Title: Spectroscopic investigations of lattice dynamics in multidomain ferroelectrics Author: Elizabeth Vakkechalil John Department: Department of Condensed Matter Physics Institution: Department of Dielectrics, Institute of Physics, AVČR, Na Slovance 2, Praha 8, 182 21, Czech Republic. Supervisor: Ing. Jiří Hlinka, PhD., Department of Dielectrics, Institute of Physics, AVČR., Na Slovance 2, Praha 8, 182 21, Czech Republic. Consultants: RNDr. Stanislav Kamba CSc., Ing. Ivan Gregora CSc. Fyzikální ústav AVČR, Na Slovance 2, Praha 8, 182 21, Czech Republic. Abstract: Lead based ferroelectric perovskites exhibit attractive physical and structural properties. Ferroelectric domains are known to have a very essential impact on dielectric and piezoelectric properties of ferroelectrics. Tailoring of domain structures allows to change the macroscopic symmetry of the material and to purposely modify its average tensor properties. Ferroelastic domains play also a key role in physics of epitaxial ferroelectric films. Here we studied signature of domain structure in PbTiO3 thin film grown by metalorganic chemical vapor deposition technique on different substrates, namely LaAlO3, MgO, NdGaO3, SrTiO3 (100), SrTiO3 (110), SrTiO3 (111) doped with 0.5% Nb and LSAT. Certain aspects of domain structure can be...

The pyroelectric ceramic thin films and detectors based on PbTiO3 that exhibits a low dielectric constant and a high pyroelectric coefficient were fabricated by a sol-gel method in this thesis. The lanthanum (La) and calcium (Ca) were adopted as dopants. The PLT and PCT thin films were deposited on Pt/SiO2/Si substrates by spin coating. 1,3 propanediol was used as solvent to minimize the number of cycles of spin coating and drying processes to obtain the desired thickness of thin film. By changing the dopant content and the heating temperature, the effects of various processing parameters on the thin films growth are studied. The effects of various dopant contents on the response of pyroelectric detectors are also discussed. Experimental results reveal that the dopant contents will influence strongly on the characteristics of thin films such as microstructure, dielectricity, ferroelectricity and pyroelectricity. With the increase of dopant content, the grain size, the coercive field (Ec) and the remanent polarization (Pr) of thin films decrease. The relative dielectric constant (£`r) and the pyroelectric coefficient (g) of thin films increase with increasing the dopant content. In addition, the results also show that the PLT(10) and the PCT(25) thin films exhibit large figures of merit Fv for voltage responsivity (Rv) and Fm for specific detectivity (D*) at the heating temperature of 700¢J. In the pyroelectric properties of thin film detectors, Rv and D* increased with an increase of dopant content. However, Rv and D* decreased when La and Ca content exceeded 10 mol% and 25 mol%, respectively. The PLT(10) and the PCT(25) pyroelectric thin film detectors exist both the maximums of Rv and D*. The results are consistent with the evaluations of Fv and Fm of thin films.

Rhombohedral perovskite BiFeO3 is a single phase multiferroic compound exhibiting both magnetic (Neel temperature ~370˚C) and ferroelectric (Curie point ~840˚C) ordering well above the room temperature. Ferroelectricity in BiFeO3 is due to stereochemically active 6slone pair in Biion which causes large relative displacements of Bi and O ions along the [111] direction. Long range spiral modulation of the canted antiferromagnetic spin arrangement in Feeffectively cancels the macroscopic magnetization due to Dzyaloshinskii–Moriya interaction and thereby prevents linear magneto-electric effect. Synthesizing dense pure BiFeO3 by conventional solid state method is difficult due to the formation of thermodynamically stable secondary phases such as Bi2Fe4O9, Bi25FeO39 and Bi46Fe2O72. To stabilize the perovskite phase and to suppress the cycloid several groups have adopted different strategies such as thin film growth, different synthesis methods and chemical substitution. Of the various substitutions reported in the literature, PbTiO3 substitution has shown very interesting features, such as (i) unusually large tetragonality (c/a~1.19), (ii) formation of morphotropic phase boundary (MPB) and (iii) high curie point Tc~650C. MPB ferroelectric systems such as lead zirconate titanate (PZT) are known to exhibit high piezoelectric response due to the coupling between strain and polarization. Hence the existence of magnetic ordering in BiFeO3-PbTiO3 offers an interesting scenario where polarization, strain and magnetization may couple together. The high Curie point also makes the system an interesting candidate for high temperature piezoelectric application. However its potential as a high temperature piezoelectric material has not been realized yet. A detailed review of literature suggests a lack of clear agreement with regards to the composition range of the reported MPB itself. Different research groups have reported different composition range of MPB for this system even for almost similar synthesis conditions. The present thesis deals with broadly two parts, firstly with the preparation of pure BiFeO3 by co-precipitation and hydrothermal methods and its thermal stability and secondly resolving the cause of discrepancy in range of MPB reported in BiFeO3-PbTiO3 solid solution. Detailed examination of this system (BiFeO3-PbTiO3) around the reported MPB composition by temperature dependent X-ray, electron and neutron diffraction techniques, in conjunction with a systematic correlation of sintering temperature and time with microstructural and phase formation behavior revealed the fact that the formation of MPB or the single ferroelectric phase is critically dependent on the grain size. This phenomenon is also intimately related to the abnormal grain growth in this system. Chapter 1 gives the brief overview of the literature on the topics relevant to the present study. The literature survey starts with a brief introduction about the perovskite oxides; their ferroelectric, magnetic and multiferroic properties were discussed in further sections. A brief outline on the grain growth mechanism is described. An overview of BiFeO3 and various synthesis methods, different chemical substitutions and their effect on properties are provided. A brief review of published literature on BiFeO3-PbTiO3 solid solution and its properties is also presented. Chapter 2 deals with the synthesis of pure BiFeO3, heat treatment and characterisation. BiFeO3 was synthesised by (a) co-precipitation and (b) hydrothermal methods. In co-precipitation method, calcination of precipitate at different temperature resulted in the formation of BiFeO3 along with secondary phases (Bi2Fe4O9 and Bi24FeO39). The optimum calcination temperature to prepare pure BiFeO3 was found to be 560C. The synthesized pure BiFeO3 exhibits weak ferromagnetic hysteresis at room temperature, the degree of which increases slightly at 10K (-263C). The hydrothermal treatment was carried out in (a) carbonate and (b) hydroxide precipitates with KOH as mineralizer. BiFeO3 prepared using hydroxide precipitate was stable till 800C whereas with carbonate precipitate it was stable only till 600C. Chapter 3 deals with the stability of phases in (1-x)BiFeO3 -(x)PbTiO3 solid solution. Samples prepared by conventional solid state route sometimes remain as dense pellet and on certain occasions it disintegrate completely into powder observed after sintering. Irrespective of the composition, sintering time and temperature, powder X-ray Diffraction (XRD) pattern of the survived pellet (crushed into powder) shows coexistence of rhombohedral (R3c) and tetragonal (P4mm) phases and the disintegrated powder (without crushing) show 100% tetragonal (P4mm) phase. Very high spontaneous tetragonal strain (c/a-1) ~0.19 at MPB is believed to be the origin for disintegration. But in all the survived pellets at least a minor fraction of rhombohedral phase (5-7%) is present. Systematic sintering studies with the time and temperature shows, decreasing the sintering temperature and time will increase the lifetime of the pellet and by increasing the sintering temperature and time the pellet will disintegrate. In this work we have conclusively proved that the wide composition range of MPB reported in the literature is due to kinetic arrest of the metastable rhombohedral phase and that if sufficient temperature and time is given, the metastable phase disappears. The suppression/formation of minor rhombohedral phase is expected due to the play of local kinetic factors during the transformation process. This makes the system behave in an unpredictable way with regard to the fraction of rhombohedral phase that is observed at room temperature. A systematic X-ray and neutron powder diffraction study of the giant tetragonality multiferroic (1-x)BiFeO3 -(x)PbTiO3 have shown that the compositions close to the morphotropic phase boundary of this system present two different structural phase transition scenarios on cooling from the cubic phase: (i) Pm3m P4mm(T2)+P4mm(T1) P4mm (T1) and (ii) Pm3m P4mm(T2) + P4mm(T1) + R3c P4mm (T1) + R3c. The comparatively larger tetragonality of the T1 phase as compared to the coexisting isostructural T2 phase is shown to be a result of significantly greater degree of overlap of the Pb/Bi-6s and Ti/Fe-3d with the O-2p orbitals as compared to that in the T2 phase. High temperature electron diffraction studies show that the metastable rhombohedral phase is present in the cubic matrix well above the Curie point as nuclei. Life time of the metastable R3c nuclei is very sensitive to composition and temperature, and nearly diverges at x → 0.27. MPB like state appears only if the system is cooled before the metastable R3c nuclei could vanish. Issue of the metastable rhombohedral state is developed further in Chapter 4. A one-to-one correlation was found between the grain size and phase formation behavior. Fine grained (~1µm) microstructure (usually pellets) shows phase coexistence (R3c+P4mm) and the disintegrated coarse grains (~10µm) show tetragonal (P4mm) phase. Microstructural analysis revealed the disintegration was caused by abnormal grain growth along with the disappearance of metastable rhombohedral phase. Abnormal grain growth starts at the periphery/crack i.e., at the free surface and move towards the canter of the pellet. Size reduction of disintegrated coarse grains (~10µm) to fine grains (~1µm) by crushing the sample showed that the system switching form pure tetragonal (P4mm) state to the MPB state comprising of tetragonal and rhombohedral phases (R3c+P4mm). In another approach the smaller sized particles of x=0.20 were synthesized by sol gel method. It was reported that in conventional solid state route x=0.20 exhibits pure rhombohedral phase. The sol-gel sample calcined at 500C (particle size ~15nm) stabilizes tetragonal metastable phase along with the stable rhombohedral phase, the morphotropic phase boundary state. Samples calcined at higher temperature, 800C (particle size ~50nm) also showed stable rhombohedral phase. Ferromagnetic behavior was observed in the sample having phase coexistence and the sample with pure rhombohedral phase showed antiferromagnetic behavior. Hence this material is a promising candidate which can be tuned to exhibit different behavior just by adopting different grain size. Chapter 5 deals with the magnetic structure of (1-x)BiFeO3 -xPbTiO3 solid solution with change in composition and temperature. Magnetic structure was studied using powder neutron diffraction in the composition range x=0.05 -0.35. Rietveld analysis was carried out for the nuclear and magnetic phases, by considering R3c phase for the nuclear structure. To account for the magnetic Bragg peak at d=4.59Å, three antiferromagnetic models were considered for the magnetic structure: (i) helical spin arrangement as in BiFeO3, (ii) commensurate G-type antiferromagnetic ordering with moments in the a-b plane (of the hexagonal cell), and (iii) commensurate G-type ordering with moments parallel to the c-axis (of the hexagonal cell). The third model was found to be suitable to explain the magnetic peak accurately and the better fitting of magnetic peak was observed in this model compared to others. At room temperature the MPB compositions have rhombohedral and tetragonal nuclear phases along with the rhombohedral magnetic phase. Addition of PbTiO3 in BiFeO3 not only changes the magnetic structure but also reduces the magnetic moment due to the substitution of Ti in Fesite. High temperature neutron diffraction studies reveal the magnetic transition at ~300C for x=0.20, ~95C for x=0.27 and ~150C for x=0.35. The Neel temperature observed in neutron diffraction studies were also confirmed by DSC and by temperature dependent dielectric studies. For x=0.20, anomalous variation in the lattice parameters and the octahedral tilt angle was observed across the magnetic transition temperature. In the magnetic phase, the c-parameter was contracted and the octahedral tilt angle slightly increased. This result suggests a coupling between spin, lattice and structural degrees of freedom around the transition temperature. Temperature dependent powder neutron diffraction study at low temperature from 300K (27C) to 4K (-269C) in x=0.35 shows the evolution of tetragonal magnetic phase at 200K (-73C) whose intensity is increasing with decrease in temperature. Below 200K, x=0.35 has rhombohedral and tetragonal magnetic and nuclear phases. While in x=0.27 at low temperature, rhombohedral magnetic and nuclear phases are present along with the tetragonal nuclear phase alone (the tetragonal magnetic phase is absent). We propose this discrepancy in the Neel temperature and the magnetic phase formation can be due to the probabilistic nature of the existence of metastable rhombohedral phase which was discussed earlier.

Piezoelectric materials find use as actuators and sensors in automotive, aerospace and other related industries. Automotive applications such as fuel injection nozzles and engine health monitoring systems require operating temperatures as high as 300-500 oC. The commercially used piezoelectric material PbZr1-xTixO3 (PZT) is limited to operating temperatures as low as 200 oC due to the temperature induced depolarization effects. PZT, in the undoped state exhibits a piezoelectric coefficient (d33) of 223 pC/N and ferroelectric-paraelectric transition temperature (Tc) of 386 oC. The enhanced properties of PZT occur at a region between the tetragonal and rhombohedral phases, called the Morphotropic Phase Boundary (MPB). Therefore, search for new materials with higher thermal stability and better sensing capabilities were focused on systems that exhibit a PZT-like MPB. This led to the discovery of (x)BiScO3-(1-x)PbTiO3 (BSPT), which exhibits an MPB with enhanced Tc (450 oC) and exceptionally high piezoelectric response (d33 = 460 pC/N). Theoretical studies have shown that the mechanism of enhanced piezoresponse in ferroelectric systems is related to the anisotropic flattening of the free energy profiles. An alternative view point attributes the anomalous piezoelectric response to the presence of high density of low energy domain walls near an inter-ferroelectric transition. Diffraction is a versatile tool to study the structural and microstructural changes of ferroelectric systems upon application of electric field. However, characterization of electric field induced structural and microstructural changes is not a trivial task, since in situ electric field dependent diffraction studies almost invariably give diffraction patterns laden with strong preferred orientation effects, due to the tendency of the ferroelectric/ferroelastic domains to align along the field direction. Additionally, diffraction profiles of MPB compositions exhibit severe overlap of Bragg peaks of the coexisting phases, and hence, it is difficult to ascertain with certainty, if the alteration in the intensity profiles upon application of electric field is due to change in phase fraction of the coexisting phases or due to preferred orientation induced in the different phases by the electric field. The characterization of electric field induced phase transformation in MPB systems, has therefore eluded researchers and has been considered of secondary importance, presumably due to the difficulties in unambiguously establishing the structural changes upon application of electric field. In fact, majority of the in situ electric field dependent diffraction studies have been carried out on compositions just outside the MPB range, i.e. on single phase compositions. In such studies, the focus has been mainly on explaining the piezoelectric response in terms of motions of the non-180° domain walls and field induced lattice strains. In this dissertation, the BSPT system has been systematically investigated with the view to understand the role of different contributing factors to the anomalous piezoelectric response of compositions close to the MPB. Using a comparative in situ electric field dependent diffraction study on a core MPB composition exhibiting highest piezoelectric response and a single phase monoclinic (pseudo-rhombohedral) composition just outside the MPB, it is demonstrated that, inspite of the significantly large domain switching and lattice strain (obtained from peak shifts) in the single phase composition, as compared to the MPB composition, the single phase composition shows considerably low piezoelectric response. This result clearly revealed that the anomalous piezoelectric response of the MPB composition is primarily associated with field induced inter-ferroelectric transformation and the corresponding field induced interphase boundary motion. A simple strategy has been employed to establish the field induced structural transformation for the MPB compositions, by overcoming the experimental limitation of in situ electric field dependent diffraction studies. The idea stemmed from the fact that, if the specimens for diffraction study can be used in powder form instead of pellet, the problems associated with preferred orientation effects can be eliminated, and the nature of field induced structural changes can be accurately determined. A comparative study of the diffraction profiles from poled (after subjecting the specimen to electric field) and unpoled (before subjecting the specimen to electric field) powders could precisely establish the nature of electric field induced phase transformation for the MPB compositions of BSPT and provided a direct correlation between the electric field induced structural changes and the enhanced piezoelectric response. A new ‘powder poling’ technique was devised, which involves application of electric field to powder form of the specimen. Using this technique, it was possible to study separately, the effect of stress and electric field on the nature of structural transformation. A unique outcome of this study was, it could demonstrate for the first time, analogous nature of the stress and electric field induced structural transformation. A comparative study of the dielectric response of poled and unpoled samples was used to show a counterintuitive phenomenon of field induced decrease in polarization coherence for the MPB compositions. This approach was used to suggest that the criticality associated with the MPB extends beyond the composition boundary conventionally reported in literature based on bulk diffraction techniques (x-ray and neutron powder diffraction). The layout of the dissertation is as follows: Chapter 1 gives a brief introduction of the fundamental concepts related to ferroelectric materials. The theories that explain the enhanced piezoresponse of MPB based ferroelectric systems have been outlined. Detailed information of the existing literature is presented in the relevant chapters. Chapter 2 presents the details of the solid state synthesis of BSPT compositions and structural analysis using diffraction studies. The dielectric measurements were used to establish the Tc for the different compositions. The enhanced ferroelectric and piezoelectric properties were observed for the MPB compositions, which were shown to exhibit coexistence of tetragonal and monoclinic phases from structural studies. The critical MPB composition exhibiting highest piezoelectric and ferroelectric properties was established to be x = 0.3725. The thermal stability of the critical MPB composition was established to be 400 oC using ex situ thermal depolarization studies. The common approach of structural analysis in the unpoled state failed to provide a unique relationship between the anomalous piezoelectric response and the structural factors at the MPB, emphasizing the need to characterize these system using electric field dependent structural studies. Chapter 3 presents the results of in situ electric field dependent diffraction measurements carried out at Argonne National Laboratory, USA. The quasi-static field measurements could successfully quantify the non-180o domain switching fractions and the field induced lattice strains. The changes in the integrated intensities were used to obtain the non-180o domain switching fraction and the shift in peak positions were used to quantify the field induced lattice strains. The in situ studies could successfully explain the macroscopic strain response for the single phase pseudo-rhombohedral (monoclinic) composition on the basis of domain switching mechanisms and field induced lattice strains. The MPB compositions were shown to have additional contributions from interphase boundary motion, resulting from change in phase fraction of the coexisting phases. The results emphasized the need to investigate the electric field induced transformation for MPB compositions, in order to give a comprehensive picture of the various contributions to the macroscopic piezoreponse. While Rietveld analysis could be used to investigate the phase transformation behaviour upon application of electric field, textured diffraction profiles obtained using in situ studies, in addition to the severely overlapping Bragg reflections of the coexisting phases for the MPB compositions hindered reliable estimation of the structural parameters. An alternate approach to investigate the field induced phase transformation is presented in Chapter 4. The stroboscopic measurements on the MPB composition showed evidence of non-180o domain wall motion even at sub-coercive field amplitudes as low as 0.1 kV/mm. Chapter 4 presents the results of the ex situ electric field dependent structural study, wherein the diffraction profiles collected from poled powders is compared to that of unpoled powders. The diffraction profiles from the poled powders did not exhibit any field induced crystallographic texture and could successfully be analyzed using Rietveld analysis. High resolution synchrotron diffraction studies (ESRF, France) carried out on closely spaced compositions revealed that, the composition exhibiting the highest piezoelectric response is the one, which exhibits significantly enhanced lattice polarizability of both the coexisting (monoclinic and tetragonal) phases. The enhanced lattice polarizability manifests as significant fraction of the monoclinic phase transforming irreversibly to the tetragonal phase after electric poling. The monoclinic to tetragonal transformation suggested the existence of a low energy polarization rotation pathway towards the [001]pc direction in the (1 1 0)pc pseudocubic plane of the monoclinic phase. The results are discussed on the basis of the existing theories that explain piezoresponse in MPB systems and are in support of the Polarization rotation model, in favor of a genuine monoclinic phase. Chapter 5 discusses the ferroelectric-ferroelectric stability of the MPB compositions in response to externally applied stress and electric field independently. Using the newly developed ‘powder poling’ technique, which is based on the concept of exploiting the irreversible structural changes that occur after application of electric field and stress independently, it was possible to ascertain that, both moderate stress and electric field induce identical structural transformation - a fraction of the monoclinic phase transforms irreversibly to the tetragonal phase. The powder poling technique was also used to demonstrate field induced inter-ferroelectric transformation at sub-coercive field amplitudes. In addition, the analysis of the dielectric response before and after poling revealed a counterintuitive phenomenon of poling induced decrease in the spatial coherence of polarization for compositions around the MPB and not so for compositions far away from the MPB range. Exploiting the greater sensitivity of this technique, it was demonstrated that, the criticality associated with the inter-ferroelectric transition spans a wider composition range than what is conventionally reported in the literature based on bulk x-ray/neutron powder diffraction techniques. Chapter 6 presents the closure and important conclusions from the present work and summarizes the key results, highlighting the proposed mechanism of enhanced piezoresponse in BSPT. The last part of the chapter deals with suggestions for future work from the ideas evolved in the present study. vi

The increasing miniaturization of electric and mechanical components makes the synthesis and assembly of nanoscale structures an important step in modern technology. Functional materials, such as the ferroelectric perovskites, are vital to the integration and utility value of nanotechnology in the future. In the present work, chemical methods to synthesize one-dimensional (1D) nanostructures of ferroelectric perovskites have been studied. To successfully and controllably make 1D nanostructures by chemical methods it is very important to understand the growth mechanism of these nanostructures, in order to design the structures for use in various applications. For the integration of 1D nanostructures into devices it is also very important to be able to make arrays and large-area designed structures from the building blocks that single nanostructures constitute. As functional materials, it is of course also vital to study the properties of the nanostructures. The characterization of properties of single nanostructures is challenging, but essential to the use of such structures. The aim of this work has been to synthesize high quality single-crystalline 1D nanostructures of ferroelectric perovskites with emphasis on PbTiO3 , to make arrays or hierarchical nanostructures of 1D nanostructures on substrates, to understand the growth mechanisms of the 1D nanostructures, and to investigate the ferroelectric and piezoelectric properties of the 1D nanostructures. In Paper I, a molten salt synthesis route, previously reported to yield BaTiO3 , PbTiO3 and Na2Ti6O13 nanorods, was re-examined in order to elucidate the role of volatile chlorides. A precursor mixture containing barium (or lead) and titaniumwas annealed in the presence of NaCl at 760 °C or 820 °C. The main products were respectively isometric nanocrystalline BaTiO3 and PbTiO3. Nanorods were also detected, but electron diffraction revealed that the composition of the nanorods was respectively BaTi2O5/BaTi5O11 and Na2Ti6O13 for the two different systems, in contradiction to the previous studies. It was shown that NaCl reacted with BaO(PbO) resulting in loss of volatile BaCl2 (PbCl2 ) and formation and preferential growth of titanium oxide-rich nanorods instead of the target phase BaTiO3 (or PbTiO3 ). The molten salt synthesis route may therefore not necessarily yield nanorods of the target ternary oxide as reported previously. In addition, the importance of NaCl(g) for the growth of nanorods below the melting point of NaCl was demonstrated in a special experimental setup, where NaCl and the precursors were physically separated. In Paper II and III, a hydrothermal synthesis method to grow arrays and hierarchical nanostructures of PbTiO3 nanorods and platelets on substrates is presented. Hydrothermal treatment of an amorphous PbTiO3 precursor in the presence of a surfactant and PbTiO3 or SrTiO3 substrates resulted in the growth of PbTiO3 nanorods and platelets aligned in the crystallographic <100> orientations of the SrTiO3 substrates. PbTiO3 nanorods oriented perpendicular to the substrate surface could also be grown directly on the substrate by a modified synthesis method. The hydrothermal method described in Paper II and III was developed on the basis of the method described in Appendices I and II. In Paper IV, a template-assisted method to make PbTiO3 nanotubes is presented. An equimolar Pb-Ti sol was dropped onto porous alumina membranes and penetrated into the channels of the template. Single-phase PbTiO3 perovskite nanotubes were obtained by annealing at 700 °C for 6 h. The nanotubes haddiameters of 200 - 400 nm with a wall thickness of approximately 20 nm. Excess PbO or annealing in a Pb-containing atmosphere was not necessary in order to achieve single phase PbTiO3 nanotubes. The influence of the heating procedure and the sol concentration is discussed. In Paper V, a piezoresponse force microscopy study of single PbTiO3 nanorods is presented. The piezoelectric properties were studied in both vertical and lateral mode. Piezoelectric activity and polarization switching was observed in the vertical mode, demonstrating the ferroelectric nature of the nanorods. The nanorods decomposed after repeated cycling of the dc bias at one spot on the nanorod, which resulted in parts of the nanorod disappearing and/or accumulation of particles on the surface of the nanorod. In Paper VI, a method to contact single nanorods by electron beam induced deposition of platinum is presented. An organometallic compound, (trimethyl)-methylcyclopentadienylplatinum(IV), was used as precursor. A home-made apparatus was constructed for the purpose and was mounted onto a scanning electron microscope. Calculations based on apparatus geometry and molecular flow were used to estimate the deposition time and the height of the deposits. The location and height of the deposits were controlled so that single nanorods could be successfully contacted at the ends of the nanorods. Fabrication of a sample device for piezoresponse force microscopy studies of single nanorods using an axial dc bias setup is described in Appendix IV. A proposed experimental setup for such studies is also presented.