect of different calcination and
sintering conditions on the physical properties of
stoichiometric, nonstoichiometric (Ca-excess and Mn-excess)
and 0.1 to 10 at. \% of Yb-doped CaMnO$_{3}$ ceramics were
investigated in dependence of temperature T and partial
pressure of oxygen p(O$_{2}$). After finding the required
parameters to produce desired crack free-ceramics such as
calcination temperature, sintering gas composition types and
heating/cooling rates, etc., electrical characterizations
were performed including DC conductivity and impedance
spectroscopic measurements. Bulk conductivity measurements
are performed by impedance spectroscopy accompanied by
modeling the compounds in terms of an electrical equivalent
circuit in a wide range of temperatures and frequencies.
These experiments reveal the main role of grain boundaries
and electronic and ionic contributions in conductivity. A
novel schematic illustration based on the
double-Schottky-barrier model for polycrystalline ceramics
is proposed which clearly describes the contribution of
different resistance components in electric transport
properties. Migration of oxygen vacancies and their
participation in conductivity are discussed in the present
study and the results are confirmed by observing oxygen
released using a ZrO$_{2}$ oxygen sensor during dilatometry
measurements in a wide range of temperatures. The defect
chemistry model is proposed to clarify the details of the
chemistry of point defects. This theoretical model
accompanied by experimental DC-conductivity measurements,
dilatometry analysis, SEM, EDX, XRD-measurements, Raman
spectroscopy, iodometric titration and thermogravimetric
(TGA) experiments reveal ionic as well as electronic charge
transport conductivity contribution in dependence ofthe
oxygen partial pressure p(O$_{2}$) for donor-doped
Yb$_{x}$Ca$_{1-x}$MnO$_{3}$ systems. A comparison of the
experimental observations and the theoretical defect
chemical models clearly show the way for controlling charge
carriers in dependence of p(O$_{2}$) and dopant
concentrations. A negative slope of electrical conductivity
versus p(O$_{2}$)indicates that n-type conductivity occurs.
A p(O$_{2}$) independent conductivity (plateau region) is
observed for both undoped and donor-doped CaMnO$_{3}$.
Electrical measurements accompanied by thermal analysis and
phase purity assessment reveal that the origin of the
plateau region in conductivity is due to intrinsic or
extrinsic electronic compensation. In this region probably
due to formation of secondary phases oxygen ions do not
considerably influence the electron and hole concentrations.
In addition, the origin of the drastic decrease in
conductivity at reduction region is elucidated. Overall, the
present experiments clearly demonstrate the effect of donor
dopant concentration, formation of oxygen vacancies and
corresponding change in density of Mn$^{3+}$-Mn$^{4+}$ pair
sites on phase transition, charge migration and conductivity
mechanism of the complex systems
Yb$_{x}$Ca$_{1-x}$MnO$_{3}$. The obtained information
probably will be useful for better understanding the
conduction mechanism in future technological applications.},
cin = {PGI-7},
cid = {I:(DE-Juel1)PGI-7-20110106},
pnm = {899 - ohne Topic (POF3-899)},
pid = {G:(DE-HGF)POF3-899},
typ = {PUB:(DE-HGF)3 / PUB:(DE-HGF)11},
url = {https://juser.fz-juelich.de/record/848213},
}