Curie-Weiss Law and Ferroelectric Materials

A McLaren Kelvin Building, Department of Physics and Astronomy, University of Glasgow, Glasgow G12 8QQ, UK E-mail: 1003280m@student.gla.ac.uk
Abstract. The Curie-Weiss Law was investigated and confirmed using capacitors with ceramic dielectrics, namely barium titanate and strontium titanate (BaTiO3 and SrTiO3 respectively), and the Curie temperature of SrTiO3 was found to be 52.5K. This was done by recording the capacitance of each capacitor at temperatures ranging from about 280K to 330K for BaTiO3 and about 100K to 300K for SrTiO3. A silvered mica capacitor was used as a control.

1. Introduction A capacitor is a device which can be used to store small amounts of electrical charge or energy in an electric field, and which is able to be charged or discharge rapidly. This makes them very useful, for example in electronic circuits, for powering camera flashbulbs, and in high-pass filters in signal processing [1]. The simplest type of capacitor is made from two parallel plates of a conductive material, with area A, separated by a distance, d. The ratio of the charge a capacitor can hold over the voltage across it is called the capacitance, C, measured in Farads (F). For a parallel plate capacitor, this is given by C=oA/d (1) where o=8.85x10-12F/m is the permittivity of free space [2]. Inserting an insulating material known as a dielectric between the plates can increase the capacitance of a capacitor. When a potential difference is applied across the capacitor, a charge of the opposite sign is induced on the surface of the dielectric due to a redistribution of positive and negative charge within the dielectric material [3]. This effect is called polarization, and has the result of reducing the net electric field between the plates of the capacitor and therefore increasing the capacitance. The ratio of the capacitance with the dielectric in place to the capacitance without it is a dimensionless quantity, K, known as the dielectric constant, or the relative permittivity (also represented by R). The capacitor equation can then be rewritten as C=A/d (2) where =Ko (in F/m). However, for certain materials, this dielectric constant can vary with temperature. This is due to structural changes within the dielectric at a molecular level. It is the effect of these changes that was investigated. 2. Temperature dependence of a ceramic capacitor with a barium titanate dielectric No current passes through an ideal capacitor in an AC circuit. In this case, there would be a phase difference of exactly /2 between the current and the voltage. This means it has purely imaginary

impedance. However, a real capacitor has a complex impedance as a slight amount of current is allowed to pass through it. This can be modeled in two ways. The capacitor can be represented by an ideal capacitor (of capacitance CS) in series with a resistor RS, or as an ideal capacitor (of capacitance CP) in parallel with a resistor RP. The LCR meter used in this experiment (the AVO B131 Dual Display LCR Meter) measures CP, however for analysis CS is more useful. A loss factor, D, (also known as dissipation) can be used to convert between the series and parallel models. D is defined as D = C SR S (3) where is the angular frequency of the circuit. It can be shown that CS=CP(1+D2) (4) and so measurements of CP and D can be converted in to CS. 2.1. Experimental Method Two capacitors were mounted in a metal heat sink. A 470pF silvered mica capacitor was used as a control as it was known to have a stable capacitance. A 0.1F ceramic capacitor (made with a barium titanate dielectric) was investigated. The temperature of the heat sink was gradually increased from 283K to 333K (measured with a t type thermocouple and read from a Digitron T208 thermometer), and the values of CP and D measured. The values of CS were calculated and a graph of series capacitance against temperature was then plotted for each capacitor. It should be noted that a circuit breaker was used before each measurement was taken to obtain more accurate results due to the iterative process used by the LCR meter. This circuit breaker had a small capacitance (measured to be 3.1pF), which was subtracted from all results before they were plotted. 2.2. Results It can be seen from figure 1 that the silvered mica capacitor showed very little variation in capacitance. The range of the results is 4.6nF, less than 1% of the mean value. This is most likely due to the selected 1% tolerance level of the LCR meter [4]. Because this type of capacitor is designed to be stable over a large range of temperatures, this result was expected.
Capacitance Variation with Temperature for Silvered Mica 525 520 515

Series Capacitance (nF)

510 505 500 495 490 485

285

290

295

300

305 310 315 Temperature (K)

320

325

330

Figure 1. Graph of Capacitance Variation for Silvered Mica

The ceramic capacitor showed a distinct variation of capacitance with temperature, as shown in figure 2.
Capacitance Variation with Temperature for Barium Titanate 110 105 100

Series Capacitance (nF)

95 90 85 80 75 70

290

300

310 320 Temperature (K)

330

340

Figure 2. Graph of Capacitance Variation for Barium Titanate It was clearly seen that, as the temperature was increased the capacitance rose to a maximum value of 108.7nF at around 304.6K, before falling rapidly as the temperature was increased further. The first point on the graph is anomalously high. This was attributed to the circuit breaker not being fully depressed before the first reading was taken, and should be ignored. 2.3. Background Theory Mica is a compound, which exists as parallel planes with a hexagonal structure, similar to that of carbon graphite. As a result, it is not easily polarized since its component particles are not free to move. On the other hand, barium titanate exists as an ionic compound. When heated from 275K to 395K, it undergoes a structural change from an orthorhombic to a tetragonal lattice [5]. When a voltage is applied across the capacitor, the positive and negative ions move to become polarized. At this stage, the material is known as being ferroelectric. However, as the temperature is increased, the thermal motion of the particles competes with this and randomizes the ions. The point at which the thermal motion begins to dominate is the peak of the curve in figure 2, known as the Curie temperature, T0. Above this temperature, the capacitance decays. This is known as para-electric behavior. 3. Temperature dependence of a ceramic capacitor with a strontium titanate dielectric 3.1. Experimental Method The temperature dependence of an SrTiO3 capacitor (similar to the BaTiO3 capacitor) was investigated at temperatures below the freezing point of water. As a result, the capacitor had to be in a near vacuum to prevent ice crystals from forming on the capacitor, as this could affect the results. This was achieved by housing both the SrTiO3 capacitor and a silvered mica capacitor (of known capacitance 270pF) inside a brass chamber, mounted on a copper rod. The chamber was evacuated and the rod

immersed in liquid nitrogen. After allowing an hour for the rod and capacitors to reach a sufficiently low and stable temperature (at 102K), the rod was removed from the liquid nitrogen and allowed to gradually warm up to room temperature. Measurements of the parallel capacitance and loss of the ceramic capacitor were taken as the capacitors warmed at intervals of roughly 50pF, and the mica capacitor was measured to act as a control. The average reading for the mica capacitor was found to be 327.0pF. This value includes the capacitance of the circuit breaker and the leads, as well as the capacitor itself. The known value for the mica capacitor was subtracted, leaving a so-called stray capacitance of 57pF. This was subtracted from all values of the capacitance of the ceramic capacitor before they were plotted. 3.2. Results It was found that the loss of the ceramic capacitor was small enough (~0.001) that it could be ignored. The capacitance was plotted against temperature for the ceramic capacitor, shown in figure 3.
Capacitance Variation with Temperature for Strontium Titanate 1400

1200

Series Capacitance (pF)

1000

800

600

400

200 100

120

140

160

180 200 220 Temperature (K)

240

260

280

300

Figure 3. Graph of Capacitance Variation for Strontium Titanate Again, the tolerance level of the LCR meter was 1% and the uncertainty in the temperature was 0.05K, both of which are too small to be seen on the graph. The graph clearly shows the capacitance decaying to some constant high temperature value. This is consistent with the expected para-electric behavior. 3.3. Analysis The Curie-Weiss Law states that for a material exhibiting para-electric behavior, its relative permittivity is given by R=HT+0/(T-T0) (5) where HT is the limit of the relative permittivity at high temperatures, 0 is a parameter giving the Curie-Weiss response of the dielectric, and T is the temperature. By rearranging equation 2 and by plotting a graph of R against 1/(T-T0) (and the residuals), the Curie temperature, T0, was found using a least squares fit for a straight line.

Graph to find the Curie Temperature of Strontium Titanate 1600

Er(T) of strontium titanate

1400 1200 1000 800 600 400 200 0.004

y = 6.9e+004*x + 34

0.006

0.008

0.01

0.012 0.014 1/(T-To) (1/K) residuals

0.016

0.018

0.02

0.022

15 10 5 0 -5 -10 -15 0.004

0.006

0.008

0.01

0.012

0.014

0.016

0.018

0.02

0.022

Figure 4. Straight line fit to find Curie temperature of SrTiO3

It was found that the best fit was achieved at a temperature of T0=(52.50.3)K. The error in this value was found using the curve-fitting tool on MATLAB. This value is high compared to the accepted value of 38K [6]. A possible reason for this is that the chamber, which the capacitors were housed in, was not properly evacuated. It is also possible that the thermocouple used in measuring the temperature had some unknown systematic uncertainty associated with it. It can also be seen from figure 3 that the first data point (corresponding to the last data point in figure 4) is lower than expected. This is perhaps because the temperature is too low for the strontium titanate to be exhibiting Curie-Weiss behavior. Ignoring this point may lead to a better fit, and therefore a better Curie temperature. 4. Conclusion It was successfully shown that ceramic capacitors have temperature dependent permittivities and that, at sufficiently high temperatures, strontium titanate obeys the Curie-Weiss Law. It was also shown that capacitors with covalent dielectrics do not exhibit temperature dependence, but are stable over a large range of temperatures. It was realized that this could be used as a test to see if a substance was a covalent or ionic compound. References [1] Castello R and Gray P R 1985 A high-performance micropower switched-capacitor filter IEEE

[2] [3] [4] [5] [6]

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