Seán T. Barry

Anomalous permittivity and plasmon resonances of copper nanoparticle conformal coatings on optical fibers

The conformal coating of a 50 nm-thick layer of copper nanoparticles deposited with pulse chemical vapor deposition of a copper (I) guanidinate precursor on the cladding of a single mode optical fiber was monitored by using a tilted fiber Bragg grating (TFBG) photo-inscribed in the fiber core. The pulse-per-pulse growth of the copper nanoparticles is readily obtained from the position and amplitudes of resonances in the reflection spectrum of the grating. In particular, we confirm that the real part of the effective complex permittivity of the deposited nano-structured copper layer is an order of magnitude larger than that of a bulk copper film at an optical wavelength of 1550 nm. We further observe a transition in the growth behavior from granular to continuous film (as determined from the complex material permittivity) after approximately 20 pulses (corresponding to an effective thickness of 25 nm). Finally, despite the remaining granularity of the film, the final copper-coated optical fiber is shown to support plasmon waves suitable for sensing, even after the growth of a thin oxide layer on the copper surface.

Gas-Phase Thermolysis of a Guanidinate Precursor of Copper Studied by Matrix Isolation, Time-of-Flight Mass Spectrometry, and Computational Chemistry

The fragmentation of the copper(I) guanidinate [Me(2)NC(NiPr)(2)Cu](2) (1) has been investigated with time-of-flight mass spectrometry (TOF MS), matrix-isolation FTIR spectroscopy (MI FTIR spectroscopy), and density functional theory (DFT) calculations. Gas-phase thermolyses of 1 were preformed in the temperature range of 100-800 degrees C. TOF MS and MI FTIR gave consistent results, showing that precursor 1 starts to fragment at oven temperatures above 150 degrees C, with a close to complete fragmentation at 260 degrees C. Precursor 1 thermally fragments to Cu((s)), H(2)(g), and the oxidized guanidine Me(2)NC(=NiPr)(N=CMe(2)) (3). In TOF MS experiment, 3 was clearly indentified by its molecular ion at 169.2 u. Whereas H(2)(+) was detected, atomic Cu was not found in gas-phase thermolysis. In addition, the guanidine Me(2)NC(NiPr)(NHiPr) (2) was detected as a minor component among the thermolysis products. MI thermolysis experiments with precursor 1 were performed, and species evolving from the thermolysis oven were trapped in solid argon at 20 K. These species were characterized by FTIR spectroscopy. The most indicative feature of the resulting spectra from thermolysis above 150 degrees C was a set of intense and structured peaks between 1600 and 1700 cm(-1), an area where precursor 1 does not have any absorbances. The guanidine 2 was matrix-isolated, and a comparison of its FTIR spectrum with the spectra of the thermolysis of 1 indicated that species 2 was among the thermolysis products. However, the main IR bands in the range of 1600 and 1700 cm(-1) appeared at 1687.9, 1668.9, 1635.1, and 1626.6 cm(-1) and were not caused by species 2. The oxidized guanidine 3 was synthesized for the first time and characterized by (1)H NMR and FTIR spectroscopy. A comparison of an FTIR spectrum of matrix isolated 3 with spectra of the thermolysis of 1 revealed that the main IR bands in the range of 1600 and 1700 cm(-1) are due to the presence of 3. The isomers exhibit the NMe(2) group cis or trans to the iPr group, with cis-3 being significantly less stable than trans-3. At higher temperature secondary thermal fragments had been observed. For example at 700 degrees C, TOF MS and MI FTIR data showed that species 2 and 3 both eliminate HNMe(2) to give the carbodiimides iPrNCNiPr (CDI) and iPrNCN[C(=CH(2))Me] (4), respectively. A DFT study of the decomposition of compound 1 was undertaken at the B3LYP/6-31+G(d,p) level of theory employing dispersion-correcting potentials (DCPs). The DFT study rationalized both carbodiimide deinsertion and beta-hydrogen elimination as exergonic decomposition pathways (DeltaG = -44.4 kcal/mol in both cases), but experiment showed beta-hydrogen elimination to be the favorable route.

Polarization-dependent properties of the cladding modes of a single mode fiber covered with gold nanoparticles.

The properties of the high order cladding modes of standard optical fibers are measured in real-time during the deposition of gold nanoparticle layers by chemical vapor deposition (CVD). Using a tilted fiber Bragg grating (TFBG), the resonance wavelength and peak-to-peak amplitude of a radially polarized cladding mode resonance located 51 nm away from the core mode reflection resonance shift by 0.17 nm and 13.54 dB respectively during the formation of a ~200 nm thick layer. For the spectrally adjacent azimuthally polarized resonance, the corresponding shifts are 0.45 nm and 16.34 dB. In both cases, the amplitudes of the resonance go through a pronounced minimum of about 5 dB for thickness between 80 and 100 nm and at the same time the wavelengths shift discontinuously. These effects are discussed in terms of the evolving metallic boundary conditions perceived by the cladding modes as the nanoparticles grow. Scanning Electron Micrographs and observations of cladding mode light scattering by nanoparticle layers of various thicknesses reveal a strong correlation between the TFBG polarized transmission spectra, the grain size and fill factor of the nanoparticles, and the scattering efficiency. This allows the preparation of gold nanoparticle layers that strongly discriminate between radially and azimuthally polarized cladding mode evanescent fields, with important consequences in the plasmonic properties of these layers.

Absolute near-infrared refractometry with a calibrated tilted fiber Bragg grating

The absolute refractive indices (RIs) of water and other liquids are determined with an uncertainty of ±0.001 at near-infrared wavelengths by using the tilted fiber Bragg grating (TFBG) cladding mode resonances of a standard single-mode fiber to measure the critical angle for total internal reflection at the interface between the fiber and its surroundings. The necessary condition to obtain absolute RIs (instead of measuring RI changes) is a thorough characterization of the dispersion of the core mode effective index of the TFBG across the full range of its cladding mode resonance spectrum. This technique is shown to be competitive with the best available measurements of the RIs of water and NaCl solutions at wavelengths in the vicinity of 1550 nm.

A Family of Heteroleptic Titanium Guanidinates: Synthesis, Thermolysis, and Surface Reactivity

A family of new mixed-ligand titanium guanidinate compounds was synthesized as potential atomic layer deposition precursors, and the surface chemistry on silica of a promising candidate (Cp(2)Ti[(N(i)Pr)(2)CN(H)(i)Pr]) was explored. Generally, these compounds have very good thermal stability with onsets of volatility between 127 and 168 degrees C, with melting points generally ranging from 147 to 165 degrees C. The reactivity of [(i)PrN(H)C(N(i)Pr)(2)]TiCp(2) was studied with high surface area silica between 180 and 330 degrees C. The surface reactivity was found to differ if the silica was preheated to 350 or 900 degrees C; this was attributed to the hydroxyl nucleation site density of the silica, which is known to vary with the temperature. The surface reaction products were characterized by solid-state NMR, and these agreed well with a calculated model. When the silica was pretreated to 350 degrees C, the precursor appeared to chemisorb primarily through the loss of a Cp ligand, while with a 900 degrees C pretreatment, the chemisorption occurred primarily through a loss of the guanidinate ligand. The adsorption enthalpies to silica were calculated for the different surface species.

Copper iminopyrrolidinates: a study of thermal and surface chemistry.

Several copper(I) iminopyrrolidinates have been evaluated by thermogravimetric analysis (TGA) and solution based (1)H NMR studies to determine their thermal stability and decomposition mechanisms. Iminopyrrolidinates were used as a ligand for copper(I) to block previously identified decomposition routes of carbodiimide deinsertion and β-hydrogen abstraction. The compounds copper(I) isopropyl-iminopyrrolidinate (1) and copper(I) tert-butyl-iminopyrrolidinate (2) were synthesized for this study, and compared to the previously reported copper(I) tert-butyl-imino-2,2-dimethylpyrrolidinate (3) and the copper(I) guanidinate [Me(2)NC((i)PrN)(2)Cu](2) (4). Compounds 1 and 2 were found to be volatile yet susceptible to decomposition during TGA. At 165 °C in C(6)D(6), they had half-lives of 181.7 h and 23.7 h, respectively. The main thermolysis product of 1 and 2 was their respective protonated iminopyrrolidine ligand. β-Hydrogen abstraction was proposed for the mechanism of thermal decomposition. Since compound 3 showed no thermolysis at 165 °C, it was further studied by chemisorption on high surface area silica. It was found to eliminate an isobutene upon chemisoption at 275 °C. Annealing the sample at 350 °C showed further evidence of the decomposition of the surface species, likely eliminating ethene, and producing a surface bound methylene diamine.

Atmospheric pressure chemical vapor deposition of electrochromic tungsten oxide films

Abstract Tungsten oxide, WOx, is a coloring layer commonly used in electrochromic windows and displays. Successful commercialization of these devices will require the deposition of WOx layers with extremely uniform thickness and material properties over large areas at high speeds and low cost. We present a new atmospheric pressure chemical vapor deposition process that should be able to meet these goals. New liquid tungsten precursors have been found to have properties suitable for this application: sufficient volatility, reactivity to oxygen at substrate temperatures of 200–300°C, lack of reactivity to air and water at room temperature, and low viscosity (7 centiPoise at 40°C). The precursors are tungsten pentacarbonyl 1-methylbutylisonitrile and tungsten pentacarbonyl n-pentylisonitrile, C5H11NCW(CO)5. These liquid precursors can be synthesized readily from commercially available reactants. Data on the composition and structure of the tungsten oxide films are presented, along with spectroscopic characterization of the films in transparent (oxidized) and colored (reduced) states.

Heteroleptic iminopyrrolidinates of aluminium

A series of iminopyrrolidine (ip) compounds were synthesized with excellent yields as potential ligands for novel organometallic precursors for atomic layer deposition. The idea behind these ligands was that carbodiimide (CDI) deinsertion would not occur as the quaternary carbon was tethered to one chelate nitrogen. To our advantage a melting point trend was evident within the ip ligands and reflected in the family of heteroleptic aluminium species when the ip ligands were reacted with TMA or TEA. The alkane elimination reaction occurred at room temperature yielding clean products with high yields. Crystal structures were collected for compounds 7 [ipipAlMe(2)], 12 [tbipAlMe(2)], and 14 [sbipAlEt(2)] demonstrating that the heteroleptic aluminium species were dimers. This was also evident in the mass spectra collected for each compound as the parent peak was that of the dimer minus a methyl. Thermolysis studies were carried out on all the ipAlMe(2) species to observe the decomposition at an isotherm over several days. The decay of the methyl peak was monitored as a ratio against TMS within the solution and was shown to be a first order decomposition. From these studies it was clear that nbip (9), iso-bip (10), and tbip (12) were the most stable complexes with half-lives of 24.8, 9.00, and 10.3 days, respectively.

Anisotropic effective permittivity of an ultrathin gold coating on optical fiber in air, water and saline solutions

The optical properties of an ultrathin discontinuous gold film in different dielectric surroundings are investigated experimentally by measuring the polarization-dependent wavelength shifts and amplitudes of the cladding mode resonances of a tilted fiber Bragg grating. The gold film was prepared by electron-beam evaporation and had an average thickness of 5.5 nm ( ± 1 nm). Scanning electron imaging was used to determine that the film is actually formed of individual particles with average lateral dimensions of 28 nm ( ± 8 nm). The complex refractive indices of the equivalent uniform film in air at a wavelength of 1570 nm were calculated from the measurements to be 4.84-i0.74 and 3.97-i0.85 for TM and TE polarizations respectively (compared to the value for bulk gold: 0.54-i10.9). Additionally, changes in the birefringence and dichroism of the films were measured as a function of the surrounding medium, in air, water and a saturated NaCl (salt) solution. These results show that the film has stronger dielectric behavior for TM light than for TE, a trend that increases with increasing surrounding index. Finally, the experimental results are compared to predictions from two widely used effective medium approximations, the generalized Maxwell-Garnett and Bruggeman theories for gold particles in a surrounding matrix. It is found that both of these methods fail to predict the observed behavior for the film considered.

Atomic layer deposition of Cu with a carbene-stabilized Cu(I) silylamide

The metal–organic Cu(I) complex 1,3-diisopropyl-imidazolin-2-ylidene copper hexamethyl disilazide has been tested as a novel oxygen-free precursor for atomic layer deposition of Cu with molecular hydrogen. Being a strong Lewis base, the carbene stabilizes the metal centre to form a monomeric compound that can be vaporised and transported without visible degradation. A significant substrate dependence of the growth process not only with respect to the film material but also to the structure of the films was observed. On Pd surfaces continuous films are grown and no phase boundary can be observed between the Cu film and the Pd, while island growth is observed on Ru substrates, which as a consequence requires thicker films in order to achieve a fully coalesced layer. Island growth is also observed for ultra-thin (<10 nm) Pd layers on Si substrates. Possible explanations for the different growth modes observed are discussed.