Effects of Mechanical Processing on Semiconducting Properties of Barium Titanate

Semiconducting barium titanate elements with positive temperature coefficient of resistance (PTCR) are usually subjected to different degrees of stress levels during processing operations like grinding, ultrasonic drilling, and slicing, etc. In this work we have examined the influence of these operations on the semiconducting properties of PTCR barium titanate using X-ray diffraction and electrical resistivity measurements.     

PTCR Characteristics in Barium Titanate Ceramics with Curie Points Between 60° and 360°C

PTCR characteristics in porous semiconducting barium titanate ceramics with Curie points from 60° to 360°C were investigated. The magnitude of the PTCR effect in these cerumics decreases self-onsistently with increasing Curie point within this temperature range. A PTCR efSect of more than 4 orders of magnitude was ahserved, for a Ba_0.44Pb_0.6TiO₃ ceramic with a Curie point of 360°C .     

Effect of Microstructure on the PTCR Effect in Semiconducting Barium Titanate Ceramics

The microstructural influence on the PTCR effect in semiconducting barium titanate ceramics was studied and a method for preparing the ceramic bodies exhibiting a PTCR effect of more than seven orders of magnitude was established. Commercial barium titanyl oxalate was used as a starting material and Sb₂O₃ was added as a doping substance. The average grain sizes of the ceramic bodies prepared were 2 to 5 μm over a sintering range of 60 to 92%, to examine in detail the microstructural influence on the PTCR effect. No extra element, such as Mn or Cr, was added to develop the PTCR effect in the present PTCR materials.     

Depletion-layer Dielectric Properties of Positive Temperature Coefficient of Resistance Barium Titanate

For pure and impurity-added positive temperature coefficient of resistance (PTCR) barium titanate ceramic samples, a −11°C shift of the Curie point at the grain-boundary/depletion-layer region was observed. This result is obtained by fitting the PTCR grain-boundary resistance and capacitance data to a theory which combines a double-depletion-layer model with the Devonshire thermodynamic theory of barium titanate. The parameters used in the fitting are obtained from independent experiments. The shift of the Curie point is believed to result from the grain-boundary clamp ing effect near the cubic-tetragonal phase transition point.     

Engineering grain size and electrical properties of donor-doped barium titanate ceramics

A semiconducting lanthanum-doped barium titanate ceramic has been fabricated for battery safety applications by simple means from nanoparticles prepared at room temperature by kinetically controlled vapor diffusion catalysis. The material, characterized by electron microscopy, X-ray diffraction and electrical measurements, exhibits a difficult to achieve combination of submicron grain size (∼500 nm) and attractive electrical properties of room temperature resistivity below 100 Ω cm and a 12-fold increase in resistivity through the Curie temperature (positive thermal coefficient of resistivity, PTCR). Systematic investigation of sintering conditions revealed that a short period of heating at 1350 °C under air is necessary to suppress abnormal grain growth, while precise control of the cooling rate is needed to achieve the targeted electrical properties. Cooling must be sufficiently fast to avoid complete back-oxidation, yet slow enough to facilitate oxygen adsorption at the grain boundaries to produce the thin oxide layer apparently responsible for the observed PTCR.     

Effect of Soaking Time on the Temperature Coefficient of Resistivity of Semiconducting Barium Titanate PTCR Ceramics

The influence of soaking time at 1200°C on the temperature coefficient of resistivity (TCR) of semiconducting barium titanate ceramics has been investigated. It is found that soaking duration has influence on the room-temperature resistivity, the maximum resistivity, the temperature ( T _max) at which the maximum resistivity appears, and TCR of the positive temperature coefficient of resistivity (PTCR) ceramics. The increased room-temperature resistivity with the increase of soaking time is contributed mainly by the increase of grain boundary resistivity examined by the complex-plane impedance method. The obtained surface acceptor density ( N _s) by capacitance–voltage measurement is found to increase with the soaking duration. The higher N _s contributes to higher built-in potential and results in lower T _max and higher maximum resistivity. Therefore, the increased surface acceptor density from increasing the soaking time at 1200°C increases the temperature coefficient of resistivity of PTCR ceramics.     

Spontaneous Polarization Screening Effect and Trap-State Density at Grain Boundaries of Semiconducting Barium Titanate Ceramics

The grain-boundary trap-state density and the polarization screening effect were studied for a series of semiconducting PTCR barium titanate ceramic samples with different manganese (Mn) additives and different thermal treatments. The grain-boundary resistance and capacitance data were measured by the ac complex impedance method. The grain-boundary data obtained were analyzed using a simple double-depletion-layer model and an absolute-zero-temperature approach for the Fermi distribution function for the boundary trap states. The energy density distributions of the boundary trap states were found to be V-shaped for the energy range studied, from 0.35 to 1.35 eV, as measured from the conduction band downward. The "neutral" Fermi level at the grain boundary is taken as 1.35 eV and the bulk Fermi level is taken as 0.15 eV from the conduction band. For the samples without the Mn additive, the PTCR effect is controlled by the trap densities located near 0.35 eV. The trap centers are believed to be barium and oxygen vacancies, or chemisorped oxygens. For the samples with Mn additives, the trap densities increase dramatically near 1.35 eV and play a dominant role in the PTCR effect. These trap centers are believed to be Mn⁴⁺ ions at the titanium sites. The charge-compensation effect of spontaneous polarizations on the trap charges was found to be linearly proportional to the total amount of trap charges at that temperature.     

Fabrication and characterization of a multilayer PTCR thermistor

A method has been developed to decrease the room temperature resistance of a PTCR barium titanate ceramic by introducing internal electrodes in a configuration analogous to multilayer capacitors. A multilayer thermistor containing four (n=4) tape cast layers of PTCR barium titanate was fabricated with internal electrodes. A reference sample of the same PTCR barium titanate without internal electrodes was fabricated with the same external dimensions as those of the multilayer thermistor. As predicted by theory, it was found that the resistance of the multilayer thermistor is approximately 16 (n²=16) times smaller than the test specimen with little change in the PTCR effect of the multilayer thermistor.     

Barrier Layers in Semiconducting Barium Titanate Glass-Ceramics

Methods were developed for the reduction and subsequent oxidation of glass-crystallized barium titanate for obtaining surface and grain-boundary barrier-layer dielectrics, together with the solid state chemistry compatible with glassmelting, crystallization, and the diffusion processes involved. The material obtained can be described as an interconnected dispersion of semiconducting BaTiO₃ crystallites sealed in a mostly glassy silicate matrix. Oxidation of this semiconductor leads to surface layers with very high dielectric strength, up to 10⁶ V/cm, and resistivity of the order of 10¹⁴ω·cm. The properties of compound barriers consisting of a space charge layer and a thin insulating film are also described and conditions leading to glass-ceramic materials having a positive temperature coefficient of resistance (PTCR) by the use of an anionic dopant are discussed.     

Single-Grain Boundaries in PTC Resistors

Thin semiconducting barium titanate ceramic bars consisting of single grains joined together in series have been prepared, and the positive temperature coefficient of resistivity (PTCR) characteristics of strictly single-grain boundaries in the materials were investigated. The resistivity ( R )-temperature ( T ) characteristics obtained for the present samples can be classified into typically three categories: (1) normal type PTCR characteristics, similar to those observed in usual ceramic samples, (2) saw-tooth type PTCR characteristics, characterized by an abrupt increase in resistivity by more than three orders of magnitude at the Curie point, immediately follwoed by a monotonous decrease in it, and (3) flat type R–T characteristics, with substantially little or no resistivity jump. Of these R–T characteristics, normal type PTCR characteristics were the most frequently observed (about 60%; a total of 65 samples were examined). Flat type R–T characteristics were least frequently (about 10%) observed. Single boundaries with these three types of PTCR characteristics exhibited essentially the same ferroelectric capacitance–temperature characteristic; this demonstrates that the temperature dependence of the dielectric constant above the Curie point was not responsible for the PTCR anomalies. Single boundaries with normal and saw-tooth type PTCR characteristics showed significantly nonlinear current-voltage characteristics above the Curie point, which may be interpreted to be caused by a current strongly affected by traps (or surface acceptor states) present at the grain boundaries.     

添加剂对BaTiO_3基PTC陶瓷性能的影响

本文研究了Ｎｂ_２Ｏ_５、 Ｙ（ＮＯ_３）_３、 ＴｉＯ_２、及 Ａｌ_２Ｏ_３、 ＳｉＯ_２对 ＢａＴｉＯ_３半导体陶瓷性能的影响。结果表明室温电阻率的波动随不同施主掺杂物量的改变而不同。Ｙ（ＮＯ_３）_３在较宽范围内变化时,试样的室温电阻率能保持较好的稳定性。同时对ＴｉＯ_２及Ａｌ_２Ｏ_３、ＳｉＯ_２都能提高ＰＴＣ效应的机理进行了解释。     

Processing of Laminated Barium Titanate Structures for Stress-Sensing Applications

High-purity, chemically prepared barium titanate was doped with 0.3 at.% lanthanum and, in some cases, counterdoped with 0.04 at.% manganese by precipitation. Using standard techniques, tape-cast sheets of the positive temperature coefficient of resistance (PTCR) compositions as well as the base insulating powder were made. A multilayer sensor was laminated and sintered, with upper and lower PTCR regions separated by an insulating BaTiO₃ region. The sensor was loaded using a four-point bend test configuration. The change in resistivity with increased load was observed to be linear, with positive and negative piezo-resistive coefficients for the PTCR layers under compression and tension, respectively. These trends were in general agreement with a stress-dependent permittivity and the Heywang model of grain-boundary potential barriers. Piezoresistivity values were derived from the resistivity-stress slope; these were examined as a function of temperature and sensor geometry.     

Differential Negative Resistance and Piezoresistivity in Thin Semiconducting BaTiO3 Ceramic Bars

Thin, semiconducting barium titanate (BaTiO₃) ceramic bars, with a diameter of 10 to 20 μm, consisting of single grains joined together in series have been prepared to investigate the piezoresistivity in the materials, which was evaluated from their current ( I )-voltage ( V ) characteristics under the loading condition of various bending stresses. I-V characteristics of single grain boundaries in some of the materials were found to exhibit distinct differential negative resistance (DNR) at room temperature with its feature changing with stress. The DNR appeared on the I-V curves at an electric field of several volts per one grain, and has been confirmed to be connected with the transition of current between two conduction states in the grain boundary region. The obtained results indicate that this phenomenon cannot be interpreted by a rise in the temperature of the materials up to their positive temperature coefficient of resistivity (PTCR) region above the Curie point by Joule heating due to current flow, that is their self-heating effect. This newly observed DNR phenomenon has thus been tentatively interpreted by the morphological change in the ferroelectric domain structure in the vicinity of grain boundaries under mechanical and electric stresses, on an assumption that different configurations of ferroelectric domains yield different conduction states in the grain boundary due to a difference in the degree of surface acceptor charge compensation or the anisotropic carrier mobilities in the crystal.     

Electrical Properties of PTCR Barium Titanate

When properly doped, barium titanate ceramics display positive temperature coefficient resistance (PTCR) behavior. This has been proved to be a Schottky barrier type of grain-boundary effect. However there has not yet been a complete point-to-point comparison between the experimental data and theory for the entire set of the material nonlinear dielectric properties. In this study, a methodology has been developed which allows the study of the depletion layer dielectric properties while the PTCR effect is being investigated. An equivalent dielectric constant, the value of which is to be determined from this experiment, is treated as an average of the dielectric properties of the depletion layer and is used to analyze the grain-boundary resistance and capacitance data based on a simple double-depletion-layer model. The theoretical relationship between this equivalent dielectric constant and the material dielectric properties is also explored in this study.     

Formation of Potential Barrier Related to Grain-Boundary Character in Semiconducting Barium Titanate

Resistance–temperature ( R – T ) characteristics were measured directly at single-grain boundaries in 0.1-mol%-niobium-doped barium titanate bicrystals that had been fabricated from polycrystalline sinters, to determine a geometrical grain-boundary character dependence of the positive temperature coefficient of resistivity (PTCR) effect. Both random boundaries and low-Σ boundaries exhibit a similar grain-boundary character dependence of the PTCR effect through a simple geometrical analysis, using the coincidence of reciprocal lattice points. Differences of the R – T characteristics in individual boundaries have been explained in terms of the formation of a potential barrier that is associated with the oxidation of grain boundaries during cooling, after sintering or annealing. The grain-boundary character is likely to affect the diffusivity of O²⁻ ions and, hence, is crucial to the formation of the potential barrier.     

Influence of Ba/Ti Ratio on the Positive Temperature Coefficient of Resistivity Characteristics of Ca-Doped Semiconducting BaTiO3 Fired in Reducing Atmosphere and Reoxidized in Air

The positive temperature coefficient of resistivity (PTCR) characteristics of donor-doped BaTiO₃ fired in a reducing atmosphere and reoxidized in air are investigated. The result reveals that conventional semiconducting BaTiO₃ ceramics fired in a reducing atmosphere and reoxidized at a low temperature of 800°C in air show minimal PTCR characteristics, as reported earlier; however, Ca-doped BaTiO₃ with compositions in the range of 1.005≤(Ba+Ca+La)/Ti≤1.010 exhibit pronounced PTCR characteristics, even when reoxidized at such a low temperature. The semiconducting BaTiO₃ ceramics with {(Ba+Ca+La)/Ti}=1.005 and Ca-doped to 20 mol% exhibit remarkable PTCR characteristics with a resistivity jump of two orders of magnitude when they have been reoxidized at 800°C after firing in a reducing atmosphere.     

Influence of Stoichiometry on the PTCR Effect in Porous Barium Titanate Ceramics

Porous semiconducting barium titan ate ceramics with small grain sizes (2 to 5 tun) exhibit large PTCR effects (>7 orders of magnitude). The magnitude of PTCR in the ceramic bodies is significantly affected by the grain structure. This study shows the influences of Stoichiometry on both the magnitude of PTCR and resultant grain structures in the sintered bodies .     

Piezoresistivity in PTCR Barium Titanate Ceramics: II, Mathematical Modeling

A modified grain boundary potential barrier model for positive temperature coefficient of resistance (PTCR) barium titanate is developed. It is based on Heywang's double Schottky barrier model, together with Devonshire's thermodynamic phenomenology of polarization behavior. Modifications are made to address the nonlinearity of the dielectric response with respect to electric field in the depletion region adjacent to the grain boundary, and the circular dependence of these quantities with the height of the barrier. Piezoresistivities are calculated for various PTCR compositions and sintering conditions, and these are compared to experimental results from the preceding paper.     

Interfacial Segregation in Perovskites: IV, Internal Boundary Layer Devices

A proposed model for interfacial segregation in perovskites, with induced heterogeneous defect distributions, is extended here to account for the formation of internal boundary layer devices, such as positive temperature coefficient of resistance (PTCR) thermistors and internal boundary layer capacitors (IBLC). Boundary layer effects in doped BaTiO₃ are attributed to factors which contribute to the formation of highly resistive boundary layers by a segregation-induced shift in donor incorporation and/or acceptor segregation, and the inhibiting action of segregated donors on boundary mobility and grain growth. The distribution of space charges, formed by electron transfer from conductive grains to resistive boundary layers, leads to the formation of impedance barriers in the grain-boundary vicinity. Depending on the grain size, and on relative size and spatial distribution of the space charge layer and the resistive layer, a transition from semiconducting properties to insulating properties may take place. This model accounts for the observed PTCR and IBLC phenomena.     

Shift of the Curie Point of Barium Titanate Ceramics with Sintering Temperature

Definite increases in the Curie point (T_C) of undoped and lanthanum- (La-) doped (<0.5 at.%) barium titanate (BaTiO₃) ceramics sintered at elevated temperatures in the range of 1300°-1450°C were observed. Both undoped and 0.3 at.% La-doped BaTiO₃ (chosen as a typical doping concentration to yield semiconducting materials) ceramics showed almost the same T_C behavior; their T_C values increased by ∼3.5°C as the sintering temperature was increased from 1300° to 1450°C. Semiconducting 0.3 at.% La-doped materials increased in room-temperature bulk resistivity and TC with increased sintering temperature. The bulk resistivity of the La-doped materials, which was obtained from complex impedance analysis, increased from ∼2 omega cm for the material sintered at 1350°C to ∼6 ω cm at 1450°C. The phenomenon of bulk resistivity increase with sintering temperature was observed in the materials with a doping concentration of ≥ 0.2 at.% La, but was not observed in those doped with <0.2 at.% La. The mechanisms of TC and the bulk resistivity increase observed in the present materials with increased sintering temperature are discussed based on various models found in the literature, particularly in terms of the defect chemistry in semiconducting BaTiO₃ ceramics and the influence of liquid phases present during sintering.