Sophie L. Benjamin

Area Selective Growth of Titanium Diselenide Thin Films into Micropatterned Substrates by Low-Pressure Chemical Vapor Deposition.

The neutral, distorted octahedral complex [TiCl4(SenBu2)2] (1), prepared from the reaction of TiCl4 with the neutral SenBu2 in a 1:2 ratio and characterized by IR and multinuclear (1H, 13C{1H}, 77Se{1H}) NMR spectroscopy and microanalysis, serves as an efficient single-source precursor for low-pressure chemical vapor deposition (LPCVD) of titanium diselenide, TiSe2, films onto SiO2 and TiN substrates. X-ray diffraction patterns on the deposited films are consistent with single-phase, hexagonal 1T-TiSe2 (P3̅m1), with evidence of some preferred orientation of the crystallites in thicker films. The composition and structural morphology was confirmed by scanning electron microscopy (SEM), energy dispersive X-ray, and Raman spectroscopy. SEM imaging shows hexagonal plate crystallites growing perpendicular to the substrate, but these tend to align parallel to the surface when the quantity of reagent is reduced. The resistivity of the crystalline TiSe2 films is 3.36 ± 0.05 × 10–3 Ω·cm with a carrier density of 1 × 1022 cm–3. Very highly selective film growth from the reagent was observed onto photolithographically patterned substrates, with film growth strongly preferred onto the conducting TiN surfaces of SiO2/TiN patterned substrates. TiSe2 is selectively deposited within the smallest 2 μm diameter TiN holes of the patterned TiN/SiO2 substrates. The variation in crystallite size with different diameter holes is determined by microfocus X-ray diffraction and SEM, revealing that the dimensions increase with the hole size, but that the thickness of the crystals stops increasing above ∼20 μm hole size, whereas their lengths/widths continue to increase.

Non-aqueous electrodeposition of functional semiconducting metal chalcogenides: Ge2Sb2Te5 phase change memory

We report a new method for electrodeposition of device-quality metal chalcogenide semiconductor thin films and nanostructures from a single, highly tuneable, non-aqueous electrolyte. This method opens up the prospect of electrochemical preparation of a wide range of functional semiconducting metal chalcogenide alloys that have applications in various nano-technology areas, ranging from the electronics industry to thermoelectric devices and photovoltaic materials. The functional operation of the new method is demonstrated by means of its application to deposit the technologically important ternary Ge/Sb/Te alloy, GST-225, for fabrication of nanostructured phase change memory (PCM) devices and the quality of the material is confirmed by phase cycling via electrical pulsed switching of both the nano-cells and thin films.

Controlling the nanostructure of bismuth telluride by selective chemical vapour deposition from a single source precursor

High quality, nanostructured Bi2Te3, with an unprecedented degree of positional and orientational control of the material form on the nanoscale, is readily obtained by low pressure chemical vapour deposition using a new molecular precursor. This system offers a convenient method that delivers key structural requirements necessary to improve the thermoelectric efficiency of Bi2Te3 and to develop the nascent field of topological insulators.

Niobium(V) and tantalum(V) halide chalcogenoether complexes – towards single source CVD precursors for ME2 thin films

A series of pentavalent niobium and tantalum halide complexes with thio-, seleno- and telluro-ether ligands, [MCl5(E(n)Bu2)] (M = Nb, Ta; E = S, Se, Te), [TaX5(TeMe2)] (X = Cl, Br, F) and the dinuclear [(MCl5)2{o-C6H4(CH2SEt)2}] (M = Nb, Ta), has been prepared and characterised by IR, (1)H, (13)C{(1)H}, (77)Se, (93)Nb and (125)Te NMR spectroscopy, as appropriate, and microanalyses. Confirmation of the tantalum(V)-telluroether coordination follows from the crystal structure of [TaCl5(TeMe2)], which represents the highest oxidation state transition metal complex with telluroether coordination structurally authenticated. The Ta(V) monotelluroether complexes are much more stable than the Nb(V) analogues. In the presence of TaCl5 the ditelluroether, CH2(CH2Te(t)Bu)2, is decomposed; one of the products is the dealkylated [(t)BuTe(CH2)3Te][TaCl6], whose structure was determined crystallographically. Crystal structures of [(MCl5)2{o-C6H4(CH2SEt)2}] (M = Nb, Ta) show ligand-bridged species. The complexes bearing β-hydrogen atoms on the terminal alkyl substituents have also been investigated as single source reagents for the deposition of ME2 thin films via low pressure chemical vapour deposition. While the tantalum complexes proved to be unsuitable, the [NbCl5(S(n)Bu2)] and [NbCl5(Se(n)Bu2)] deposit NbS2 and NbSe2 as hexagonal platelets onto SiO2 substrates at 750 °C and 650 °C, respectively. Grazing incidence and in-plane X-ray diffraction confirm both materials adopt the 3R-polytype (R3mh), and the sulfide shows preferred orientation with the crystallites aligned predominantly with the c axis perpendicular to the substrate. Scanning electron microscopy and Raman spectra are consistent with the X-ray data.

Chemical vapour deposition of antimony chalcogenides with positional and orientational control: precursor design and substrate selectivity

A series of alkylchalcogenostibines, Me2SbSenBu, MeSb(SenBu)2, Sb(SenBu)3 and MeSb(TenBu)2, have been designed and synthesised as potential precursors for chemical vapour deposition (CVD) by reaction of nBuELi (E = Se, Te) with the appropriate halostibine, Me3−nSbCln (n = 1, 2, 3), and characterised by 1H, 13C{1H} and 77Se{1H} or 125Te{1H} NMR spectroscopy as appropriate. MeSb(SenBu)2 and MeSb(TenBu)2 are very effective single source precursors for the low pressure CVD of high quality crystalline thin films of Sb2Se3 and Sb2Te3, respectively, confirmed by scanning electron microscopy, energy dispersive X-ray spectroscopy, Raman spectroscopy and thin film X-ray diffraction. Hall conductivity, carrier mobility, carrier density and, in the case of Sb2Te3, Seebeck coefficient measurements reveal electronic characteristics comparable with Sb2E3 deposited by atomic layer deposition or molecular beam epitaxy, suggesting materials quality and performance suitable for incorporation into electronic device structures. Choice of substrate and deposition conditions were found to significantly affect the morphology and preferred orientation of Sb2Te3 crystallites, enabling deposition of films with either 〈1 1 0〉 or 〈0 0 1〉 alignment. Use of micro-patterned substrates allowed selective deposition of crystalline 2D micro-arrays of Sb2Te3 onto exposed TiN surfaces only.

Nanoscale arrays of antimony telluride single crystals by selective chemical vapor deposition

Arrays of individual single nanocrystals of Sb2Te3 have been formed using selective chemical vapor deposition (CVD) from a single source precursor. Crystals are self-assembled reproducibly in confined spaces of 100 nm diameter with pitch down to 500 nm. The distribution of crystallite sizes across the arrays is very narrow (standard deviation of 15%) and is affected by both the hole diameter and the array pitch. The preferred growth of the crystals in the <1 1 0> orientation along the diagonal of the square holes strongly indicates that the diffusion of adatoms results in a near thermodynamic equilibrium growth mechanism of the nuclei. A clear relationship between electrical resistivity and selectivity is established across a range of metal selenides and tellurides, showing that conductive materials result in more selective growth and suggesting that electron donation is of critical importance for selective deposition.

[Pd4(μ3-SbMe3)4(SbMe3)4]: A Pd(0) tetrahedron with μ3-bridging trimethylantimony ligands

The palladium(II) chlorostibine complex [PdCl2(SbMe2Cl)2]2 has a dimeric structure in the solid state, stabilized by hyper-coordination at the Lewis amphoteric Sb centers. Reaction with 8 equiv of MeLi forms [Pd4(μ3-SbMe3)4(SbMe3)4], whose structure comprises a tetrahedral Pd(0) core with four terminal SbMe3 ligands and four μ3-SbMe3 ligands, one capping each triangular Pd3 face. Density functional theory calculations, supported by energy decomposition analysis and the natural orbitals for chemical valence scheme, highlight significant donor and acceptor orbital contributions to the bonding between both the terminal and the bridging SbMe3 ligands and the Pd4 core.

Compositionally tunable ternary Bi2(Se1−xTex)3 and (Bi1−ySby)2Te3 thin films via low pressure chemical vapour deposition

The inherently rapid ligand substitution kinetics associated with the novel and chemically compatible precursors, [MCl3(EnBu2)3] (M = Sb, Bi; E = Se, Te), enable CVD growth of ternary Bi2(Se1−xTex)3 and (Bi1−ySby)2Te3 thin films with very good compositional, structural and morphological control, for the first time. X-ray diffraction data follow Vegards law and Raman bands shift linearly with the atom substitutions, indicating very well-distributed solid solutions.

Total synthesis and structural revision of a mangrove alkaloid

We report the total synthesis of an alkaloid isolated from the mangrove fungi Hypocrea virens, based on the originally claimed structure, via a photochemical sequence. Inconsistencies between data sets led to a revision of the proposed structure followed by a concise synthetic sequence to deliver the revised natural product.

1,8-bis(2-hydroxy-3,5-di-tert-butylbenzyl)-4,11-dibenzyl-1,4,8,11-tetraazacyclotetradecane

A cyclam (1,4,8,11-tetraazacyclotetradecane)-based macrocycle bearing two benzyl and two 2-hydroxy-3,5-di-tert-butylbenzyl pendent arms was synthesized and characterized using spectroscopic techniques and single crystal X-ray diffraction. The macrocycle crystallizes in the triclinic space group P-1, with the asymmetric unit containing one-half of the molecule. The structure is stabilized by hydrogen-bonding which exists between the phenolic protons and the nitrogen atoms of the macrocyclic ring. The presence of this hydrogen bonding is observed in the 1H-NMR due to the deshielded nature of the phenolic OH peak (δ 9.99). Cyclic voltammetry of the ligand revealed a single quasi-reversible peak at −0.58 V (Epc = −0.48 V and Epa = −0.68 V), which is due to the electrochemical oxidation of the phenol to the phenoxyl radical.