Adam Berlie

Colossal Dielectric Behavior of Ga+Nb Co-Doped Rutile TiO2

Stimulated by the excellent colossal permittivity (CP) behavior achieved in In+Nb co-doped rutile TiO2, in this work we investigate the CP behavior of Ga and Nb co-doped rutile TiO2, i.e., (Ga(0.5)Nb(0.5))(x)Ti(1-x)O2, where Ga(3+) is from the same group as In(3+) but with a much smaller ionic radius. Colossal permittivity of up to 10(4)-10(5) with an acceptably low dielectric loss (tan δ = 0.05-0.1) over broad frequency/temperature ranges is obtained at x = 0.5% after systematic synthesis optimizations. Systematic structural, defect, and dielectric characterizations suggest that multiple polarization mechanisms exist in this system: defect dipoles at low temperature (∼10-40 K), polaronlike electron hopping/transport at higher temperatures, and a surface barrier layer capacitor effect. Together these mechanisms contribute to the overall dielectric properties, especially apparent observed CP. We believe that this work provides comprehensive guidance for the design of new CP materials.

Plasmon-loss imaging of polymer-methanofullerene bulk heterojunction solar cells

The plasmon feature in an electron energy loss spectrum provides unique insight into poly(3-hexylthiophene) (P3HT)-phenyl-C61-butyric acid methyl ester (PCBM) solar cells. Analysis of the intensity, shape, and energy of the plasmon reveals information about the type of phase, distribution of P3HT semi-crystalline fibres, and PCBM packing density at high spatial resolution. Plasmon-loss imaging has also revealed nano-scale residual solvent pockets with preferentially dissolved PCBM. A robust tomography method for reconstructing the 3D morphology of the bulk heterojunction thin-film via plasmon-loss images is also presented. The analysis techniques can be used to investigate morphology evolution during thin-film processing and its effect on device performance.

Controlling nickel nanoparticle size in an organic/metal-organic matrix through the use of different solvents.

Nickel nanoparticles have been created in an organic-based matrix by the reaction of Ni(COD)2 (COD = 1,5-bis-cyclooctadiene) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (TCNQF4). The size of the nickel nanoparticles can be controlled by the use of different solvents and inclusion of tetrahydrofuran (THF) within the reaction to stabilise the Ni(0) atoms from the Ni(COD)2. Materials are characterised with a combination of X-ray diffraction, electron microscopy and magnetometry and it is found that samples made using a halocarbon solvent resulted in clustered bulk Ni particles (size ≤ 10 nm) with anomalously high superparamagnetic blocking temperatures. Using an isocyanide solvent produces smaller (size ∼ 1 nm), well dispersed particles that show little evidence of superparamagnetic blocking in the range of temperatures investigated (>2 K). In all samples there is another component which dominates the magnetic response at low temperatures and shows an interesting temperature dependent scaling behaviour when plotted as M vs. B/T which we believe is related to the organo-metallic matrix that the particles are trapped within. We propose that the enhanced blocking temperature of particles synthesised using halocarbon solvents can be attributed to inter-particle dipolar interactions and nanoparticle-matrix exchange interactions.

Magnetic ordering of defects in a molecular spin-Peierls system

With interest in charge transfer compounds growing steadily, it is important to understand all aspects of the underlying physics of these systems, including the properties of the defects and interfaces that are universally present in actual experimental systems. For the study of these defects and their interactions a spin-Peierls (SP) system provides a useful testing ground. This work presents an investigation within the SP phase of potassium TCNQF4 where anomalous features are observed in both the magnetic susceptibility and ESR spectra for temperatures between 60 K and 100 K. Muon spin spectroscopy measurements confirm the presence of these anomalous magnetic features, with low temperature zero-field data exhibiting the damped oscillatory form that is a characteristic signature of static magnetic order. This ordering is most likely due to the interaction between structurally correlated magnetic defects in the system. The critical behaviour of the temperature dependent muon spin rotation frequency indicates that a 2D Ising model is applicable to the magnetic ordering of these defects. We show that these observations can be explained by a simple model in which the magnetic defects are located at stacking faults, which provide them with a 2D structural framework to constrain their interactions.

Dipolar glass and magneto-electric coupling within a π-stacked organic system

There is much interest in the search for novel materials that show ferroelectric as well as magneto-electric coupling, such as that observed in multiferroics. Within organic based materials the electronic polarisation can originate from a charge distribution across a molecule or molecules, and so one must search for systems that have an electronic (and magnetic) dipole that is intrinsic. One such material is tetraethylammonium bis-7,7,8,8-tetracyanoquinodimethane (TEA(TCNQ)2) which is a charge transfer system with a single electron that is delocalised across a TCNQ dimer. We show that dielectric measurements yield anomalies at the cation freezing structural distortion and when singlet–triplet excitations freeze. In both cases the electric response is glassy and at low temperature the corresponding magnetic measurements evidence the strong magneto-electric coupling within the material showing scaling behaviour similar to spin glass systems.

A muon spin relaxation study of the metal-organic magnet Ni(TCNQ)2

An investigation of the magnetism of the deuterated form of the metal-organic ferromagnet Ni(TCNQ)2 using the muon spin relaxation technique, is reported. Ni(TCNQ-D4)2 was synthesized in a similar manner to the protio-form, and the crystalline product formed was found to have a Curie temperature of TC=20 K. This transition temperature was 18% larger than that of the protio-form synthesized in our laboratory. Muon spin relaxation measurements were performed in Zero Field (ZF) and in Longitudinal Fields (LF) of up to 0.45 T. The ZF data confirmed that the sample undergoes a bulk ferromagnetic transition at a temperature similar to that observed by the bulk magnetization data. However, ZF measurements also showed that another transition occurs below approximately 6 K, which is believed to be a transition to a magnetic glassy state. The LF results indicate that a significant dynamical component to the magnetism is present below TC as LF fields up to 0.45 T cannot completely re-polarise the spins of the implan...

A sample holder for measuring the magnetic properties of air-sensitive compounds

A sample holder is reported which has allowed the magnetic characterization of air-sensitive compounds to be made in a Quantum Design Magnetic Properties Measurement System as a function of the applied field (0–5 T), and at temperatures ranging from 2 to 290 K. The sample holder is in the form of a specially designed tube, which is made from high purity quartz, utilizes PTFE (polytetrafluoroethylene) plugs and is reusable. This construction also offers the benefit that no heat treatment of the holder is required during sample loading, making the sample holder suitable for thermally sensitive compounds. The application of this sample holder is demonstrated for the case of Ni(cod)2 (cod = 1,5-cyclooctadiene), a compound that decomposes when exposed to air and/or heat. This materials instability has, so far, prevented the magnetic characterization of the compound, with nickel nanoparticles, a product of the decomposition, usually being measured instead.

A 3D antiferromagnetic ground state in a quasi-1D π-stacked charge-transfer system

With the rising interest in organic based materials for spintronic and multiferroic applications it is important to fully understand their electrical and magnetic properties and to identify correlations between their structural and physical attributes. One material that still holds some ambiguity is triethylammonium bis-7,7,8,8-tetracyanoquinodimethane (TEA(TCNQ)2). This charge transfer compound has one electron delocalised across two TCNQ molecules along quasi-1D stacks. Previous work has shown that there is magneto-electrical coupling associated with the magnetic transition at ∼120 K, however the magnetism and magnetic ground-state are not well understood. Within this manuscript we provide evidence for a long range magnetic order that is 3D in nature.

Study of the B-site ion behaviour in the multiferroic perovskite bismuth iron chromium oxide

A simple, near-ambient pressure solid-state method was developed to nominally synthesize BiFe0.5Cr0.5O3. The procedure allowed the gram-scale production of multiferroic samples with appreciable purity and large amounts of Cr incorporation that were suitable for systematic structural investigation by neutron, X-ray, and electron diffraction in tandem with physical characterization of magnetic and ferroelectric properties. The rhombohedrally distorted perovskite phase was assigned to the space group R3c by way of X-ray and neutron powder diffraction analysis. Through a combination of magnetometry and muon spin relaxation, it is evident that there is magnetic ordering in the BFCO phase consistent with G-type antiferromagnetism and a TN ∼ 400 K. There is no clear evidence for chemical ordering of Fe and Cr in the B-site of the perovskite structure and this result is rationalized by density functional theory and bond valence simulations that show a lowered energy associated with a B-site disordered structure. ...

Absence of quantum criticality and bulk 3D magnetism in green dioptase

Green dioptase is a naturally occurring antiferromagnetic mineral that in recent years has been suggested as a candidate to exhibit quantum fluctuations at both above and below T N. Our work uses muon spectroscopy to study the dynamic and static properties of the magnetism in zero applied field. We observe the antiferromagnetic transition through tracking out the evolution of the muon spin precession frequency as a function of temperature. T N is calculated to be 15 K and the critical exponent of the transition matches with that of a 3D Heisenberg system. We also note that no evidence for any quantum magnetic fluctuations is observed either above or below T N.