Nanoscale ferroelectrics machined from single crystals

This paper summarises some of the most recent work that has been done on nanoscale ferroelectrics as a result of a joint collaborative research effort involving groups in Queen's University Belfast, the University of Cambridge and the University of St. Andrews. Attempts have been made to observe fundamental effects of reduced size, and increasing morphological complexity, on ferroelectric behaviour by studying the functional response and domain characteristics in nanoscale single crystal material, whose size and morphology have been defined by Focused Ion Beam (FIB) patterning. This approach to nanoshape fabrication has allowed the following broad statements to be made: (i) in single crystal BaTiO3 sheets, permittivity and phase transition behaviour is not altered from that of bulk material down to a thickness of similar to 75 nm; (ii) in single crystal BaTiO3 sheets and nanowires changes in observed domain morphologies are consistent with large scale continuum modeling.

Thin film capacitor cut from single crystals using focused ion beam milling

The focused ion beam microscope (FIB) has been used to fabricate thin parallel-sided ferroelectric capacitors from single crystals of BaTiO3 and SrTiO3. A series of nano-sized capacitors ranging in thickness from similar to660 nm to similar to300 nm were made. Cross-sectional high resolution transmission electron microscopy (HRTEM) revealed that during capacitor fabrication, the FIB rendered around 20 nm of dielectric at the electrode-dielectric interface amorphous, associated with local gallium impregnation. Such a region would act electrically in series with the single crystal and would presumably have a considerable negative influence on the dielectric properties. However, thermal annealing prior to gold electrodes deposition was found to fully recover the single crystal capacitors and homogenise the gallium profile. The dielectric testing of the STO ultra-thin single crystal capacitors was performed yielding a room temperature dielectric constant of similar to300, as is the case in bulk. Therefore, there was no evidence of a collapse in dielectric constant associated with thin film dimensions.

Regular nanodomain vertex arrays in BiFeO3 single crystals

Domain patterns consisting of triangular nanodomains of less than 50 nm size, arranged into long regular vertex arrays separated by stripe domains, were observed by (scanning and high-resolution) transmission electron microscopy and piezoresponse force microscopy in BiFeO3 single crystals grown from solution flux. Piezoresponse force microscopy analysis together with crystallographic analysis by selected area and nanobeam electron diffraction indicate that these patterns consist of ferroelectric 109 degrees domains. A possibility for conserving Kittel's law is discussed in terms of the patterns being confined to the skin layer observed recently on BiFeO3 single crystals.

Origin of Ferroelastic domains in Free-Standing Single Crystal Ferroelectric Films

The origin of the unusual 90 degrees ferroelectric/ferroelastic domains, consistently observed in recent studies on mesoscale and nanoscale free-standing single crystals of BaTiO3 [Schilling , Phys. Rev. B 74, 024115 (2006); Schilling , Nano Lett. 7, 3787 (2007)], has been considered. A model has been developed which postulates that the domains form as a response to elastic stress induced by a surface layer which does not undergo the paraelectric-ferroelectric cubic-tetragonal phase transition. This model was found to accurately account for the changes in domain periodicity as a function of size that had been observed experimentally. The physical origin of the surface layer might readily be associated with patterning damage, seen in experiment; however, when all evidence of physical damage is removed from the BaTiO3 surfaces by thermal annealing, the domain configuration remains practically unchanged. This suggests a more intrinsic origin, such as the increased importance of surface tension at small dimensions. The effect of surface tension is also shown to be proportional to the difference in hardness between the surface and the interior of the ferroelectric. The present model for surface-tension induced twinning should also be relevant for finely grained or core-shell structured ceramics.

Domain annihilation due to temperature and thickness gradients in single-crystal BaTiO3

The manner in which 90? ferroelectric-ferroelastic domains respond to changes in temperature has been mapped in BaTiO3 single crystals using atomic force microscopy. Domain periodicity remains unaltered until approximately 2 ? C below the Curie temperature (TC ), whereupon domains coarsened dramatically. This behavior was successfully rationalized by considering the temperature dependence of the parameters associated with standard models of ferroelastic domain formation. However, while successful in describing the expected radical increase in equilibrium period with temperature, the model did not predict the unusual mechanism by which domain coarsening occurred; this was not continuous at a local level but instead involved discrete domain annihilation events. Subsequent insights from a combination of free energy analysis for the system and further experimental data from an analogous situation, in which domain period increases with increasing crystal thickness, suggested that domain annihilation is inevitable whenever a component of the relevant gradient that affects domain period is orientated parallel to the domain walls. Consistent with this thesis, we note that, for the observations presented herein, the thermal gradient possessed a significant component parallel to the domain walls. We suggest that domain annihilation is a general feature of domain structures in gradient fields.

Thickness independence of true phase transition temperatures in barium strontium titanate films

The functional properties of two types of barium strontium titanate (BST) thin film capacitor structures were studied: one set of structures was made using pulsed-laser deposition (PLD) and the other using chemical solution deposition. While initial observations on PLD films looking at the behavior of T-m (the temperature at which the maximum dielectric constant was observed) and T-c(*) (from Curie-Weiss analysis) suggested that the paraelectric-ferroelectric phase transition was progressively depressed in temperature as BST film thickness was reduced, further work suggested that this was not the case. Rather, it appears that the temperatures at which phase transitions occur in the thin films are independent of film thickness. Further, the fact that in many cases three transitions are observable, suggests that the sequence of symmetry transitions that occur in the thin films are the same as in bulk single crystals. This new observation could have implications for the validity of the theoretically produced thin film phase diagrams derived by Pertsev [Phys. Rev. Lett. 80, 1988 (1998)] and extended by Ban and Alpay [J. Appl. Phys. 91, 9288 (2002)]. In addition, the fact that T-m measured for virgin films does not correlate well with the inherent phase transition behavior, suggests that the use of T-m alone to infer information about the thermodynamics of thin film capacitor behavior, may not be sufficient. (C) 2004 American Institute of Physics.

Intrinsic dielectric response in ferroelectric nano-capacitors

Measurements on 'free-standing' single-crystal barium titanate capacitors with thickness down to 75 nm show a dielectric response typical of large single crystals, rather than conventional thin films. There is a notable absence of any broadening or temperature shift of the dielectric peak or loss tangent. Peak dielectric constants of similar to25 000 are observed, and Curie-Weiss analysis demonstrates first order transformation behaviour. This is in dramatic contrast to results on conventionally deposited thin film capacitor heterostructures, which show large dielectric peak broadening and temperature shifts (e.g. Parker et al 2002 Appl. Phys. Lett. 81 340), as well as an apparent change in the nature-of the paraelectric-ferroelectric transition from first to second order. Our data are compatible with a recent model by Bratkovsky and Levanyuk (2004 Preprint cond-mat/0402100), which attributes dielectric peak broadening to gradient terms that will exist in any thin film capacitor heterostructure. The observed recovery of first order transformation behaviour is consistent with the absence of significant substrate clamping in our experiment, as modelled by Pertsev et al (1998,Phys. Rev. Lett. 80 1988), and illustrates that the second order behaviour seen in conventionally deposited thin films cannot be attributed to the effects of reduced dimensionality in the system, nor to the influence of an intrinsic universal interfacial capacitance associated with the electrode- ferroelectric interface.

YF[MoO4] and YCl[MoO4]: Two halide derivatives of yttrium ortho-oxomolybdate: Syntheses, structures, and luminescence properties

The halide derivatives of yttrium ortho-oxomolybdate YX[MoO4] (X = F, Cl) both crystallize in the monoclinic system with four formula units per unit cell. YF[MoO4] exhibits a primitive cell setting (space group P2(1)/c, a = 519.62(2) pm, b = 1225.14(7) pm, c = 663.30(3) pm, beta = 112.851(4)degrees), whereas the lattice of YCl[MoO4] shows face-centering (space group C2/m; a = 1019.02(5) pm, b = 720.67(4) pm, c = 681.50(3) pm, beta = 107.130(4)degrees). The two compounds each contain crystallographically unique Y3+ cations, which are found to have a coordination environment of six oxide and two halide anions. In the case of YF[MoO4], the coordination environment is seen as square antiprisms, and for YCl[MoO4], trigon-dodecahedra. are found. The discrete tetrahedral [MoO4](2-) units of the fluoride derivative are exclusively bound by six terminal Y3+ cations, while those of the chloride compound show a 5-fold coordination around the tetrahedra with one edge-bridging and four terminal Y3+ cations. The halide anions in each compound exhibit a coordination number of two, building up isolated planar rhombus-shaped units according to [Y2F2](4+) in YF[MoO4] and [Y2Cl2](4+) in YCl[MoO4], respectively. Both compounds were synthesized at high temperatures using Y2O3, MoO3, and the corresponding yttrium trihalide in a molar ratio of 1:3:1. Single crystals of both are insensitive to moist air and are found to be coarse shaped and colorless with optical band gaps situated in the near UV around 3.78 eV for the fluoride and 3.82 eV for the chloride derivative. Furthermore, YF[MoO4] seems to be a suitable material for doping to obtain luminescent materials because the Eu3+-doped compound shows an intense red luminescence, which has been spectroscopically investigated.

Mercuric bis(N-imino-methyl-formamidate), Hg(Imf)(2)

Single crystals of mercuric bis(N-imino-methyl-formamidate), Hg(Imf)(2), were obtained from aqueous solutions of 1,2,4-triazole and Hg(NO3)(2)center dot 2H(2)O. The crystal structure [monoclinic, P2(1)/c (no. 14), a = 499.6(2), b = 1051.2(4), c = 711.1(3) pm, beta = 117.55(1)degrees, Z = 2, R, for 890 reflections with I-0 > 2 sigma(I-0): 0.0369] contains linear centrosymmetric Hg(Imf)(2) molecules with Hg-N distances of only 203.5(7)pm. Two plus two intra- and intermolecular nitrogen atoms add to an effective coordination number of 6.