Electrical properties of some single crystal dodecaborides /|nby Jyoti Burte. -- 260 St. Catharines [Ont. : s. n.],

PreVi011.3 ':i or~ : indicat e('. tk~t ho t~)rE's sed ~-Al B 12 1i~2, ~' a semiconductor. r:Toreove r , the s i mpl.(~ electronic t heory also indi cates that ~ -AIB1 2 should be a semico nductor, since thf're is one nonbonding e 'Le ctrofl per AlB12- uni t. JPor these reasons, we decided to measure t he electrical n ropert i ~ s of ~ -AlB1 2 single crystal s . Singl e crystal s of¥- AIB 12 ab ou t 1 x 1 r1n1 . size were grown from a copper mel t at 12500 C. The melt technique coupled. 1,vi th slow cooling vilas used because of i ts advantages such as : siTYInle set- up of the expe rimon t ; only e ;l.sil y available c hemi cals are required and it i s a c omparatively strair::bt forvvard y,le t hod still yielding crystal s big enouGh for OtU' purpose . Copper rms used as a solvent , i nst8ad of previOl.wly used aluminum , because it allows c.l.'ystal growth at hig he r t emneratures. HovlGver, the cry s tals of ] -AlB12 shm'red very hi gh res i s t ance a t r oom temperature . From our neasureJ'lents we conclude that the r esistivity of j3- Al B12 is, at least, given as ~ = 4. x 107 oblD .em •• Those results are inc ons i s t ent wi 'uh the ones .. reported by IIiss Khin fo r bot- pressed j3-AlB12 g i ven a s = 7600 ohm . em . or I e s s . ' Since tbe hot pressing was done at about 800 - ' 9000C i n ~ rap hi te moul ds 1,7i th 97% AlB12- p oVJder, vie thi nk there is pas s ib i 1 i ty th a.t lower borides or borot] carbide are , being formed, ':.Jhich are k11 own to be good semiconductors . v7e tried to ro-pe r-AlB12 by addi'J,'?: agents s uch as l:Ig , IG.-InO 4. ' HgS04 , KI12PO 4·' etc. to t he melt .. However , all these re age 11 t eel either reduced the yield and size of t lJe crystals or r;ave crystals of high r esis'can ce again. We think tba t molten copper keeps t he i mpurities off . There is also a pos s i bil i ty t hc:!,t these doping agents get oxidi~::;ed at '1 250°C • Hence, we co ~ clud e that J -AIB12 has v~ ry high r es i stance at r oom temperature . This was a l s o C011 - fi rmed by checki ng the siYlgle and. polycrystals of .~-AIB12 from Norton Co., Ontario and Cooper Nletallurgical Association. Boron carbide has been reported to be a semiconductor with ~ - 0.3 to 0.8 ohm . cm. for hotpres sed s araples. Boron carbide b e inq: struct urally related to ¥-AIB12 , we de cided to study the electrical prone rties of it~ Single crystals. These crystals were cut from a Single melt grovvn crystal a t Norton Co., Ontario. The resistivity of th," se crystal s was measured by the Van der Pam-v' s ~ nethod, which \vas very c onvenient fo r our crystal sha-pp.s. Some of the crystals showed resistivity ~ == 0.50 ob,Tn.cr] . i n agreement with the previously reported results . However , a few crystals showed lower resistivity e.g . 0 .13 and 0.20 ohm.cra • • The Hall mobility could .not be measured and th8reiore i s lower than 0 .16 em 2 v - 1 sec -1 • This is in agreement \vith t he re1)orted Hall mobility for pyrolytic boron . _ 2 -1 -1 carbide as 0.13 cm v sec • We also studied the orientation of the boron carbide crystals by the Jjaue-method. The inclination of c-axis with res pect to x-ray be81Il was det ermined . This was found to be 100 t o 20° f or normal resistivity sarnples (0.5 ohm . cm.) and 27 - 30° for t he lower r esistivity samples (0.1 ~5 to 0.20 ohm.cm .). This indica tes the possibility that th.e r es if.1tivity of B13C3 i s orientation dependent.

Tetrathiafulvalene and 2,2'-Bipyridine: Bridging both Worlds in the Pursuit of Novel Molecular Materials

The preparation and characterization of two families of building blocks for molecule-based magnetic and conducting materials are described in three projects. In the first project the synthesis and characterization of three bis-imine ligands LI - L3 is reported. Coordination of LI to a series of metal salts afforded the five novel coordination complexes Sn(L4)C4 (I), [Mn(L4)(u-CI)(CI)(EtOH)h (II), [CU(L4)(u-sal) h(CI04)2 (sal = salicylaldehyde anion) (III), [Fe(Ls)2]CI (IV) and [Fe(LI)h(u-O) (V). All complexes have been structurally and magnetically characterized. X-ray diffraction studies revealed that, upon coordination to Lewis acidic metal salts, the imine bonds of LI are susceptible to nucleophilic attack. As a consequence, the coordination complexes (I) - (IV) contain either the cyclised ligand L4 or hydrolysed ligand Ls. In contrast, the dimeric Fe3+ complex (V) comprises two intact ligand LI molecules. In. this complex, the ligand chelates two Fe(III) centres in a bis-bidentate manner through the lone pairs of a phenoxy oxygen and an imine nitrogen atom. Magnetic studies of complexes (II-V) indicate that the dominant interactions between neighbouring metal centres in all of the complexes are antiferromagnetic. In the second project the synthesis and characterization two families of TTF donors, namely the cyano aryl compounds (VI) - (XI) and the his-aryl TTF derivatives (XII) - (XIV) are reported. The crystal structures of compounds (VI), (VII), (IX) and (XII) exhibit regular stacks comprising of neutral donors. The UV -Vis spectra of compounds (VI) - (XIV) present an leT band, indicative of the transfer of electron density from the TTF donors to the aryl acceptor molecules. Chemical oxidation of donors (VI), (VII), (IX) and (XII) with iodine afforded a series of CT salts that where possible have been characterized by single crystal X -ray diffraction. Structural studies showed that the radical cations in these salts are organized in stacks comprising of dimers of oxidized TTF donors. All four salts behave as semiconductors, displaying room temperature conductivities ranging from 1.852 x 10-7 to 9.620 X 10-3 Scm-I. A second series of CT salts were successfully prepared via the technique of electrocrystallization. Following this methodology, single crystals of two CT salts were obtained. The single crystal X-ray structures of both salts are isostructural, displaying stacks formed by trimers of oxidized donors. Variable temperature conductivity measurements carried out on this series of CT salts reveal they also are semiconductors with conductivities ranging from 2.94 x 10-7 to 1.960 X 10-3 S em-I at room temperature. In the third project the synthesis and characterization of a series of MII(hfac)2 coordination complexes of donor ligand (XII) where M2+ = Co2+, Cu2+, Ni2+ and Zn2+ are reported. These complexes crystallize in a head-to-tail arrangement of TTF donor and bipyridine moieties, placing the metal centres and hfac ligands are located outside the stacks. Magnetic studies of the complexes (XV) - (XVIII) indicate that the bulky hfac ligands prevent neighbouring metal centres from assembling in close proximity, and thus they are magnetically isolated.

Laser induced surface damage, thermal transport and microhardness studies on certain organic and semiorganic nonlinear optical crystals

N-alkyl-2,6-dimethyl-4(1H)-pyridinones, salts of 4-dimethylaminopyridine and 2-amino-5-nitropyridine are considered to be potential candidates for nonlinear optical (NLO) applications, in particular for the generation of blue-green laser radiation. Single crystals were grown following the slow evaporation technique at constant temperature. Single-shot laserinduced surface damage thresholds in the range 3–10 GW/cm2 were measured using a 18 ns Q-switched Nd:YAG laser. The surface morphologies of the damaged crystals were examined under an optical microscope and the nature of damage identified. The Vicker’s microhardness was determined at a load of 98.07 mN. The thermal transport properties, thermal diffusivity (α), thermal effusivity (e), thermal conductivity (K) and heat capacity (Cp), of the grown crystals were measured by an improved photopyroelectric technique at room temperature. All the results are presented and discussed.

Magnetic properties and domain-wall motion in single-crystal BaFe10.2Sn0.74Co0.66O19

The magnetic properties of BaFe12O19 and BaFe10.2Sn0.74Co0.66O19 single crystals have been investigated in the temperature range (1.8 to 320 K) with a varying field from -5 to +5 T applied parallel and perpendicular to the c axis. Low-temperature magnetic relaxation, which is ascribed to the domain-wall motion, was performed between 1.8 and 15 K. The relaxation of magnetization exhibits a linear dependence on logarithmic time. The magnetic viscosity extracted from the relaxation data, decreases linearly as temperature goes down, which may correspond to the thermal depinning of domain walls. Below 2.5 K, the viscosity begins to deviate from the linear dependence on temperature, tending to be temperature independent. The near temperature independence of viscosity suggests the existence of quantum tunneling of antiferromagnetic domain wall in this temperature range.

Quadratic tranverse anisotropy term due to dislocations in Mn12 acetate crystals directly observed by EPR spectroscopy

High-sensitivity electron paramagnetic resonance experiments have been carried out in fresh and stressed Mn12 acetate single crystals for frequencies ranging from 40 GHz up to 110 GHz. The high number of crystal dislocations formed in the stressing process introduces a E(Sx2-Sy2) transverse anisotropy term in the spin Hamiltonian. From the behavior of the resonant absorptions on the applied transverse magnetic field we have obtained an average value for E=22 mK, corresponding to a concentration of dislocations per unit cell of c=10-3.

Electrical And Photoacoustic Studies On Phase Transitions In Certain Ammonium Containing Crystals

In the present thesis a series of exhaustive investigations have been carried out on a number of crystalline samples with special reference tx> the jphase transitions exhibited by them. These include single crystals of pure, doped or deuterated specimens of certain ammonium containing crystals viz., (NH )34H(SO4)2, (NH4)2HPO4, (NH4)2Cr2O7 znui NH4H2PO4. ac/dc electrical conductivity, dielectric constant, ionic thermocurrent as wwifil as photoacoustic measurements have been carried out on most of them over a wide range of temperature. In addition investigations have been carried out in pure and doped single crystals of NaClO3 and NaNO3 using ionic thermocurrent measurements and these are presented here. Special attention has been paid to reveal the mechanism of electrical conduction in various phases of "these crystals and to evaluate the different parameters involved in the conduction as well as phase transition process. The thesis contains ten chapters ‘

Temperature dependent polarized Raman spectra of nonaaqualanthanoid (Pr) single crystal

Polarized Raman spectral changes with respect to temperature were investigated for Pr(BrO3)3·9H2O single crystals. FTIR spectra of hydrated and deuterated analogues were also recorded and analysed. Temperature dependent Raman spectral variation have been explained with the help of the thermograms recorded for the crystal. Factor group analysis could propose the appearance ofBrO3 ions at sites corresponding to C3v (4) and D3h (2). Analysis of the vibrational bands at room temperature confirms a distorted C3v symmetry for the BrO3 ion in the crystal. From the vibrations of water molecules, hydrogen bonds of varying strengths have also been identified in the crystal. The appearance υ1 mode of BrO3− anion at lower wavenumber region is attributed to the attachment of hydrogen atoms to the BrO3− anion. At high temperatures, structural rearrangement is taking place for bothH2Omolecule and BrO3 ions leading to the loss ofwater molecules and structural reorientation of bromate ions causing phase transition of the crystal at the temperature of 447 K.

Mononuclear single helices of lanthanum(III) and europium(III). Metal dependent diastereomeric excess

Using the 1: 2 condensate of benzildihydrazone and 2-acetylpyridine as a tetradentate N donor ligand L, LaL(NO3)(3) (1) and EuL(NO3)(3) (2), which are pale yellow in colour, are synthesized. While single crystals of 1 could not be obtained, 2 crystallises as a monodichloromethane solvate, 2 center dot CH2Cl2 in the space group Cc with a = 11.7099(5) angstrom, b = 16.4872(5) angstrom, c = 17.9224(6) angstrom and beta = 104.048(4)degrees. From the X-ray crystal structure, 2 is found to be a rare example of monohelical complex of Eu(III). Complex 1 is diamagnetic. The magnetic moment of 2 at room temperature is 3.32 BM. Comparing the FT-IR spectra of 1 and 2, it is concluded that 1 also is a mononuclear single helix. H-1 NMR reveals that both 1 and 2 are mixtures of two diastereomers. In the case of the La(III) complex (1), the diastereomeric excess is only 10% but in the Eu(III) complex 2 it is 80%. The occurrence of diastereomerism is explained by the chiralities of the helical motif and the type of pentakis chelates present in 1 and 2.

Nonlinear refractive index of RECOB (RE = Gd and La) crystals

The Z-scan technique is employed to obtain the nonlinear refractive index (n (2)) of the Ca(4)REO(BO(3))(3) (RECOB, where RE = Gd and La) single crystals using 30 fs laser pulses centered at 780 nm for the two orthogonal orientations determined by the optical axes (X and Z) relative to the direction of propagation of the laser beam (k//Y// crystallographic b-axis). The large values of n (2) indicate that both GdCOB and LaCOB are potential hosts for Yb:RECOB lasers operating in the Kerr-lens mode locking (KLM) regime.

Effect of Different Solvent Ratios (Water/Ethylene Glycol) on the Growth Process of CaMoO(4) Crystals and Their Optical Properties

In this paper, calcium molybdate (CaMoO(4)) crystals (meso- and nanoscale) were synthesized by the coprecipitation method using different solvent volume ratios (water/ethylene glycol). Subsequently, the obtained suspensions were processed in microwave-assisted hydrothermal/solvothermal systems at 140 degrees C for 1 h. These meso- and nanocrystals processed were characterized by X-ray diffraction (X R I)), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR). ultraviolet visible (UV-vis) absorption spectroscopies, held-emission gun scanning electron microscopy (FEG-SEM). transmission electron microscopy (TEM). and photoluminescence (PL) measurements. X RI) patterns and FT-Raman spectra showed that these meso- and nanocrystals have a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 827 cm(-1), which is associated with the Mo-O anti-symmetric stretching vibrations into the [MoO(4)] clusters. FEG-SEM micrographs indicated that the ethylene glycol concentration in the aqueous solution plays an important role in the morphological evolution of CaMoO(4) crystals. High-resolution TEM micrographs demonstrated that the mesocrystals consist of several aggregated nanoparticles with electron diffraction patterns of monocrystal. In addition, the differences observed in the selected area electron diffraction patterns of CaMoO(4) crystals proved the coexistence of both nano- and mesostructures, First-principles quantum mechanical calculations based on the density functional theory at the B3LYP level were employed in order to understand the band structure find density of states For the CaMoO(4). UV-vis absorption measurements evidenced a variation in optical band gap values (from 3.42 to 3.72 cV) for the distinct morphologies. The blue and green PI. emissions observed in these crystals were ascribed to the intermediary energy levels arising from the distortions on the [MoO(4)] clusters clue to intrinsic defects in the lattice of anisotropic/isotropic crystals.

Triple Structural Transition below Room Temperature in the Antifilarial Drug Diethylcarbamazine Citrate

A very unusual triple structural transition pattern below room temperature was observed for the antifilarial drug diethylcarbamazine citrate. Besides the first thermal, crystallographic, and vibrational investigations of this first-line drug used in clinical treatment for lymphatic filariasis, a noteworthy behavior with three structural transformations as a function of temperature was demonstrated by differential scanning calorimetry, Raman spectroscopy, and single-crystal X-ray diffractometry. Our X-ray data on single crystals allow for a complete featuring and understanding of all transitions, since the four structures associated with the three solid-solid phase transformations were accurately determined. Two of three structural transitions show an order-disorder mechanism and temperature hysteresis with exothermic peaks at 224 K (T(1)`) and 213 K (T(2)`) upon cooling and endothermic ones at 248 K (T(1)) and 226 K (T(2)) upon heating. The other transition occurs at 108 K (T(3)) and it is temperature-rate sensitive. Molecular displacements onto the (010) plane and conformational changes of the diethylcarbamazine backbone as a consequence of the C-H center dot center dot center dot N hydrogen bonding formation/cleavage between drug molecules explain the mechanism of the transitions at T(1)`/T(2). However, such changes are observed only on alternate columns of the drug intercalated by citrate chains, which leads to a doubling of the lattice period along the a axis of the 235 K structure with respect to the 150 and 293 K structures. At T(2)`/T(1), these structural alterations occur in all columns of the drug. At T(3), there is a rotation on the axis of the N-C bond between the carbamoyl moiety and an ethyl group of one crystallographically independent diethylcarbamazine molecule besides molecular shifts and other conformational alterations. The impact of this study is based on the fascinating finding in which the versatile capability of structural adaptation dependent on the thermal history was observed for a relatively simple organic salt, diethylcarbamazine citrate.

Crystallization and preliminary X-ray analysis of S-III-SPIII, a phospholipase A2 isolated from the venom of Bothrops jararacussu.

Large single crystals have been obtained of S-III-SPIII, a phospholipase A(2) from the venom of Bothrops jararacussu. The crystals belong to the orthorhombic system space group C222, and diffract X-rays to a resolution of 1.9 Angstrom. Preliminary analysis reveals the presence of one molecule in the crystallographic asymmetric unit. The crystal structure is currently being determined using molecular replacement techniques.

Crystallization and preliminary X-ray analysis of SIII-SPIII, a ahospholipase A2 isolated from the venom of Bothrops jararacussu

Large single crystals have been obtained of SIII-SPIII, a phospholipase A2 from the venom of Bothrops jararacussu. The crystals belong to the orthorhombic system space group C222, and diffract X-rays to a resolution of 1.9 Å. Preliminary analysis reveals the presence of one molecule in the crystallographic asymmetric unit. The crystal structure is currently being determined using molecular replacement techniques.

Microstructure and metal-insulator transition in single crystalline KMo4O6

High quality KMo4O6 single crystals with tetragonal structure (space group P4/mbm) have been prepared by fused salt electrolysis. The crystals were studied by scanning electron microscopy (SEM), X-ray diffractometry, electrical resistivity, and magnetization measurements. X-ray powder diffraction patterns and SEM have given some information on the growth of single crystals. Electrical resistivity as a function of temperature shows that the KMo4O6 compound is a bad metal with resistivity change of approximately 30% in the temperature range from 2 to 300K. A metal-insulator transition (MIT), observed at approximately 110K, has been also confirmed for this material. Magnetization as a function of temperature agrees with previous report, however a magnetic ordering has been observed in M(H) curves in the whole temperature range.

Electrical spectroscopy of rubrene bulk and thin film crystals

One of the most diffused electronic device is the field effect transistor (FET), contained in number of billions in each electronic device. Organic optoelectronics is an emerging field that exploits the unique properties of conjugated organic materials to develop new applications that require a combination of performance, low cost and processability. Organic single crystals are the material with best performances and purity among the variety of different form of organic semiconductors. This thesis is focused on electrical and optical characterization of Rubrene single crystal bulk and thin films. Rubrene bulk is well known but for the first time we studied thin films. The first Current-voltage characterization has been performed for the first time on three Rubrene thin films with three different thickness to extract the charge carriers mobility and to assess its crystalline structure. As results we see that mobility increase with thickness. Field effect transistor based on Rubrene thin films on $SiO_2$ have been characterize by current-voltage (I-V) analyses (at several temperatures) and reveals a hopping conduction. Hopping behavior probably is due to the lattice mismatch with the substrate or intrinsic defectivity of the thin films. To understand effects of contact resistance we tested thin films with the Transmission Line Method (TLM) method. The TLM method revealeds that contact resistance is negligible but evidenced a Schottky behavior in a limited but well determined range of T. To avoid this effect we carried out annealing treatment after the electrode evaporation iswe performed a compete I-V characterization as a function of in temperature to extract the electronic density of states (DOS) distribution through the Space Charge Limited Current (SCLC) method. The results show a DOS with an exponential trenddistribution, as expected. The measured mobility of thin films is about 0.1cm^2/Vs and it increases with the film thickness. Further studies are necessary to investigate the reason and improve performances. From photocurrent spectrum we calculated an Eg of about 2.2eV and both thin films and bulk have a good crystal order. Further measurement are necessary to solve some open problems