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ELECTIUCAL PROPERTIES OF NANOCRYSTALLINE AIP04
51 Introduction ..
The enhanced electrical properties of nanocrystalline materials exhibiting unusual properties play a vital role in the development of new m a t e r i a ~ s . The '~ electronic, optical, catalytic and electrical properties of nanostrucmred materials are many times superior to their bulk form and depend strongly on size, shape, composition and preparation conditions? The large surface to volume ratio and the variations in electronic structure. have dramatic effects on transport and catalytic properties. The major po:rtion of atoms located at surfaces or interfaces greatly influence the transport of ions and electrons through solids. In addition short-range rearrangement or redistribution of ions and electrons may cause electrical or chemical polarization. This effect is more dominant in nanophase dielectric materials. Each interface will polarize in its unique way when the system is subjected to an applied electric field.6 Studies on the effect of temperature and frequency on the dielectric behavior and a.c. electrical conductivity offer valuable information about the conduction phenomenon in nanostructured materials.' Dielectric behavior can effectively be used to study the electrical properties of grain boundaries, since majority of atoms of nanomaterials reside at grain b o ~ n d a r i e s . ~ , ~ Impedance spectroscopic studies give valuable information about the grain and grain boundary characteristics of nanophase materials. The origin of resistance or capacitance, its dispersion with small signal frequencies and the role of defects be obtained from these s t ~ d i e s . ' ~ In determining the electrical properties of nanocrystalline materials, the grain boundaries and grain interfaces play important roles.""3 Grain boundaries 'of nanophase materials are in a disordered state with large defect densities, which can act as traps for charge caniers jiom adjoining The dielectric properties
of materials are mainly due to contributions from electronic, ionic, dipolar and space charge .Among these, the most important contribution for
polycrystalline materials in bulk form is the electronic polarization, present in the optical range of frequencies. The next contribution is from ionic polarization, which arises due to the relative displacement of positive and negative ions. Dipolar or orientation polarization arises from molecules having a permanent electric dipole moment that can change its orientation when an electric field is applied. Space charge polarization or interfacial polarization arises from accumulation of charge carriers at structural interfaces.I9 These mobile charges are impeded by interfaces, since they are trapped in the material and are not supplied or discharged at an electrode. Space charges resulting from these phenomena appear as an increase in capacitance as far as the exterior circuit is concerned. For the electrical characterization of materials including solid electrolytes, ceramics and nanocrystals, impedance spectroscopy is accepted as an important too1.1~2~5~2a24 Impedance spectra usually include features that are directly related to the grain boundary structure of particles. 25-27 The impedance spectroscopic analysis of nanophase ZnO has been reported1 and the spectrum was interpreted on the basis of resistive grain boundaries and conductive grain cores. Win and ~eitjans'studied the frequency dependent ionic conductivity of nanocrystalline CaF2 through impedance spectroscopy. I!lectric:al properties of nano-CeOz have also been
reported through impedance spectroscopy." In this chapter, the variation of dielectric constant, dielectric loss and a.c. electrical conductivity of n- AlPOj samples of different grain sizes are studied as a function of sample temperature and frequency of the applied electric field. The enhancement of the dielectric properties due to nanocrystallization and with reduction in grain size of the sample are analyzed in terms of existing theories and references of previous works in this field. The impedance spectroscopic analysis of the sample is canied out and the grain boundary parameters of the sample are deduced.
Nano-sized aluminium phosphate ( A l p 0 3 in three different grain sizes was prepared from the thennolysis of new polymer matrix based precursor solutions.
Fig. The nanoparticles were consolidated into pellets of diameter 13 mm and thickness 1-2 mm by applying a pressure of about 0. and are of high purity.4 GPa. The .).Electrical Properties of N~mocrystalline Alp06 - 119 The resulting powders are nano-sized.5. Both faces of the pellets were coated with colloidal silver. In the present study. In order to determine the crystal structure of nanocrystalline A1P04.3. The variation of dielectric constant for nano Alp04 samples of different grain sizes with frequency of the applied field is presented in Fig.59 nm and 12. The capacitance (C. Conducting leads were attached to both faces of the pellets and the samples were then encapsulated using nonconducting epoxy powder. A is the cross sectional area of the given sample. All the samples are found to be of cubic structure. the encapsulated pellets were immersed in an oil bath. Results and Discussion 5.04 nm respectively.0 rnol L".2. stoichiometric amounts of the reactants were taken such that the concentration of the reactants were 1. eo is the permittivity of free space and lan 6 is dielectric loss factor. the calculated 'd' values are compared with the standard ICDD-PDF data of cubic AIP04.34 nm.1 mol L" to produce nanosized A1P04 samples of average grain sizes16. A2 & A3). For electrical conductivity measurements.1 . the modulus of complex impedance (JZI) and phase angle (8)of the samples were measured using a Hewlett-Packard 4192A impedance analyzer over the frequency range 100 Hz -3 MHz and over the temperature range 300K to 373K.3(i) Dielectric constant The real and imaginary parts of the dielectric constant E' and E" of the given samples were calculatecl from the measured values of capacitance Cpand dielectric loss using the formulae E" = E' tan 6 (5.3. the temperature of which could be regulated with an accuracy of &.IoC. 13. 0.5. 5. (samples A l .2) where d is the thickness.5 mol L-' and 0. Details of the preparation28are given in the synthesis part of section 2.
the corresponding variations are from 192 to 8 and from 110 to 5 respectively. Variation of dielectric constant of n-AIPO. sample A 3 with frequency . It is seen that the dielectric constant at 300 K is very small which suddenly increases and attains the maximum .5.7.5. but at very high frequencies no variation of E' with grain size is observed. Similar variations are observed for higher frequencies. The variations of dielectric constant with temperature for nano-Alp04 of different grain sizes are shown in Fig.5 to Fig. The dielectric constant of sample A3 at 323 K decreases from a value of 273 at 100 Hz to 8 at 3 MHz. log f Fig. 5. It can be seen that the dielectric constant (E' ) at 323 K and at 100 Hz decreases from 273 to 108 when the particle size increases from 12 nm to 16 nm. For samples A2 and Al.1.4.5.Chapter 5 120 dielectric constants of all the samples are high at low frequencies that decrease rapidly with the applied frequency at all temperatures. The variation of dielectric constant with grain size of nano-A1P04 is shown in Fig.
sample A2 with frequency log f / Fig.2. 5.Electrica[ Properties of Nanocrystalline A1P04 121 log f Fig. 5.Variation of dielectric constant of n-AIPO. sample A1 with frequency .3. Variation of dielectric consta?t of n.AIPO.
Vanation of dielectric constant (e') with temperature of sample A3 .5.- c 0 n -=-0- --A- -r- 1KHz IOKHZ 100KHz 1MHz 45MHz vI . -0- 280 1 KHz C -r- 100 K H ~ m v.Chapter 5 _ . I a .-l 'U 0 80 u 40 \-A - -. ' . C 160 0 . Variation of dielectric constant (E') with grain size of nano-AIPO.. 5. I I . 122 __ -- - .p ...-.- .-.4. 1 ' 290 300 310 320 330 340 350 360 370 380 T(K) Fig. at 323K . 120 L 0 \\. ' I ~ 1 i ! A ! i I 12 33 14 15 1 6 17 Grain size (nm) Fig.5. I 1 . L i ---. 1 ' I ._ .
Electrical Properties of Na. Variation of dielectric constant (E') with temperature of sample A1 . Variation of dielectric constant (E') with temperature of sample A2 0 .5.5.tocrystalline ALP04 123 T(K) Fig.L U m a () I T(K) Fig.6.7.
Their results clearly indxcate the presence of dielectric relaxation in these materials.nO and Zn0-AlzQ3nanocomposites. This is attributed to the trapping of electrons by traps present in grain boundaries. it is from 47 to 5 respectively Valuable information about various aspects has been brought out from the measurement of dielectric properties: of nanostructured materials. in ~ ~ . Large dielectric constant at low frequencies were reported for different materials by many authors. These boundaries contain defects such as dangling bonds. Joshy and Abdul IChadarS investigated the grain boundary properties of nano-2.Chapter 5 124 value at 323 K and then decreases as temperature increases.5. The enhanced electrical conductivity of nanophase A and c ~ and changes in the dielectric properties of nanophase ZnS. In the case of sample A2.29-37 Biju and ~ h a d ' dstudied the dielectric relaxation mechanism by ~ considering nanostructured NiQ as a carrier dominated dielectric with high density of hopping charge carriers. They reported the conductivity due to grain boundaries is higher than that due to grains. The dielectric properties of nanophase AgzHgb and Ag2Hgb-Al203 nanocomposites were investigated by Sankara Narayanan Potty and Abdul ~ h a d a r ~ ~ the and observed changes in the dielectric properties were attributed to the grain boundary properties of nanophase materials. For high frequencies the dielectric constants of all the samples are much lower and does not vary appreciably with temperature.~ their A large volume percentage of nanocrystalline materials consist of grain or interface boundaries. This effect is more prominent at low frequencies as shown in the figures. of various grain sizes through impedance analysis. The maximum value of the d~electric constant of AlP04 sample A3 decreased from 120 at 1 KHz to 8 at 3 MHz. . Cochrane and 13etchersostudied the ionic conductivity in silver iodide and reported a very high dielectric constant at the low frequency region. BaTiO3 I ~ ~ ~ s comparison with~ bulk have also been reported. Ponpandian and ~ a r a ~ a n a s a m ~ ~ ~ s t the i electrical conductivity and ud ed dielectric properties of nanocrystall~neZnFezO. the corresponding variation is from 65 to 8 and for sample Al. Abdulla and ~ u s u studied the frequency dependence of dielectric constants of some Mgf ~ ~ Zn fenites and they observeti very large value of E' at low frequencies.
the ion and vacancy can exchange positions by a simple jump of the cation to a neighboring position. Also. the d.39In addition ion jump polarization may also be greater in nanocrystalline materials since there will be a number of positions in the grain boundaries for the ions to occupy.~ interpreted as due to random hopping of mobile ions from site to site.40 In nanocrystalline materials.'4A2which become electrically active as a result of charge trapping. at low frequencies the dielectric loss is inversely proportional to frequency.c. Space charges resulting from these phenomena appear as an increase in capacitance. The dipole moment can easily follow the changes in electric f i e ~ d . " .c. Along with these. When an electric field is applied. The space charges can move on the application of an external electric field and when they are trapped by the defects.c. lot of dipole moments are formed. Thus the high values of the dielectric constant in the present study may be attributed to the increased ion jump orientation effect and the increased space charge effect exhibited by nanoparticles. should be larger than that of conver~tional materials. ~ ~ . This is space charge polarization. ~ ~ at especially low frequencies. which occur mainly in interfaces?' Thus the dielectric constant of nanostructured materials. which leads to an increase in the dielectric constant. leading to a decrease in the value of E'. increased d. 125 vacancies.. conductivity can be expected due to hopping by the presence of high density of trap sites. vacancy clusters etc:" These defects can cause a positive or negative space charge distribution at interfaces. c o n d u ~ t i v i t As ~ ~ ~ frequenc:~ increases beyond a particular limit. An assembly of space charge caniers in a dielectric requires enough time to line up their axes parallel to an alternating . the space charges cannot sustain with the field and hence the polarization decreases. Most of the atoms in nanocrystalline materials reside in grain boundaries. which decides the dielectric properties in materials with small particle sizes.conductivity observed in fast ion conductors is . Hence the space charge effect will be a pnsminent factor.conductivity effects can also enhance the value of the dielectric c o n ~ t a n t The large d. c .Electrical Properties of Nanocrystal'line AlPO. The charge displacement occurs by an atom jump rather than movement about an equilibrium position. as far as the exterior circuit is concerned. Hence the contributions to dielectric constant increases through space charge polarization and rotation direction polarization. which indicates large d .
c.Chapter 5 126 electric field. . at some stage the space charge carriers will have started to move before the field reversal. 5.3) The d. as described above.~ sufficiently high temperature.conductivity effects enhance the value of the dielectric c o n ~ t a n tAlso. the dielectric will get the time for this. The dielectric loss of a material is given as4' where a is the conductivity and o is the frequency. the space charge carriers cannot keep up with the field and their directions lag behind the field.~' increased space charge polarization and conductivity effects at the beginning of the rise in temperature is the reason for the sharp increase of the dielectric constant at low frequencies. usually dielectric losses occur due to absorption current. resulting a decrease in dielectric constant. tr = S 0 exp (-EAT) I (5. leading to a rather frequency independent dielectric constant. As temperature increases. which also involve energy losses. requires a part of electric energy to overcome the forces of internal friction. The observation that &' decreases sharply with frequency and remains almost a constant at very high frequencies. At low frequencies. But if the frequency of the field reversal increases beyond a certain limit. the :.pace charge and ion jump polarization are lagging behind the applied field. d.3(ii) Dielectric Loss In dielectric materials. Another part of electric energy is utilized for rotations of dipolar molecules and other kinds of'molecular transfer from one position to another. should be attributed to the increased inertiad6of the dipoles.conductivity increases exponentially as. at .c. The dielectric constant of nano-Alp04 initially increases sharply with temperature to a sufficiently high value and thereafter decreases with temperature. the dielectric loss is dominated by the conductivity of The the sample resulting an increase in dielectric con~tant. resulting a lowering of dielectric constant of the materiaLd5As the frequency of the alternating field continuously increases. The orientation of molecules along the direction of the applied electric field in polar dielectrics. At sufficiently high temperatures.
which decreases to 0.8 . The same behaviour is observed with lower values for all other temperatures except room temperature.Electrical Properties of Nan:ocrystullineAlp04 127 The variations of dielectric loss factor (tan 6) of nano-Alp04 samples of different grain size with frequency are shown in Fig. tan 6 initially increases with temperature.S. It can be seen that tan 6 decreases with increase of frequency and at higher frequencies the loss angle has almost the same value at all temperatures.5. it is from 0.ll - Fig.5.3 to 10. which decreases to 0. the value of dielectric loss at 1 KHz increases from 0. For sample A3. sample A3 with frequency . where tan 6 do not change with frequency.1 respectively. For sample A l . The corresponding variations for sample A2 is from 0. The corresponding variations for samples A2 is from 13 to 0. from 10 to 0.13. the dielectric loss at 323 K is 16 at 100 Hz.6 at 3 MHz.8. attains a maximum value and thereafter decreases at a slower rate.5.S.lO.3 at 300 K to 12 at 323 K and then decreases to 0.Fig.1. For all samples in the present study.4 and for Al. The variations of tan ii for different temperatures are shown in Fig.8 at 373 K. Variation of dielectric loss (tan 6) of n-AIPO.1 to 8 and log f Fig. For nano-A1P04 sample A3.
sample A1 with frequency .5.9. sample A2 with frequency -------t-- 2 3 4 5 6 7 log f Fig.5. Variation of dielectric loss (tan 6) of n.Chapter 5 128 log f Fig.AIPO.AIPO. Variation of dielectric loss (tan 6) of n.10.
Electrical Properties of Nunocrystalline ALP04 - 129 12 10 -A- /-0. sample A 2 with temperature 2.11. sample A3 with temperature T(K) ~ i ~ 5 . Variation of dielectric loss (tan6)of AIPO.5.-• A/-A-~ -r- 100KHz 1MHz 04 02 00 *--7 T(K) Fig. . 1Variation of dielectric loss (tan8)of AIPO.
Chapter 5 ~ ~ 130 -. properties of the material may vary in different parts of the volume.13. space charge formation etc. etc. The nature of variations are similar.1 respectively.1MHz -*- &/A -\ A . Inhomogeneity is inevitable in a technical ceramic material.5. inclusions of hygroscopic water. but with reduced values for all other higher frequencies as shown in the figures. which results in dielectric losses. Variat~on dielectric loss (tan6)of AIPO.." As a result. defects. the grain boundaries have an amorphous or glassy structure. /-• 1OKHz . Due to the presence of dangling bonds at the surface. together produces an absorption current. Thus a nanophase ceramic acts as a lossy dielectric" with high dielectric loss at low .--7- *--*-t 290 l ----* *-- - 300 T 310 - 320 - r 330 .48-51All the inhomogenities. The formation of space charges under the action of an external electric field will initiate the redistribution of charges within the volume of the dielectric. impurities. the surface layers of nanoparticles will be highly reactive and there is a chance of adsorption of gases like oxygen or nitrogen. to some extent. In nanophase materials. pores filled with air. Absorption current4' in nonpolar dielectrics can be attributed to the inhomogeneity in the elecbical properties of dielectrics. Dielectrics always have. I 340 . I ~ I ~ I ~ I ~ I ~ i 350 360 370 380 T(K) Fig. sample A1 with temperature of then to 0.A 1OOKHz -r. These adsorbed gases cart also cause an increase in dielectric loss.
Also.with frequency for all samples. conductivity will give rise to dielectric 10sses. which decreases at higher frequencies.5. The .' ohm-' cm". For sample A2. the value varies from 0. It can be seen that owincreases .2 x 10.5.c. which increases to 37 x 10. eo is the permittivity of free space. electrical conductivities (no. at 323 K.c. at higher frequencies reduce as temperature increases.1 x 1 0 .C.3(iii)A.' ohm-'cm-' at 3 MHz.'' ohm-lcm-' when the frequency increases from 100 Hz to 3 MHz.' cm-I to 23 x 10. a at 3 MHz increases from 12 x 10. with temperature for different fixed frequencies of all the three nano samples of AIP04 are shown in Fig. which decreases as temperature . cm-I at 300 K to 37 x. In nanophase materials.2 x 10.5. For sample Al.Electrical Properties of Nanocrystalline ALP04 131 frequencies.19. For nano-AIR34 sample A3. The value of oocat room temperature (300 K) rises to a peak value at about 323 K and then decreases slowly for all samples. The variation of 0.) of nanoAIR34 samples with different grain sizes are shown in Fig. is the real part of the measured complex dielectric constant and tan 6 is the dielectric loss factor.17-Fig. For sample A3.~ ohm-' cm" a:. electrical conductivity of the samples can be calculated using the equation oat = 22xfc0 .5.sf tan 6 (5. is the same for all samples at all temperatures. omat 323 K and at 1 0 Hz is 0.'~ The absences of peaks in the frequency versus dielectric loss curves of the present samples show the wide distribution of relaxation times6 5.' ohm-' ..c.Fig.14. The nature of frequency dependence of on.' ohm-' cm-' to 18 x 10. the corresponding variation is from 0. 10" ohm-' cm-' at 323 K. enhancement in d.16. the frequency varies from 100 Hz to 3 MHz. inhomogeneities like defects and space charge formation in the interface layers produce an absorption c:urrent resulting in a dielectric loss.5) E' where f is the frequency. conductivity The a. The frequency dependence of a. values of a. ~ ohm.
15. conductivity (0.5. conductivity (0.) with frequency of sample A2 . Variation of a. Variation of a.) with frequency of sample A3 log f Fig.c.Chapter 5 132 Fig.c.5.14.
34-37 Enhanced electrical conductivity observed in nano AgI has been attributed to defect structure of n a n ~ ~ a r t i c l eIn . conductivity (aac) with frequency of sample A1 increases and falls to 2 x 10-5ohm-' cm-I at 373 K. The nature remains similar. Variation of a.5.2 An increased ionic conductivity was also observed for nanostructured yttria stabilized ~ i r c o n i a .16. Improved electrical conductivity has been reported for many nanophase materials. it is from 7 x 10. 2 3 4 5 6 7 I I log f Fig.21." ohm-' cm-I at 373 K. The corresponding variation for ohm-' cm-I at 300 K to 23 xlo-' ohm-' cm" at 323 K.20. For sample Al. 10.~ ohm-' cm" at 300 K to 18 :u 10" ohm" cm'l at 323 K and then to 8 x 10" ohm-' cm- ' at 373 K.c. but no much appreciable variations as frequencies are decreased. nano ~ e 0 2 "the enhanced s ~~ electrical properties are explained on the basis of interfacial defect formation. ~ ~ .Electrical Properties of Nanocrystalline AIPOd 133 I . sample A2 is from 8 ~ 1 0 ' " which decreases to 9 x 10. Puin and ~eitjans'reported frequency dependent conductivity of nano CaFz and they observed an increase of the conductivity compared to single crystalline CaFz by more than four orders of magnitude.
Variation of a.c.5.5.17.conductivity (o.- v A-A -----* /--• b340 350 360 /+===-n-L-.290 300 310 320 I 330 4 370 380 T(K) Fig.Chapter 5 134 Fig. Variation of a.c.conductivity (oac)with temperature of sample A2 .18.Jwith temperature of sample A 3 1KHz --0lOKHz -A100KHz -v1MHz &5MHz -.
19. conductivities strongly depend on the particle size. every material! will have some free charges. the frequency dependent data indicated that the enhancement was due to grains rather than grain boundary or surface conduction.conductivity (o.c.)with temperature of sample A1 The a. conductivity has been attributed to losses due to bound charges.^^.c.c. conductivity. Variation of a. these charges can follow the field and cause conduction current giving rise to energy losses. the concentration and heat treatment of the sample and the premelting of the electrolytes.Electrical Properties o f Nanocrvstalline Alp04 135 Fig. and under the applied low frequency.c.c.5s" ~ o l l a k ~ ~shown that the temperature dependence of conductivity is due to has .^' and hopping barrier model.c. Many authors presented different arguments on the frequency dependence of a.c.. The a. conductivity am given by52 is where a& is the d. Hence measured a. mode^^'. However. They are the quantum mechanical tunneling multiple hopes. conductivity was explained by many authors5'"' on the basis of excess ion vacancies due to the high conduction of the space charge layer. conductivity and aoc the true value of the a. Also. is The enhancement of a. conductivity exhibited by nanocrystalline materials in the high frequency region.5.c.
which was explained due to the fact that the conduction process through the grain cores and grain boundaries have identical time constants.y and temperature dependence of a. exhibited by a large number of nanocrystalline materials. Also the arcs were found to be highly depressed. which indicates a distribution of relaxation times. Complex plane impedance analysis of polycrystalline BaTi03. This hopping mechanism is compatible with the highly disordered or amorphous structure of the grain boundary layers of nanophase materials. The impedance analysis of nanophase ZnO (grain size 13 nm)' exhibited two partially overlapping semicircles corresponding to grain and grain boundary contributions. 5.all reported the impedance spectra of nanophase ZnO (grain size 60 nm) and found only one semicircle in the impedance spectrum.3(iv) Impedance spectroscopic analysis The complex plane impedance analysis of a number of polycrystalline as well as nanocrystalline materials have been reported. Chiang et.6'.c. field will alter this energy difference and produces a net polarization.all' reported the impedance spectroscopic analysis of nanocrystalline CeOz and observed a low frequency arc corresponding to grains. This which lags behind the field.c. which is out of phase with the applied electric field. 1-5.The nature of frequenc. The complex impedance spectrum of nano Ca& was reported to contain a small segment of the electmje polarization arc at low frequency and a large and depressed arc due to grain boundary at high frequency.Alz03nanocomposite5was found to consist of only one arc. showed a smaller arc due to grain and a large grain boundary arc2' The high value of impedance at grain boundary was explained . But the impedance specua of ZnO. conductivity.c. having high densities of localized levels.20-24 Lee et. which was explained as the grain boundary arc.61362 polarization. The physical significance of this type of frequency dependence comes from the fact that an alternating current can affect an electron confined to two traps.62The time it spends in each trap will depend on the energy difference of the two trap states. suggests an electronic hopping mechanism. is measured as a. conductivity of the present samples. An applied a.
20 - Fig. having grain size 12 nm (Fig.26Resistances due to grain and grain boundary are given by the intercepts of the high and low frequency arcs with the x-axis. aL2'studied the impedance of high purity ZrOz.3 nm). The single arc for all the samples in the present study is in agreement with this observation. has the highest impedance. The arc due to grains was found to be higher than that due to grain boundaries.21 and Fig.22. The contribution to impedance due to grain is very small compared to the grain boundary contribution.20).5.5.6 nm and 16.26The two semicircles at high and low frequencies are identified as due to grain and grain boundary phenomena respectively. The nature of variation remains the same. All the plots contain depressed or distorted semicircle due to the fact that they are made up of two partially overlapping semicircular arcs. The impedance spectra of the present sample.5.22. In the present study. stabilized with CaO. Aoki et. as shown in Fig.Electrical Properties of Nanocrystalline AlP04 137 on the basis of the presence of air gaps and high electrical inhomogenities in the region of the neck between grains. and the trace of a third semicircle at low frequencies due to the electrode interface impedance. 5. Depressed arcs may arise due to several relaxation times or due to a continuous distribution of relaxation times. The single arc reported in the impedance spectrum of ZnO by Lee et al' has been interpreted as due to grain boundary contribution. 5. The two wellseparated semicircles found at higher frequencies were attributed to contributions from the grain interiors and grain boundaries. nanocrystalline Alp04 of different grain sizes at thn:e different temperatures are shown in Fig. In these cases. Similar variations are observed for samples A2 and Al. having different grain sizes. Sample A3. but the diameters of the semic:ircles gradually increase as temperature rises. . only the high frequency arc is prominent. with higher grain sizes (13. the impedance values are diminished. The impedance spectra of polycrystalline ceria showed1 a small arc corresponding to grain contribution and a large semicircle due to grain boundary contribution. The results also reveal that the impedance of nanostructured materials depends on both grain size and temperature of measurement.
5. sample A2 for different temperatures f : 0 2 0 0 50 A 1 1 0 I I 8 1 50 100 150 Z'(k ohm) A 0 0 0 0 0 0 0 a 100 1 A00 0 0 50 Z'(k ohm) 150 a v 200 I s 250 .5.____---.21. lmpedance spectra of n-AIPO.__ - _ 300 F l A A 353K E r 0 Y loo A.20. sample A3 for different temperatures zlOl?150 s E 0 Fig. I 3 A0 : 0 I A A 0 0 1 Fig. Impedance spectra of n-AIPO.
Impedance spectra n.5. sample A1 for different temperatures Fig.AIPO.22.5.Electrical Properties of Nailocrystalline AlP04 139 Z'(k ohm) Fig. A typical impedance spectrum showing all fitting parameters .23.
21 170 220 240 180 200 220 28 24 15 37 2. due to Sample Temperature Rgb Tgb Cgb Ogb (kn) (rad/sec) (deg ) (pF) (X10-6n 'cm ') 313 K A1 323 K 353 K 313 K A2 323 K 353 K 313 K A3 73 130 175 611 2680 1675 2108 1353 1050 1929 1412 1103 8 10 14 2. (5. The diameter of the arc increases as temperature increases.54 4.98 3.4 1 5.54 4. The Cole-Cole expression69for the resulting complex impedance can be written as z ( = Ro + * mgb) I + ( i mgb rgbjI-agb R .24 2. frequency tgb = Rgb Cgb. The parameter a.b measures the deviation of the shape of the impedance plot from the ideal semicircular shape of the grain boundary.25 3. are respectively the intercepts with the real impedance axis at the high frequency end and low frequency end.88 3.54 - - 323 K 353 K 39 34 Table 5. The mean relaxation time for the grain boundary processes.5.02 5.12 - 4.Chapter 5 140 A typical impedance spectrum showing all fitting parameters is given in Fig.87 3.36 3. The contribution to the total resistance of the sample Rgb by the grain boundary is given by the diameter of the arc.69as: shown in the figure. The resistance R due to grain boundary is given by the intercept of the arc with the x-axis.97 2.7) where R and R.67 3.1: Grain boundary parameters of nano Alp04 samples .5.R. pgb is the angle of depression of the semicircle center due to the tilting of the semicircle.23.1. which is the inverse of the peak and thus the grain boundary capacitance C8b can be calculated.The results show that the conductivities of each sample.79 3. a g b is given by The computed parameters of the various grain boundary contributions are tabulated in table.87 4.41 3.
the presence of grain boundaries in nanocrystalline materials is responsible for the observed variations in the conductivities nanocrystalline AIP04. attains a peak value and then decreases at a slower rate. observed in the present study may be due to impurity phases. The dielectric constant initially increases with temperature to a sufficiently high value and thereafter decreases as temperature is further increased. tan 6 was found to increase with temperature. The a. The presence of grains and grain boundaries in nanophase materials are very important in determining their electrical properties.Electrical Properties of Nartocrystalline AlP04 141 grain boundaries (ugh). Also." A significant fraction of atoms in nanophase materials reside in grain boundary environments where they occupy positions relaxed65 from normal sites. which is characteristic of ionic conductors. The lesser conductivity in the grain boundaries. Thus. Since the grain boundary resistance is very large compared with grain resistance. The intergranular porosity largely alters the diameter of the grain boundary arc in the impedance spectrum. it is confirmed that. 67Thus the overall impedance behavior of the three samples arises mainly from contributions due to grain boundaries. conductivity in the present study is attributed mainly through grains.c.68 It can be seen from the figures that the grain conductivity (diameter of the grain boundary arc) increases as particle size decreases. The dielectric constants (E' ) of all the samples are high at low frequencies that decrease with frequency at all temperatures.66. which is a measure of the grain boundary resistance. 5. . The impedance of nanocrystalline A1P04 in the present investigation was found to arise from both grain and grain boundary contributions of which the major component is the latter. porosity and the large area of grain boundary region.4. increase with temperature. The grain boundary resistivity may be attributed to partial or complete blocking of charge carriers due to the presence of defects at the grain boundaries .63. Dielectric loss (tan 6 ) decreases with frequency and at higher frequencies the loss angle has the same low value at all temperatures. Conclusion The dielectric propexties of nanocrystalline Alp04 having three different grain sizes were investigated over a wide range of frequencies 100 Hz -3 MHz and over the temperature from 300 K to 373 K.
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